Photo-responsive antibacterial metal organic frameworks

Abstract

The misuse and overuse of antibiotics have caused the emergence of antibiotic-resistant bacteria, making bacterial infections more challenging. The increasing prevalence of multidrug-resistant pathogens has driven researchers to explore novel therapeutic strategies. Phototherapy strategies that utilize photo-responsive biomaterials for their antibacterial properties have gained widespread attention due to their capability of precisely controlling bacterial inactivation with minimal side effects. Despite their potential, photodynamic therapies suffer from phototoxicity and low efficiency of photosensitizers, while photothermal therapy risks overheating, which may harm healthy tissues, thus restricting its broader application. Metal organic frameworks (MOFs) have unique physicochemical properties, which provide a promising way to deal with these challenges. MOFs can function as reservoirs, loading and releasing antibacterial agents, such as antibiotics or metal ions, upon light illumination by virtue of their metastable coordination bonds. Their porous structures enable controlled drug release and encapsulation of photosensitizers. Furthermore, MOFs' tunable composition and pore structure allow for the light-triggered generation of heat and reactive oxygen species, enhancing their antibacterial effectiveness. By doping MOFs with functional materials, it is possible to achieve multi-mode antibacterial effects. In this review, we will outline recent advancements of photo-responsive antibacterial MOFs, categorize their underlying mechanisms of action and highlight their prospects in addressing bacterial resistance.

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Xiaojie Yan

Xiaojie Yan is an undergraduate student at the School of Life Sciences, Shanghai University, Shanghai. He currently majors in Biopharmaceuticals. His current research focuses on the antibacterial mechanism of photo-responsive metal organic frameworks.

Yu Chen

Yu Chen received his PhD degree from Shanghai Institute of Ceramics, Chinese Academy of Sciences (SICCAS). He is now a full professor at Shanghai University. His research focuses on materdicine, nanomedicine and nanobiotechnology, which involve the design, fabrication and biomedical applications of mesoporous nanoparticles, two-dimensional nanosheets and 3D-printing bioscaffolds. The focused biomedical applications include drug/gene delivery, molecular imaging, catalytic biomaterials, chemoreactive nanomedicine, energetic nanomedicine, theragenerative biomaterials and in situ localized disease therapy.

Liang Chen

Liang Chen received his PhD degree from Donghua University and then started as a postdoctoral fellow at Fudan University in 2018. He is currently an associate professor at Shanghai University. His research interests are focused on the design and synthesis of functional porous biomaterials for biomedical applications, including disease theranostics, regenerative medicine, and nano-bio interactions.

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1. Introduction

Infection by pathogenic microorganisms, like bacteria, fungi, and viruses, is a major contributor to morbidity and mortality worldwide.^1–3 In daily human life, bacterial contamination is ubiquitous, as bacteria are present in water sources, the atmosphere, processing of food, and the medical care industry, greatly threatening human health.^4–6 Penicillin's discovery in 1928 marked the golden age of antibiotics, and broad-spectrum antibiotics became widely used to treat bacterial infections.^7–9 However, due to the abuse of antibiotics, growing numbers of bacteria have developed resistance to these drugs, prompting the immense need for novel antimicrobial strategies or drug delivery systems.^10–13 Recently, phototherapy (PT) has aroused wide attention due to its controllable nature and minimal side effects, leading to its development as a novel strategy for pathogen inactivation.¹⁴ Unlike traditional antibiotic treatments, PT is a mild therapeutic approach in which light can penetrate specific tissues or organs with almost no adverse effects on healthy tissues, thereby achieving precision medicine.¹⁵ Researchers have dedicated substantial efforts to designing advanced photo-responsive materials and applying them across various fields,^16,17 including metal oxides, metal sulfides, metallic nanoparticles (NPs), carbon-based materials, polymer materials, and metal organic frameworks (MOFs). Despite the promising results of these materials in recent years, intrinsic limitations remain to be overcome. For instance, metal or metal oxide NPs can be toxic to the host,^18,19 and carbon-based materials exhibit poor stability and biocompatibility, especially under high concentrations, limiting their widespread application.²⁰ Additionally, semiconductor photocatalytic materials also suffer from limited light absorption capabilities and insufficient catalytic activity, resulting in relatively low efficiency.^21–23 Therefore, low-dose, highly reactive, long-lasting, and biocompatible photo-responsive antimicrobial materials have become a research focus.

Metal organic frameworks (MOFs) are composed of organic linkers and metal ions, with features of low density, crystalline surface and high porosity.^24,25 Due to their characteristics, such as unsaturated metal sites, high surface area, and porous structure, MOFs have been used widely, including in the fields of electrochemistry, organic catalysis, and photocatalysis.²⁶ In recent years, MOF-based photocatalysts have been applied in the antimicrobial field because of their easy functionalization and tailorable photocatalytic properties.^27,28 In particular, the remarkable performance of MOFs as photosensitizers (PSs) and photothermal agents in energy conversion processes has attracted significant attention. These characteristics spur researchers to design antimicrobial MOFs,²⁹ with promising therapeutic outcomes. The various mechanisms by which MOFs facilitate antibacterial action through light activation are summarized as follows (Scheme 1): (i) antibacterial drug release, where MOFs unload antibacterial drugs upon exposure to light irradiation; (ii) photodynamic therapy (PDT), where ROS is produced by MOFs under the stimulus of light to inactivate bacteria; (iii) photothermal therapy (PTT), wherein MOFs convert photonic energy into heat to eradicate bacterial cells; (iv) combined drugs-PTT, where MOFs release antibacterial drugs under light irradiation and hyperthermia produced by photo-responsive MOFs; (v) drugs–PDT, where light activation enhances the release of antibacterial drugs alongside ROS generation; (vi) PTT–PDT, integrating both thermal and ROS-based mechanisms to kill bacteria more effectively; and (vii) a multi-modal treatment strategy that combines drugs/chemodynamic therapy (CDT)–PTT–PDT effects for synergistic antibacterial functions. These integrated approaches seek to overcome the limitations of single-mode treatments, offering a more robust and versatile therapeutic outcome. Finally, this review discusses the potential and challenges of photo-responsive MOFs in antibacterial applications, and presents their advantages, limitations, and the critical areas requiring further research to optimize their clinical use in combating bacterial infections.

Scheme 1 Schematic diagram of different modes of photo-responsive antibacterial MOFs. Created with https://BioRender.com.

2. Photo-responsive MOFs

Compared to endogenous stimuli which utilize infected tissues' microenvironment, exogenous stimuli rely on external physical fields like light irradiation, hyperthermia, or ultrasound.³⁰ Currently, MOF-based materials responsive to endogenous stimuli have demonstrated significant antibacterial effects.³¹ However, variations in individuals and internal environments pose challenges in regulating MOF-based materials under endogenous stimuli.³² In contrast, exogenous stimuli are more controllable, and thus photo-responsive MOFs, as a precise therapeutic strategy under external light irradiation, have been widely used for the treatment of antibiotic-resistant bacteria (Table 1).^33,34 In particular, near-infrared (NIR) with wavelengths ranging from 780 to 1700 nm, is commonly chosen as the light stimulus due to its superior tissue penetration ability and high safety compared with other wavelengths.³⁵ This promotes the development of NIR-responsive antimicrobial photo-responsive biomaterials. MOFs have the excellent properties of absorbing the NIR and converting the energy for bacterial inactivation, and the underlying mechanism (Scheme 2) includes photo-responsive release of antibacterial drugs, PTT, PDT, PDT–PTT synergistic effects,^36,37 and drugs–PDT–PTT synergistic effects etc.

Table 1 Photo-responsive antibacterial MOFs

System types	MOF-based composites	Wavelength	Payload/bacteria	Main achievements	Ref.
Light-responsive release of antibacterial active ingredients	2-N-nitroso-N-methyl-terephthalic acid (MeNNO-H2BDC) @MIL-88B/MeNNO-H2BDC@NH2-MIL-88B (NNO@MIL-88B/NNO@NH2-MIL-88B)	Visible light	MeNNO-H2BDC E. coli, P. aeruginosa	(1) Successful combination of nitric oxide (NO)-releasing materials into the photo-responsive MOFs through post-synthetic modification	38
				(2) Remarkable and controllable photo-responsive NO release under the exposition of visible light with efficient antibacterial properties
	Sodium nitroprusside @MOF@Au-maleimide (SNP@MOF@Au-Mal)	808 nm	SNP	(1) Accurate antibacterial therapy by targeting P. aeruginosa in recognition of the bacterial pili	39
			P. aeruginosa	(2) Efficient antibacterial effect with high production of NO in situ to bacteria
	Ag@MOF@Polydopamine (Ag@MOF@PDA)	808 nm	Ag NPs	(1) Synergistic drug–PTT antibacterial capacity and on-demand release of Ag^+ ions avoiding the potential toxicity	40
			E. coli, S. aureus	(2) Elimination of both bacteria and biofilm with minor biotoxicity
	Au@SiO2@UiO-66 Polyvinylidene difluoride films (Au@SiO2@UiO-66 PVDF)	810 nm	—	(1) Enhanced release of iodine under the irradiation of NIR light	41
			E. coli, S. aureus	(2) Efficient antibacterial effects against both Gram-positive and Gram-negative bacteria
	Rifampicin&2-Nitrobenzaldehyde@ZIF-8 (RFP&o-NBA@ZIF-8)	365 nm	RFP, o-NBA	(1) On demand release degradation of ZIF and antibiotics under the photo-responsive accumulation of acid	42
			MRSA, MDR E. coli	(2) Synergistic antibacterial effects combined with the release of antibacterial zinc ions and antibiotics
Light-responsive release of antibacterial active ingredients	Micro-arc oxidation + ZIF-8 + Iodine coating system (MAO + ZI coating system)	808 nm	Iodine	(1) Enhanced antibacterial effect with the synergy of NIR-induced iodine release and ZIF-8 triggered ROS production	43
			S. aureus	(2) The promotion of osteogenic differentiation
Photodynamic therapy	PCN-224/Knitted cotton fabrics-Graphene quantum dots (PCN-224/KCF-GQDs)	532 nm	—	(1) Novel development of textile materials with enhanced ^1O2 production and high antibacterial photodynamic inactivation (aPDI) efficiency	44
			B. Subtilis, P. Aeruginosa, E. coli, S. aureus	(2) Broad-spectrum antibacterial effect against both Gram-positive and Gram-negative bacteria
	Substituted the zirconium (Zr) clusters with titanium (Ti) in the frameworks of PCN-224 (PCN-224(Zr/Ti))	Visible light	—	(1) Enhanced ROS production and extended photo-responsive spectrum from UV to visible light range	45
			E. coli, A. baumannii, MRSA, MRSE	(2) Effective elimination of multidrug-resistant bacteria without using antibiotics
	Ag NPs@MOFs	Visible light	Ag NPs	(1) Enhanced PDT effects under visible light irradiation	46
			MRSA, E. coli	(2) Excellent antibacterial effect with synergistic PDT and chemotherapeutic effects
Photodynamic therapy	ZIF-8@iCOF polyacrylonitrile	Visible light	—	(1) Enhanced generation of ^1O2 under the exposition of visible light through the improvement of structural engineering	47
			S. aureus	(2) Highly efficient antibacterial performance
	Upconversion nanoparticles@ PCN-224@L-arginine-polyvinylidene fluoride (UCNP@PCN@LA-PVDF)	980 nm	L-arginine	(1) High ROS production synergizing with antibacterial NO release	48
			P. aeruginosa, S. aureus	(2) Enhanced antibacterial performance under NIR irradiation
	CuTCPP-Fe2O3	660 nm	—	(1) Enhanced PDT effects synergizing with antibacterial metal ions release	49
			S. aureus, P. gingivalis, F. nucleatum	(2) Broad-spectrum antibacterial effect against diverse oral pathogens
	ZIF-8	Visible light	—	(1) Excellent antibacterial performance of PDT effects	50
			E. coli	(2) Almost complete inactivation of E. coli
	BIT-66	Visible light	—	(1) Excellent photo-responsive antibacterial effect	51
			E. coli	(2) Prominent reversible water uptake property
	HAS-coated MnO2@pMOF dots	Visible light	pMOF dots	(1) Enhanced PDT effects and photo-responsive self-oxygen generation	52
			E. coli, S. aureus	(2) Efficient penetration of biofilm
Photothermal therapy	Prussian blue nanoparticle hydrogel (PB NP hydrogel)	808 nm	PB	(1) PTT effects synergizing with bacteria capturing ability	53
			E. coli, S. aureus	(2) Excellent biocompatibility and antibacterial properties
Photothermal therapy	Zn-doped PBNPs	808 nm	—	(1) Enhanced PTT effects synergizing with photo-responsive antibacterial metal ions release	54
			MRSA	(2) Excellent wound healing property
	HuA@ZIF-8	808 nm	—	(1) PTT effects synergizing with photo-responsive antibacterial Zn^2+ release	55
			E. coli, S. aureus	(2) Efficient antibacterial property
	Nanoform of polyoxometalates/PCN-222 composite (NPCN-Mo)	808 nm	—	(1) Broad-spectrum and excellent antibacterial property against both bacteria and formed biofilms	56
			E. coli, S. aureus	(2) Recyclable products with synergistic effects of antibacterial and anti-adhesion
	ZnO-doped carbon nanoparticles-coated with a thermo-responsive gel layer (ZnO-CNP-TRGL)	808 nm	—	(1) Enhanced PTT effects synergizing with photo-responsive antibacterial metal ions release	57
			S. aureus	(2) High photo-thermal conversion efficiency and rapid size transformation from hydrophilic monomer to hydrophobic aggregations under NIR irradiation

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Scheme 2 Schematic illustration of the mechanisms of photo-responsive antibacterial MOFs. NORMs: Nitric oxide-releasing materials, PET: Photo-induced electron transfer, S₀: Ground state, S₁/S₂: Excited singlet state, T₁: Triplet state, ISC: Intersystem crossing, CB: Conduction band, VB: Valence band, and PCE: Photothermal conversion efficiency. Created with https://BioRender.com.

2.1 Photo-responsive release of antibacterial agents from MOFs

To deal with the problem of antibiotic resistance, antibacterial treatment methods that do not rely on antibiotics are urgently needed. Materials with antibacterial properties have been used in implants or ointment to specifically disrupt bacteria's cell membrane permeability and DNA replication, without using antibiotics.^58,59 These materials typically involve the use of components with inherent antibacterial properties, like antibacterial elements, peptides, or polymers.^60–64 Materials with antibacterial properties have been used in implants or ointment to specifically disrupt bacteria's cell membrane permeability and DNA replication, without using antibiotics.^58,59 These materials typically involve the use of components with inherent antibacterial properties, like antibacterial elements, peptides, or polymers.^60–64 For instance, metal ions such as silver can destroy bacterial cell membranes and thereby inactivate bacteria, hence are often doped in many medical appliances.^64,65 Despite their good efficiency in curing bacterial infections and avoidance of antibiotics misuse, lots of materials have low drug-loading capacity, burst release of drugs, and uncertain antibacterial modes,^66,67 significantly limiting their clinical application. Due to MOF's ordered nanostructure, they have porous structures, high surface area, sufficient drug-loading ability, and clear degradation behavior.^6,68,69 Specifically, MOFs can serve as a carrier for drug loading and controlled release by delicately choosing the organic ligands or reaction conditions, and is applicable in various medical scenarios.^70,71 Of particular interest, MOFs are more likely used in curing bacterial infections because of their unique composition/structural properties, such as their response to bacterial activity, generation of ROS, and antibacterial drug-loading ability.

Nitric oxide (NO) is an endogenous gaseous signalling molecule that plays important roles in immune responses, wound healing, and various physiological and pathophysiological processes.^72–75 Additionally, NO causes nitrosylation and oxidative stress, thus directly denaturing membrane proteins, enabling it to be a potential antibacterial drug.⁷⁶ Light-activated nitric oxide-releasing materials (NORMs) have attracted particular attention because they can achieve local NO release through non-invasive light stimulation. However, a majority of light-activated NORMs is primarily responsive to ultraviolet (UV) irradiation, with phototoxicity and poor tissue penetration ability, thus limiting NORMs' application in biomedicine.^77,78 Hao et al.³⁸ incorporated a pre-functionalized NO donor into photosensitive Fe-MOFs through a post-modification strategy to achieve visible light-triggered NO release (Fig. 1A). To extend NORMs' responsive spectrum to visible light, the team firstly focused on N-nitrosamine derivatives, typical UV-responsive NO donors.^79,80 Harnessing the photo-induced electron transfer (PET) process in MOFs' photocatalytic activity,^81,82 they hypothesized that attaching N-nitrosamine donors to photo-responsive MOFs could extend the excitation wavelength for NO release. The mechanism involves transferring electrons from the photo-responsive MOFs' subunit to the NO donor when the subunit is excited by visible light (Fig. 1B). Therefore, NO release can be triggered using visible light. The original Fe-MOF has a remarkable property of absorbing photon energy under visible light irradiation and its Fe₃O subunit then interacts with the NO donor,^83,84 releasing NO in a controllable manner and thus efficiently killing bacteria (Fig. 1C).

Fig. 1 (A) Synthetic routes of NORMs through post-modification strategy and NO release under visible light irradiation. (B) The PET mechanism of visible-light-driven NO release. (C) Bacterial colony and corresponding bacterial viability rates incubated with different materials under visible light irradiation compared with dark conditions. Reproduced from ref. 38 with permission from Wiley-VCH GmbH, Copyright 2023.

Heat generated by photothermal MOFs under NIR light can be utilized to release antibacterial drugs, such as iodine ions and nitric oxide. By utilizing photothermal effects to induce secondary reactions, Han et al.⁴¹ proposed a MOF-based composite membrane, AuNR@SiO₂@UiO-66, where the microporous UiO-66 could adsorb and load high concentrations of iodine ions. Upon NIR irradiation, the gold nanorods (Au NR) in the composite membrane generated photothermal effects that promoted the rapid release of iodine ions, exhibiting broad-spectrum antibacterial activity. Furthermore, Han et al.³⁹ developed a NIR-responsive NO-generating nanoparticle, named SNP@MOF@Au-Mal, for P. aeruginosa targeted treatment (Fig. 2A). SNP@MOF@Au-Mal was constructed by loading sodium nitroprusside (SNP), a photothermal-sensitive NO donor, into MIL-101(Fe), followed by the in situ growth of a gold shell to absorb NIR light. The surface was further modified with maleimide-functionalized polyethylene glycol (PEG) chains to facilitate specific recognition of P. aeruginosa by the bacterial pili (Fig. 2D). Experiments showed SNP@MOF@Au-Mal could effectively target and attach to P. aeruginosa, thereafter disrupting bacterial membranes, and enhancing the permeability of antibacterial agents. Additionally, the nanoparticle system exhibited excellent NIR absorption and could trigger NO release while generating ROS, achieving an efficient synergistic antibacterial effect (Fig. 2B, C and E).

Fig. 2 (A) Illustration of SNP@MOF@Au-Mal selectively attaching to P. aeruginosa and releasing NO under NIR irradiation. (B) The CLSM imaging (different time periods of P. aeruginosa incubating with RB-PEG5000-Mal). (C) Bacterial colony of P. aeruginosa incubated with SNP@MOF@Au-Mal and the comparison groups under NIR irradiation compared with under dark conditions. (D) Selectivity of P. aeruginosa between Au-(PEG)5000-Mal NPs (left) and Au-(PEG)5000 NPs (right). (E) The SEM images of P. aeruginosa with different treatments. Reproduced from ref. 39 with permission from Elsevier, Copyright 2020. (F) Synthetic routes of the Ag@MOF@PDA and its drug release mechanism. (G) Bacteria colony incubated with different materials under NIR irradiation compared with under dark conditions. Reproduced from ref. 40 with permission from Wiley-VCH GmbH, Copyright 2023.

MOFs have adjustable pore sizes and high surface area, making them suitable for drug encapsulation and delivery to infection sites while enhancing therapeutic efficacy. Cyclodextrin-MOFs (CD-MOFs), composed of drug excipients such as cyclodextrin and potassium ions, have emerged as green, biocompatible, and biodegradable porous materials for biomedical applications.^85–87 However, CD-MOFs are easy to collapse rapidly in aqueous environments.^88–90 Various strategies have been designed to enhance CD-MOFs' water stability in physiological environments; however, these methods often compromise their crystalline structure and drug encapsulation capacity.^89,91 Considering the advantages of the porous structure of CD-MOFs, He et al.⁴⁰ synthesize ultra-fine Ag NPs within cubic CD-MOFs' porous crystalline structure, creating an NIR-responsive antibacterial drug release nanoplatform (Ag@MOFs). A polydopamine (PDA) shell was in situ polymerized on the surface of Ag@MOFs to enhance its water stability and photothermal properties (Fig. 2F). The synthesized Ag@MOF@PDA exhibited NIR-responsive photothermal effects and gradually released Ag⁺, achieving enduring antibacterial activity. More importantly, under the irradiation of 808 nm light, Ag@MOF@PDA showed outstanding photothermal conversion capabilities, not only directly damaging biofilms and killing bacteria but also accelerating Ag⁺ release in a controllable way, achieving effective therapeutic concentrations while reducing administration frequency and minimizing toxicity to normal tissues. Experiments demonstrated this synergistic antibacterial strategy had an excellent broad-spectrum antibacterial capability and directly eliminated mature biofilms under NIR irradiation (Fig. 2G), with remarkable biocompatibility. The results showed that after PDA's modification, Ag@MOF@PDA achieved synergistic antibacterial activity through Ag NPs-PTT and controllable Ag⁺ release, providing a potential way to treat bacterial and biofilm infections without using antibiotics.

Small molecule drugs are commonly utilized for antibacterial purposes, including antibiotics (such as vancomycin),⁹² non-antibiotic molecules (such as azelaic acid),⁹³ and antimicrobial peptides.^94,95 MOFs, as porous materials, are particularly suitable for the encapsulation of antimicrobial small molecule drugs.^96,97 These drugs can be loaded into and protected by MOFs' structure, and released under exogenous stimuli, thereby significantly enhancing their antibacterial activity.⁹⁸ Some MOFs possess acid-responsive characteristics,^99,100 which can be leveraged to release antimicrobial drugs by mediating H⁺ release via light-induced processes, degrading the MOFs in acidic environments. Zeolitic imidazolate frameworks (ZIFs) have emerged as a standout type of MOFs in the antibacterial field,^101,102 due to their high photocatalytic efficiency, pH-responsive behaviour in acidic environments¹⁰³ related to bacterial infections, and low cytotoxicity. Song et al.⁴² skillfully utilized light-triggered and acid-responsive strategies to fabricate a multifunctional organic zinc (Zn²⁺) framework composite (RFP&o-NBA@ZIF-8). They loaded the antimicrobial drug rifampicin (RFP) into ZIF-8, and modified the porous ZIF NPs with a light-responsive H⁺ generating agent, 2-nitrobenzaldehyde (o-NBA), as a gatekeeper. Under ultraviolet light (365 nm), o-NBA undergoes rearrangement to generate H⁺, creating an acidic environment that induces ZIF-8 degradation (Fig. 3A and B), thereby promoting the release of the loaded RFP (Fig. 3D). Additionally, the released Zn²⁺ upon ZIF-8's degradation also exhibited antimicrobial activity (Fig. 3C). This photo-responsive antibacterial MOF nanocomposite enabled the release of both antibiotic drugs and antimicrobial Zn²⁺ in response to light and pH, thus significantly inhibiting bacterial wound infections and accelerating wound healing (Fig. 3E–H).

Fig. 3 (A) The photo-responsive morphology change of ZIF-8 with time under the irradiation of NIR. (B) The change of pH value in different material solutions under NIR irradiation. (C) The release rate of Zn²⁺ in different material solutions under NIR irradiation. (D) The release rate of RFP in different material solutions under NIR irradiation. (E and F) The optical density (OD600) of bacteria incubated with different materials under NIR irradiation compared with under dark conditions. (G) Bacterial colony and (H) live/dead staining of bacteria incubated with different materials under NIR irradiation compared with under dark conditions. Reproduced from ref. 42 with permission from Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Copyright 2018. (I) Synthetic routes of the MAO + ZI coating system, the antibacterial mechanism under NIR irradiation, and the corresponding enhanced bone integration. Reproduced from ref. 43 with permission from Wiley-VCH GmbH, Copyright 2021.

Postoperative infections remain a significant challenge in orthopaedics due to the severe complications they cause, as well as the additional economic burden.^104–107 These infections are often associated with bacteria remaining on the surface of implants and the formed biofilms.^108,109 Iodine has broad-spectrum antibacterial efficacy without bringing antibiotic resistance in clinical use. However, due to its volatility and poor solubility, iodine has limited usage in orthopaedic antibacterial treatment. Incorporating iodine onto commonly-used titanium implant surfaces can grant them antibacterial properties.^110,111 Due to iodine's tendency to sublimate into iodine vapor, simply depositing iodine solutions onto titanium surfaces proves unstable and has limited loading rates under physiological conditions. Thus, there is a growing need for new approaches that can fix iodine onto implants and offer controlled release triggered by external stimuli.

Teng et al.⁴³ combined NIR-triggered “explosive” iodine release with the photodynamic effects of ZIF-8 to propose a “synergistic anti-infection strategy” (Fig. 3I). Firstly, ZIF-8 was in situ hydrothermally anchored onto the surface of micro-arc oxidized titanium. Then, utilizing ZIF-8 coating's high absorption capability, iodine was loaded via physical vapor deposition. Under NIR irradiation, due to differences in NIR absorption coefficients between ZIF-8 and its composite substrate,¹¹² iodine was rapidly released in an “explosive” manner from the dissociated ZIF-8, generating ROS in the liquid environment¹¹³ to exert antibacterial effects. Simultaneously, iodine and its active products (IO₃⁻ and I⁻) synergized with the produced intracellular singlet oxygen (¹O₂),^114,115 which was generated by the ZIF-8 coating, to further enhance the anti-infection function. The research group demonstrated that under NIR irradiation, this complex strategy showed significantly enhanced antibacterial effects. A NIR laser as a “switch”¹¹⁶ for iodine delivery enabled the responsive iodine release, effectively resolving the issue of iodine fixation. Furthermore, this antibacterial system enhanced bone integration, indicating that the improved antibacterial effects did not compromise the osteogenic potential of the implants. In conclusion, the results from this study indicate that iodine-loaded MOFs represent a promising strategy for treating postoperative orthopaedic infections, providing both synergistic anti-infection effects and promoting bone integration.

There has been a growing interest in utilizing stimulus-responsive materials as carriers of drugs for the controlled release of antibacterial agents, offering significant potential for antibacterial therapy. Among these, photo-responsive MOFs have emerged as a promising class of stimuli-responsive materials, addressing the limitations of conventional drug delivery systems by enabling precise spatiotemporal release of antibacterial agents from porous structures.

Although research on photo-responsive MOF-based drug delivery systems has progressed rapidly, several challenges must be overcome before they can be translated into clinical applications, such as their toxicity, antibacterial performance, degradation modes, and stability, etc. One major limitation is the shallow penetration depth of light-responsive modalities. While the field is still in its early stages, the development of multi-stimuli-responsive systems is advancing to overcome these constraints. To enhance therapeutic outcomes, further research and innovation are needed to explore NIR- and ultrasound-responsive MOF-based drug delivery platforms.

2.2 Photodynamic MOFs mediated by light

In recent years, PDT, which combines light exposure with PSs, has become a promising and feasible approach in the antimicrobial field. Under oxygen-rich conditions, PDT generates ROS that are cytotoxic to bacteria.^117–119 These ROS react highly with biological molecules, irreversibly disrupting bacterial cell membranes, degrading DNA and proteins, and oxidizing intercellular GSH, thus achieving an excellent bacterial inactivation effect.^120–122 In contrast to the traditional antibiotics, antibacterial photodynamic inactivation (aPDI) not only allows for controlled treatment duration through the light source but also avoids inducing bacterial resistance. A successful aPDI process requires three critical components: a non-toxic PS, oxygen, and photon energy, which, through photochemical reactions, produce hydrogen peroxide (H₂O₂), hydroxyl radicals (⋅OH), superoxide anions (O₂˙⁻), and/or ¹O₂, all functioning as efficient antibacterial chemical substances.

Fluorescence resonance energy transfer (FRET) is a mechanism depicting the energy transfer between two photosensitive molecules.^123–126 An excited-state donor molecule and a ground-state acceptor molecule are necessary during FRET.¹²⁷ Furthermore, the donor and acceptor should be close enough, and at the meantime there should be an overlap between the acceptor's absorption spectrum and the donor's emission spectrum.¹²⁸ Constructing FRET is an effective method for enhancing the material's photocatalytic performance, thus Nie et al.⁴⁴ fabricated a novel textile material (PCN-224/KCF-GQDs) that enhanced ¹O₂ production and high aPDI efficiency using a FRET mechanism (Fig. 4A). PCN-224 NPs, a type of porphyrin-based MOFs, are capable of producing ¹O₂, and their porous structure facilitates the diffusion of ¹O₂. PCN-224, as the acceptor, absorbed photon energy strongly in the wavelength range of 400–500 nm, while GQDs, as the donor, had an emission spectrum overlapping with the acceptor's absorption spectrum, thus enabling FRET. Experiments indicated that the combined PCN-224/GQD decreased GQD's fluorescence intensity, while increased PCN-224's fluorescence intensity, demonstrating that FRET did occur between GQD and PCN-224. Through FRET, the generation of ¹O₂ increased by 1.61 times (Fig. 4B and C), resulting in an efficient bactericidal efficiency (>99%) and broad-spectrum antibacterial ability (Fig. 4D and E).

Fig. 4 (A) The FRET mechanism of PCN-224/KCF-GQDs. (B) The photooxidation rate constant between different materials. (C) The mechanism of generating ¹O₂ during the PDT process. (D and E) Bacterial viability rates incubated with materials under different conditions. Reproduced from ref. 44 with permission from Elsevier, Copyright 2020.

Different PSs correspond to different NIR wavelengths, and thus doping MOFs with different metal elements can enhance their photosensitive properties, thereby expanding the range of photo-responsive wavelengths. Chen et al.⁴⁵ raised a strategy to improve PDT efficiency by doping Ti elements into PCN-224 MOFs through cation exchange, yielding PCN-224(Zr/Ti) materials. Experimental results revealed that the porphyrin-bridged ligand tetra(4-carboxyphenyl) porphyrin (TCPP) in Ti-doped MOFs transferred electrons to the Zr–Ti-oxo cluster more efficiently than the Zr-oxo cluster, facilitating ROS production (Fig. 5A). This modification enabled PCN-224(Zr/Ti) to extend its light response into the visible light range, instead of UV, for in vivo PDT, avoiding UV's phototoxic effect. The synthesized PCN-224(Zr/Ti) NPs could effectively generate ROS, and also had broad-spectrum antibacterial capabilities. Additionally, these NPs could be electrospun onto nanofibers, and the resulting dressing showed excellent antibacterial efficiency against MDR bacterial infections under visible light irradiation (Fig. 5B).

Fig. 5 (A) Illustration of enhanced ROS production activity by doping Ti elements into PCN-224 MOFs. (B) Photo-responsive antibacterial MOF-based dressing for treating bacterial infection. Reproduced from ref. 45 with permission from Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Copyright 2020. (C) The mechanism of AgNPs@MOFs with multi-mode antibacterial activity. Reproduced from ref. 46 with permission from Wiley-VCH GmbH, Copyright 2022. (D) Synthetic routes of bacterial-binding photo-responsive antibacterial MOFs. (E) The mechanism of the enhanced binding capability of MOFs to bacteria. (F) MOFs used for treating bacteria-infected wounds. Reproduced from ref. 129 with permission from American Chemical Society, Copyright 2022. (G) The mechanism of enhanced photocatalytic activity of CuTCPP-Fe₂O₃ after ALD surface engineering. Reproduced from ref. 49 with permission from American Chemical Society, Copyright 2021.

In PDT for antibacterial applications, MOFs typically encounter limited photon absorption and the recombination of photogenerated holes and electrons (h⁺–e⁻), which severely hampers their applications. To address this, Xie et al.⁴⁶ enhanced the photo-responsive and h⁺–e⁻ separation capabilities of MOFs-based nanocomposites by decorating MOFs with Ag NPs (Ag NPs@MOFs) (Fig. 5C). They used a photoreduction method to synthesize Ag NP-doped MOFs. Under visible light, AgNPs@MOFs disrupted bacterial translation processes and purine/pyrimidine metabolism, while the introduction of AgNPs, with their excellent antibacterial properties, endowed the system with chemotherapeutic capabilities. This also caused damage to bacterial cell membranes and the membrane ATPase proteins. The resulting nanocomposite demonstrated excellent multi-mode antibacterial activities, such as destruction of bacterial cell membranes and disruption of bacterial translation, further inhibiting bacterial resistance. Moreover, AgNPs@MOFs, which were demonstrated to be biocompatible, exhibited promising performance in MRSA-associated soft and hard tissue infections, as well as in antimicrobial therapy and tissue regeneration. Wang et al.¹²² encapsulated colloidal semiconductor quantum dots (Zn–Ag–In–S QDs, ZAIS QDs) within ZIF-8 (QDs@ZIF-8) through a self-assembly method. The numerous active sites within ZIF-8 promoted oxygen absorption and improved ZAIS QDs' dispersion and stability. Additionally, charge transfer was accelerated at the interface and effectively inhibited the recombination of photogenerated charges, thus producing more ROS. Experimental results demonstrated that the QDs@ZIF-8 showed broad-spectrum antibacterial activity in response to visible light irradiation.

In the PDT antibacterial process, the antibacterial photosensitive MOFs can minimize their damage to normal tissues by choosing bacterial binding ligands. Chen et al.¹²⁹ developed a versatile, highly biocompatible multi-component MOFs platform by using a one-pot hydrothermal synthesis method to incorporate boric acid ligands BBDC and photosensitizing TCPPCu into Zr₆ MOF (Fig. 5D). BBDC-modified MOFs could recognize bacteria through covalent interactions (Fig. 5E).¹³⁰ The TCPPCu photosensitizer in the MOF generated abundant ROS upon light exposure, significantly enhancing the PDT effect and quickly killing bacteria. The synergistic effect of BBDC-induced physical trapping of bacteria and TCPPCu-enhanced ROS generation resulted in the rapid elimination of MDR bacteria. In vivo experiments demonstrated that the multi-functional MOFs effectively healed bacteria infected wounds with a nearly two-fold faster healing rate than MOFs without the boric acid ligand (Fig. 5F).

Atomic layer deposition (ALD) surface engineering is a method that allows the deposition of materials in single atomic layers, where each new layer reacts chemically with the previous one. By employing ALD surface engineering, MOFs can achieve lower adsorption energy and more charge transfer, thus enhancing their photocatalytic activity. Li et al.⁴⁹ deposited Fe₂O₃ using atomic layer deposition onto 2D porphyrin-based MOF nanosheets (CuTCPP-Fe₂O₃) (Fig. 5G). The experimental results confirmed that the nanosheets had an enhanced photocatalytic activity after ALD surface engineering. Under NIR stimulation, the nanosheets rapidly generated ROS and released antibacterial metal ions, showing broad-spectrum antibacterial activity against various oral pathogens (>99%).

Stable, moisture-absorbing, and antibacterial photocatalytic MOFs offer an energy-efficient and cost-effective solution for air pollution control and personal protection. Ma et al.⁵¹ reported a highly crystalline, mesoporous, and water-stable photo-responsive antibacterial MOF (BIT-66), which exhibited excellent humidity control and photocatalytic antibacterial properties, making it a promising candidate for regulating humidity in enclosed spaces. BIT-66 showed excellent antibacterial performance under visible light irradiation, mainly attributed to the formation of O₂˙⁻ during photocatalysis. Furthermore, BIT-66 exhibited notable reversible moisture absorption properties (maximum absorption of 71 wt% at 98% relative humidity), suggesting its potential as a humidity-regulating adsorbent, particularly in confined environments such as air-conditioned buildings, spacecraft, and submarines. These findings might inspire the design of advanced indoor humidity control systems (Fig. 6A). Apart from BIT-66, various MOFs and their composites have also shown high ROS production in response to light irradation,^131–134 providing the prospect for developing MOF-based photo-responsive antibacterial materials.

Fig. 6 (A) Illustration of BIT-66 with excellent humidity control and photocatalytic antibacterial properties. Reproduced from ref. 51 with permission from Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Copyright 2019. (B) The mechanism of ZIF-8 with the best PDT disinfection effects utilized to prepare a MOF-based air filter. Reproduced from ref. 50 with permission from Springer Nature, Copyright 2019. (C) Synthetic routes of MMNPs. (D) The mechanism of MMNPs with enhanced PDT effects and penetration utilized for eliminating bacterial biofilm. (E) Bacterial colony incubated with different materials under different conditions. (F and G) Corresponding bacterial viability rates incubated with different materials under NIR irradiation compared with under dark conditions. Reproduced from ref. 52 with permission from Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Copyright 2019.

Recently, MOFs have increasingly been utilized for external disinfection, where the ROS generated in situ mineralize bacteria into CO₂ and H₂O.^50,51 Li et al.⁵⁰ chose ZIF-8, which demonstrated the best photo-responsive disinfection performance, to prepare a MOF-based air filter (Fig. 6B). Experimental results showed that ZIF-8 almost totally inactivated bacteria in physiological saline after 2 hours of simulated sunlight irradiation. Mechanistic studies revealed that the disinfection process primarily involved charge transfer from light-excited electrons through ligands to metal centers within ZIF-8, where Zn²⁺ captured the electrons to produce ROS (O₂˙⁻ and H₂O₂) associated with redox reactions.

Although planktonic bacteria can be efficiently eliminated by aPDI, its treatment in bacterial biofilms is tough. Even highly effective PSs require strong light irradiation and high PS concentrations to eliminate bacterial biofilms.^118,135 The challenge lies in the thick extracellular polymeric substances (EPS) which hinder PS's penetration.^136–138 Few PSs can directly interact with bacteria within the biofilm, limiting their effectiveness. More importantly, EPS encapsulation results in hypoxic conditions within biofilms,^139–142 further restricting the photodynamic efficiency of PSs. To address this, Deng et al.⁵² innovatively encapsulated ultrasmall porphyrin-based MOF dots (pMOFs, 5 nm) within a human serum albumin (HSA) shell containing manganese dioxide (MnO₂), thus constructing a pH/H₂O₂-responsive antibacterial multicomponent nanoplatform (MMNP) (Fig. 6C and D). The acidic conditions (pH = 5.5) within the bacterial biofilm triggered the responsive degradation of MnO₂ and corresponding release of pMOFs. O₂ was produced during the degradation of MnO₂, overcoming the hypoxic environment as well as enhancing aPDI efficiency, while pMOFs exhibited a high production of ROS, excellent permeability of bacterial biofilm, and good bacterial adhesion. These two materials synergistically promoted antibacterial efficiency (Fig. 6E–G).

Photodynamic MOFs are gaining widespread attention as a novel antimicrobial strategy due to their ability to eliminate bacteria without inducing resistance. The ROS generated during PDT exhibit potent bactericidal activity by initiating specific chemical reactions within bacterial cells. However, ROS have an inherently short lifetime and limited diffusion range, indicating that only those produced at or near the infection site can effectively eradicate bacteria. This constraint significantly limits the broader application of photodynamic MOFs-based treatments. To address this challenge, researchers have developed various disinfection systems that integrate PDT with other antimicrobial techniques, enhancing overall antibacterial efficacy and expanding the practical utility of photodynamic MOFs in clinical and environmental settings.

2.3 Photothermal MOFs

In general, photothermal agents (PTAs) effectively transfer the absorbed photon energy into heat when exposed to NIR light or other electromagnetic radiation. Unlike PDT, PTT achieves bacterial inactivation by elevating the local temperature.¹⁴³ The increased heat causes the deactivation of bacteria through damage of the bacterial cell membrane and the denaturation of bacterial protein.¹⁴⁴

Localized surface plasmon resonance (LSPR) usually occurs when the light is incident on noble metal NPs. As long as the incident photons' frequency matches the noble metal NPs' vibrational frequency or the metal-conducting electrons', a strong absorption of light energy occurs. Therefore, doping additional metal ions into MOFs can enhance the photo-responsive properties of the MOFs by altering their structure. Li et al.⁵⁴ used density functional theory calculations to establish geometric and electronic structural models of various Zn²⁺ doping levels in Prussian blue (PB) NPs, optimizing the Zn²⁺ doping density to enhance the photothermal effect and synergistically release antimicrobial ions for treating MRSA-infected wounds. The enhanced photothermal effect of ZnPB derived from the bandgap narrowing caused by higher Zn²⁺ doping density and red-shift LSPR toward lower energy (Fig. 7A). A series of antimicrobial experiments demonstrated that ZnPB-3, with the highest Zn²⁺ doping density, exhibited the best broad-spectrum antibacterial effect, arising from the synergistic effect of photothermal action and metal ions release. ZnPB-3 efficiently destroyed the bacterial cell membrane, thus increasing the permeability of the membrane, while the produced localized hyperthermia accelerated metal ion release. Released Zn²⁺, Fe²⁺, and Fe³⁺ ions rapidly penetrated the bacteria, disrupted the intracellular metabolic pathways and improved the overall bactericidal efficiency (Fig. 7B).

Fig. 7 (A) The mechanism of bandgap narrowing caused by higher Zn²⁺ doping density and red-shifting LSPR toward lower energy. (B) The mechanism of photothermal antibacterial therapy with the synergistic effect of metal ions release. Reproduced from ref. 54 with permission from Springer Nature, Copyright 2019. (C) The mechanism of the photo-responsive synergistic antibacterial MOF-based hydrogels. Reproduced from ref. 53 with permission from Elsevier, Copyright 2020.

Although PTT is recognized as an effective antibacterial method, avoiding the intervention of antibiotics, localized overheating may hinder wound healing in affected tissues and trigger inflammation in the infection area. Thus, preventing the infected tissue from external bacteria and damage during the wound healing process is necessary. Functional hydrogels as wound dressings have attracted increasing attention in this regard. Han et al.⁵³ modified chitosan with quaternization and C=C bonds, endowing the hydrogel surface with positive charge and strong structure. They then synthesized a photosensitive hydrogel by free radical polymerization, incorporating positively charged chitosan and PBNPs. The positively charged hydrogel tightly captured bacteria through electrostatic adsorption, and meanwhile under NIR irradiation the Fe³⁺ and Fe²⁺ in the PBNPs underwent charge transfer, thereby absorbed photon energy and generated heat, exhibiting excellent photothermal properties, disturbing the bacterial cell membrane and inhibiting bacterial respiration. Thus, the bacteria's normal metabolism was suppressed, which demonstrated an efficient and rapid bacterial eradication under the synergistic effect of photothermal action (Fig. 7C).

Among various PTAs, NIR-absorbing agents have unique features, such as non-invasiveness, no harm to tissue, and significant curative effects.^3,145–150 Despite the fact that many NIR-absorbing agents have been widely studied for PTT,^151–154 they have poor biodegradability and expensive costs, which limit their medical use. Humic acid (HuA) has been reported to have excellent photothermal conversion efficiency.¹⁵⁵ Also, HuA possesses low cost and excellent biocompatibility,¹⁵⁶ which enables it to be a promising photothermal biomaterial for PTT. Liu et al.⁵⁵in situ grew ZIF-8 on HuA modified by polyvinylpyrrolidone (HuA@ZIF-8). The synthesized HuA@ZIF-8 showed an excellent photothermal conversion ability, and the produced hyperthermia could further induce the Zn²⁺ release from the composite material (Fig. 8A). Photothermal antibacterial therapy with the synergistic effect of Zn²⁺ release endowed HuA@ZIF-8 with an outstanding antibacterial efficiency.

Fig. 8 (A) The mechanism of antibacterial HuA@ZIF-8. Reproduced from ref. 55 with permission from Elsevier, Copyright 2020. (B) Illustration of antibacterial NPCN-Mo producing hyperthermia under NIR irradiation. Reproduced from ref. 56 with permission from Royal Society of Chemistry, Copyright 2022. (C) Synthetic routes of ZnO-CNP-TRGL. (D) Illustration of ZnO-CNP-TRGL's size transformation from the hydrophilic monomer to hydrophobic aggregation. (E) The size change of different materials varying with different temperatures. Reproduced from ref. 57 with permission from Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Copyright 2019.

Mature biofilms cause severe bio-contamination, posing a threat to public safety; however, due to severe resistance, conventional antibiotic treatments are ineffective in eradicating attached bacteria. Photothermal antimicrobial agents present a feasible approach to biofilm treatment, but their low photothermal conversion efficiency and non-reusability limit their application. Another practical issue is the attachment of dead bacteria to antimicrobial surfaces, which significantly reduces long-term antimicrobial performance.^157,158 Researchers have explored several materials with passive defence strategies by incorporating hydrophilic PEG or hydrophobic fluoropolymers to form anti-adhesion surfaces.^159–161 Therefore, designing novel photothermal materials with dual-functions of bacteria inactivation and bacteria antifouling to suppress bacterial attachment is urgent. Liu et al.⁵⁶ selected PCN-222, a kind of zirconium porphyrin MOF with an approximately 3 nm pore size, and polyoxometallate H₃PMo₁₂O₄₀ (PMA) with an “electronic sponge effect” as model light-active structures and electron storage units to prepare a NIR-responsive nanostructure composite PCN-Mo (Fig. 8B). Moreover, adding modulators allowed adjustment of the particle size of these micron-sized PCN-Mo to obtain its nanoform NPCN-Mo. Compared with the PCN-222,¹⁶² both PCN-Mo and its nanoform NPCN-Mo exhibited significant improvements in NIR absorption and photothermal performance. Under NIR irradiation, the nanocomposites displayed efficient h⁺–e⁻ separation, promoting the conversion of photogenerated electrons into reducing electrons in the polyoxometallic guest, thus enhancing the photothermal conversion efficiency. Additionally, NPCN-Mo showed broad-spectrum antibacterial activity and strong biofilm resistance. To test its performance in real-world conditions,^163,164 the research team further incorporated these NPCN-Mo NPs with copolymers, poly(lactic acid), thus forming a mixed matrix membrane (MMMs) with up to 50 wt% loading of MOF. Of note, NPCN-Mo MMMs achieved dual functions of bacteria elimination and bacteria antifouling under NIR irradiation. Afterward, the research group verified NPCN-Mo's promising application in creating antibacterial coatings on filter paper, nonwoven fabric, and stainless-steel mesh. This study suggests that MOF-based photothermal materials with charge-transfer mechanisms have promising future prospects through rational structural engineering.

Various carbon-based nanomaterials have high photothermal conversion efficiency for antibacterial applications, such as graphene-based NPs and carbon nanotubes.^165–169 However, the preparation of graphene-based and carbon nanotube-based photothermal antibacterial nanomaterials usually requires multiple synthesis steps and long purification processes.^168,170,171 To facilitate the application of photothermal antibacterial nanocarbons against pathogens, simple and tunable precursors, directly turning to photothermal nanocarbons for bacteria inactivation are urgently needed. In recent years, MOFs have functioned as a novel multifunctional nanomaterial or precursor in various fields.^172–177 Apart from directly utilizing MOFs as biocatalysts or nanocarriers,¹⁷⁸ MOF-derived nanocarbons also possess excellent physicochemical properties, for instance, excellent photothermal conversion efficiency, facile doping of metal ions, large surface area, and porous structures.^179,180

Inspired by MOF-derived nanocarbons, Ye et al.⁵⁷ proposed a photo-responsive and size-variable antibacterial MOF-derived nanocarbon (ZnO-CNP-TRGL). ZIF-8, a representative MOF precursor rich in Zn²⁺ ions, has been employed as a precursor for the synthesis of antibacterial nanocarbons. The research team carbonized ZIF-8 precursors and performed a secondary oxidation to synthesize Zn²⁺ oxide-doped carbon nanoparticles (ZnO-CNPs). To achieve enhanced antibacterial efficiency while minimizing toxicity, Ye et al. in situ encapsulated ZnO-CNP in a thermo-responsive gel layer (TRGL) to impart a bacterial-capture switch functionality (Fig. 8C). The resulting nanocarbon compound exhibited high photothermal conversion efficiency. Under NIR irradiation, the carbonized NPs rapidly increased in temperature, and when the temperature exceeded 40 °C, the TRGL transitioned from hydrophilic to hydrophobic (Fig. 8D). This transformation caused the NPs to shift from a hydrophilic monomer to hydrophobic aggregation. Besides, these nanocarbons not only achieved a highly efficient antibacterial activity even at low doses, but also showed biocompatibility in vivo. This study demonstrates that MOF-derived nanocarbon photothermal materials have promising potential for the efficient and safe disinfection of wounds, highlighting their future applications in antibacterial therapies.

Photothermal MOFs represent a promising photo-responsive antibacterial approach, offering broad-spectrum efficacy without inducing bacterial resistance or adverse side effects. The localized hyperthermia generated during PTT disrupts bacterial structures, compromises cell membrane integrity, and ultimately leads to bacterial death. However, the elevated temperatures required for effective bacterial eradication can unavoidably harm surrounding healthy tissues and provoke inflammatory responses, which may hinder the wound healing process. Conversely, achieving substantial photothermal ablation of bacteria at lower temperatures remains a challenge. Therefore, ongoing efforts are crucial to developing safe, minimally invasive, and multifunctional photo-responsive antibacterial MOFs that can synergistically enhance the efficiency of PTT while minimizing damage to healthy tissues.

2.4 Light-mediated synergistic antibacterial MOFs

In recent years, a variety of antibacterial materials with drug-releasing, PTT, or PDT effects have been developed successfully.^{150,181–183} Drug-release typically involves the use of positively charged polymers and NPs,^184–187 antibiotics, antimicrobial peptides,¹⁸⁸ and antibacterial metal ions.^{150,183,189,190} Photothermal and photodynamic therapies are typically on the basis of metal/metal oxide NPs,^191–193 carbon nanomaterials,^170,194 and novel semiconductors,^195–198 which exert antibacterial effects by generating heat or ROS. However, antibacterial therapies that rely on a single sterilization mode are often insufficient to effectively or completely eliminate bacterial infections, particularly at low material concentrations. Additionally, prolonged treatment results in bacterial resistance, increasingly threatening current antibacterial treatments.^167,190,199 Therefore, synergistic therapeutic approaches are promising in enhancing antibacterial efficacy while reducing the concentration of antibacterial agents.^{166,200–203} In this section, we summarize four modes of photo-responsive synergistic antibacterial MOFs, namely, drugs–PDT synergistic antibacterial MOFs, drugs–PTT synergistic antibacterial MOFs, PTT–PDT synergistic antibacterial MOFs and drugs/CDT–PTT–PDT synergistic antibacterial MOFs (Table 2).

Table 2 Photo-responsive synergistic antibacterial MOFs

System types	MOF-based composites	Wavelength	Payload/Bacteria	Main achievements	Ref.
Drugs–photodynamic synergistic antibacterial	PCN-224-Ag-hyaluronic acid (PCN-224-Ag-HA)	Visible light	Ag NPs	(1) Antibacterial Ag^+ release synergizing with the production of ROS under the irradiation of visible light	204
			MRSA	(2) Enhanced bacterial affinity and excellent responsive antibacterial performance
	PCN-224@CeO2	638 nm	—	(1) Biofilm-inhibiting eATP deprivation synergizing with the production of ROS	205
			S. aureus	(2) Excellent inhibition of biofilm formation
	Meropenem/Dimethyloxalylglycine@PCN-224 (MEM/DMOG@PCN-224)	660 nm	DMOG, MEM	(1) Excellent antibacterial performance with synergistic drugs–PDT effects	206
			E. coli, S. aureus, P. aeruginosa	(2) Excellent wound healing property, facilitating tissue remodeling and angiogenesis
	MOFs@Ag-4-Mercaptophenylboronic acid@Berberine (MOFs@Ag-B@BBR)	Visible light	BBR, Ag NPs	(1) Enhanced photocatalytic production of ROS and synergistic effect of releasing antibacterial drugs	207
			S. aureus, MRSA	(2) Excellent wound healing property and significant reduction of inflammation
Drugs–photothermal synergistic antibacterial	Vancomycin@ZIF-8@PDA (Van@ZIF-8@PDA)	808 nm	Van	(1) High photothermal conversion efficiency and pH/NIR dual stimuli-trigged drugs release	208
			S. aureus	(2) Excellent biocompatibility and efficient antibacterial performance with low antibiotic concentration
Drugs–photothermal synergistic antibacterial	Ag-doped carbonized ZIF (C–Zn/Ag)	808 nm	Ag^+, Zn^2+	(1) Antibacterial Ag^+ and Zn^2+ release synergizing with hyperthermia	209
			E. coli, S. aureus	(2) Excellent and broad-spectrum antibacterial performance at a low dosage
	Ag@CoMOF	785 nm	Ag NPs	(1) Continuous antibacterial Ag^+ release and excellent photo-thermal conversion efficiency	210
			E. coli, B. subtilis	(2) Excellent antibacterial performance
	Thermal-responsive brushes-ZnO-doped carbon on graphene (TRB-ZnO@G)	808 nm	—	(1) Enhanced PTT effects synergizing with sustained Zn^2+ release	211
			S. aureus	(2) Unique phase-to-size transformation capabilities
Photothermal–photodynamic synergistic antibacterial	Prussian blue@MOF (PB@MOF)	660 nm red light and 808 nm NIR	PB	(1) PTT-PDT synergistic effects	212
			E. coli, S. aureus	(2) Rapid and excellent antibacterial performance and wound healing ability
	ZIF-8/dopamine incubation within 0.5 h/indocyanine green (ZIF-8/DA-0.5/ICG)	808 nm	PDA, ICG	(1) Antibacterial composite film with synergistic PTT-PDT effects	213
			E. coli, S. aureus	(2) Excellent biocompatibility and broad-spectrum antibacterial performance
	CuS@HKUST-1	808 nm	CuS	(1) PTT–PDT synergistic antibacterial effects under NIR irradiation	214
			E. coli, S. aureus	(2) Improved biocompatibility and rapid antibacterial performance
	HMIL-121-acriflavine-tetrakis (4-amoniophenyl) porphyrin (HMIL-ACF-Por)	808 nm	ACF, Por	(1) Enhanced ROS production and durable photothermal conversion capability	215
			E. coli, S. aureus	(2) Efficient anti-inflammatory, wound healing and broad-spectrum antibacterial performance
PTT-PDT synergistic antibacterial	PB-PCN-224	660 nm	PB	(1) PTT-PDT synergistic antibacterial effects against S. aureus and its biofilm	28
			S. aureus	(2) Excellent antibacterial and wound healing properties
	Cu-doped PCN-224	660 nm	Cu^2+	(1) Enhanced photothermal activity and ROS production efficiency	147
			E. coli, S. aureus	(2) Efficient bacteria killing and wound healing properties
Drugs/chemodynamic-photothermal-photodynamic synergistic antibacterial	Ag-PCN@Ti3C2-bacterial cellulose (Ag-PCN@Ti3C2-BC)	Visible light	—	(1) PTT–PDT dual antibacterial effects synergizing with photo-responsive antibacterial Ag^+ release	216
			E. coli, S. aureus	(2) Highly efficient and long-lasting antibacterial performance
	Au NCs@PCN	808 nm	—	(1) PTT–PDT dual antibacterial effects synergizing with CDT effects	217
			MRSA, Ampr E. coli	(2) Efficient antibacterial and diabetic wound healing performance

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2.4.1 Drugs–photodynamic synergistic antibacterial MOFs. In recent years, MOF-based microneedle (MN) formulations have become a strategy for improving transdermal drug delivery. Zeng et al.²⁰⁶ created a multifunctional MOF-based MN patch that simultaneously delivered antibacterial agents and biomolecules to promote chronic wound healing (Fig. 9A). Initially, they encapsulated a competitive inhibitor of prolyl hydroxylase (dimethyloxyglycine, DMOG),^218–220 which promoted chronic wound angiogenesis, into PCN-224 NPs (DMOG@PCN-224 NPs). These NPs were then combined with meropenem (MEM), an antibiotic, and loaded into a soluble MN patch made of hyaluronic acid (HA). The MN tips rapidly dissolved when applied to a wound, efficiently delivering antibacterial drugs and DMOG@PCN-224 NPs to the bacterial infected tissue. Under the irradiation of light, DMOG@PCN-224 NPs converted O₂ into ¹O₂ and functioned synergistically with MEM to achieve a potent drugs–PDT synergistic antibacterial effect, reducing the required antibiotic dosage by 10-fold. Additionally, DMOG@PCN-224 NPs degraded gradually, releasing DMOG slowly to promote epithelial tissue and neovascular formation, thereby accelerating the healing of chronic wounds. Consequently, the MOF-based multifunctional MN patch exhibited efficient antibacterial performance through drugs–PDT synergy at the wound site, and facilitated the remodeling and angiogenesis of tissue through sustained release of growth factors.

Fig. 9 (A) Synthetic routes of photo-responsive DMOG@PCN-224 NP MN patches and the mechanism of drug–PDT synergistic bacterial inactivation effects and the corresponding wound healing properties. Reproduced from ref. 206 with permission from Wiley-VCH GmbH, Copyright 2023. (B) Synthetic routes of PCN-224@CeO₂. (C) The mechanism of eATP depletion synergized with ROS production for the inhibition of biofilm formation. Reproduced from ref. 205 with permission from Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Copyright 2019. (D) Synthetic routes of PCN-224-Ag-HA. (E) The mechanism of on-demand synergistic antibacterial Ag⁺ release and ROS production. (F) The Ag⁺ release rates from PCN-224-Ag-HA under different conditions. (G) The ROS generation ability of different materials under light irradiation. (H and I) Bacterial viability rates incubated with different materials of different concentration under light irradiation. Reproduced from ref. 204 with permission from Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Copyright 2019.

Adenosine triphosphate (ATP), serving as a common energy currency, is an important small molecule in many biological processes.²²¹ Moreover, ATP matters in cellular signaling.²²² Specifically, ATP secreted into the extracellular environment can stimulate bacterial adhesion and biofilm formation through the increase of cell lysis and release of extracellular DNA (eDNA).²²³ Notably, lanthanide ions can interact with the nitrogen and oxygen lone pairs in ATP nucleobase and phosphate groups.²²⁴ Qiu et al.²⁰⁵ utilized CeO₂-modified porphyrin metal–organic frameworks (PCN-224@CeO₂) to develop a simple and robust biofilm inhibition strategy. They first synthesized PCN-224. Then, a large number of fine CeO₂ NPs were in situ reduced and doped onto PCN-224's surface, forming a typical core–shell nanostructure (Fig. 9B). The nanoceria, existing in multiple valence states (Ce³⁺/Ce⁴⁺), could coordinate with ATP's adenine and triphosphate groups (Fig. 9C). As a result, extracellular ATP (eATP) produced by bacteria could be captured by CeO₂ NPs, disrupting the initial bacterial adhesion. Moreover, under light irradiation, PCN-224@CeO₂ NPs generated cytotoxic ROS to inactivate bacteria. The eATP depletion synergized with ROS production, effectively inhibiting biofilm formation and inactivating bacteria, thus offering a new direction for designing efficient biofilm inhibition systems.

Ag NPs have attracted significant attention due to their excellent antibacterial performance and biocompatibility.^225,226 However, the sole use of Ag NPs presents several challenges, such as small Ag NP aggregation, probably reducing their antibacterial activity,²²⁷ and the rapid release of Ag⁺, which can cause harmful effects on normal tissues at high concentrations.²²⁸ Meanwhile, long-term direct contact of residual Ag NPs with normal tissues may have toxic effects on humans, for instance, silver deposition and silver deposition disease.²²⁹ MOFs, as representative porous carriers, can load metal NPs, controlling their dispersion and release, as well as function as photocatalysts to enhance antibacterial effects. Zhang et al.²⁰⁴ reported the first study to construct a robust surface-adaptive, responsive antibacterial platform by encapsulating silver ions in a photosensitive PCN-224 and coating it with HA. They used photosensitive TCPP as the organic ligand and Zr₆ clusters as the metal ions for PCN-224. The synthesized PCN-224 with a large surface area and multiple binding sites was suitable for loading Ag⁺. The silver-loaded PCN-224 were encapsulated by the HA layer with negative charges (PCN-224-Ag-HA) (Fig. 9D). Given HA's high biocompatibility and negative charge, Ag⁺ release was minimal, making PCN-224-Ag-HA less toxic to non-target bacteria and mammalian cells. However, when encountering target bacteria secreting hyaluronidase (HAase), HA on the PCN-224-Ag-HA was degraded, generating positively charged PCN-224-Ag⁺ that bound to bacteria through charge interactions. Consequently, Ag⁺ from PCN-224-Ag⁺ was rapidly released, effectively inactivating the bacteria (Fig. 9E and F). Additionally, under visible light irradiation, the NPs exhibited PDT effects, producing ROS (¹O₂) to combat bacteria (Fig. 9G). The responsive Ag⁺ release and the ROS produced in response to the irradiation of visible light enabled strong drug–PDT synergistic antibacterial effects, reflecting the material's surface-adaptive properties and responsive antibacterial abilities. Experimental results confirmed that PCN-224-Ag-HA efficiently inactivated MRSA and drug-resistant E. coli (Fig. 9H and I).

The primary advantage of drugs–PDT synergistic antibacterial MOFs lies in their ability to prevent bacterial resistance, as their mechanism of action relies on the generation of ROS, which exert broad-spectrum antibacterial effects. Furthermore, these MOFs have demonstrated remarkable potential in re-sensitizing MDR bacteria to antibiotics, making them a promising strategy for treating infections caused by resistant pathogens. Despite these advantages, the complexity of in vivo physiological environments poses a challenge for clinical translation. Thus, it is crucial to carefully consider and regulate the release of stimulus-responsive drugs to prevent their unintended activation in non-infectious tissues, ensuring both safety and therapeutic efficiency.

2.4.2 Drugs–photothermal synergistic antibacterial MOFs. According to the former research study, pH-responsive ZIF-8 nanocarriers remain stable under neutral conditions but can decompose to release Zn²⁺ in acidic environments.²³⁰ In addition, ZIF-8 has the feature of high porosity, which enables it to encapsulate antibiotics. ZIF-8 loaded with antibiotics^231–233 has demonstrated excellent antibacterial effects in treating bacterial infections. PDA, due to its simple synthesis procedure, remarkable photothermal conversion efficiency, and excellent biocompatibility,^234,235 has been widely studied. Due to dopamine's self-polymerizing property, PDA can form surface-attached nanocoatings on various materials.^236,237

To harness the features of PDA and ZIF-8, Xiao et al.²⁰⁸ proposed Van@ZIF-8@PDA, a NIR/pH dual-responsive platform based on ZIF-8 for drugs–photothermal synergistic antibacterial treatment (Fig. 10A). Vancomycin, a kind of potent antibiotic, was loaded into ZIF-8's pores. PDA was then used to encapsulate ZIF-8, enhancing its dispersion and stability in vivo, providing enhanced photothermal conversion efficiency (η = 37.7%). Through NIR light activation, the high temperature combined with pH-responsive degradability of ZIF-8, triggered responsive drug release, which played a synergistic role in eliminating planktonic bacteria before and after biofilm formation. Simultaneously, the material not only disrupted the bacterial cell structure but also degraded bacterial DNA. Under NIR irradiation, the material exhibited antibacterial efficiency of 97.5% and 98.7% against E. coli and S. aureus, respectively, with a biofilm clearance rate of 75.7% and biofilm inhibition rate of 85.6%.

Fig. 10 (A) Synthetic routes of Van@ZIF-8@PDA and the mechanism of antibacterial synergistic drug–PTT therapy. Reproduced from ref. 208 with permission from Elsevier, Copyright 2020. (B) Synthetic routes of 2D TRB-ZnO@G nanosheets. (C) Illustration of NIR-responsive phase-to-size transformation of TRB-ZnO@G, and the corresponding formation of aggregation wrapping and eliminating bacteria. (D) The mechanism of drugs–PTT-mechanical triple synergistic antibacterial activities of TRB-ZnO@G. Reproduced from ref. 211 with permission from American Chemical Society, Copyright 2019.

Recently, graphene has emerged as a promising 2D material for multiple antibacterial applications.^{170,171,238–240} Graphene-based 2D antibacterial nanomaterials can absorb NIR, and with their sharp edges, they can act as a “nano-scalpel” to physically cut bacterial membranes, extract bacterial cell membrane lipids, and induce oxidative stress.^{170,238,241,242} However, graphene-based antibacterial nanomaterials have many challenges, including complex synthesis,^170,243,244 high dose requirements,²⁴⁵ and, especially, the large amount of non-localized heat generated by graphene, which inevitably causes damage to healthy tissues.^246,247 To address these issues, Fan et al.²¹¹ reported a MOF-derived 2D carbon nanosheet, which demonstrates phase-to-size conversion and a local antibacterial capability, enhancing bacterial elimination efficiency. They first synthesized MOF-derived graphene doped with ZnO and carbon atoms (ZnO@G), and then anchored it with a thermo-responsive brush (TRB) to form TRB-ZnO@G (Fig. 10B). The local encapsulation of 2D-CNs led to significant Zn²⁺ ion penetration, which disrupted the bacterial membrane's polarization state, altered membrane permeability, and caused deactivation of the bacterial enzyme system. Moreover, the local encapsulation of TRB-ZnO@G enhanced physical disruption of bacterial membrane structures through the “nano-scalpel” effect, driven by two factors: (1) the sharp edges of 2D-CNs causing insertion and cutting of bacterial membranes, and (2) the hydrophobic phase transition of TRB-ZnO@G under NIR induction, leading to the extraction of bacterial lipid bilayers. Additionally, TRB-ZnO@G-bacterial aggregates produced localized hyperthermia under the exposure of NIR, damaging bacterial cell membranes and intracellular substances to a great extent (Fig. 10C). The locally generated hyperthermia prevented the transfer of excessive non-local heat to healthy tissues as well. Thus, TRB-ZnO@G provided a sustained and localized triple-modal antibacterial activity (chemical, mechanical, and photothermal), significantly improving its anti-infection treatment efficiency in vivo (Fig. 10D).

PTT has demonstrated the ability to eliminate both planktonic bacteria and biofilms, highlighting its potential for clinical use. Beyond direct bacterial ablation, PTT also disrupts biofilm integrity, enhancing the penetration and efficacy of antibacterial agents within these protective bacterial communities. Combing the release of antibacterial agents and PTT has been demonstrated to significantly lower the required antibiotic dosage while effectively eliminating residual bacteria, a key advantage over PTT alone. The above studies confirm that drugs–PTT synergistic antibacterial MOFs exhibit enhanced bactericidal and antibiofilm properties under NIR irradiation. This approach has also been successfully applied in vivo to treat skin abscesses caused by drug-resistant bacteria. Given its potent antibacterial efficacy and reduced reliance on high-dose antibiotics, drugs–PTT combination therapy shows immense promise for clinical applications in combating multidrug-resistant bacterial infections.

2.4.3 Photothermal-photodynamic synergistic antibacterial MOFs. Artificially synthesized materials, for example Ti₃C₂¹⁴⁵ and MoS₂,²⁴⁸ with excellent photothermal or photocatalytic properties, have garnered wide attention due to their ability to generate ROS (¹O₂, ·OH, O₂˙⁻). When light-excited h⁺–e⁻ are captured by the surrounding O₂, bacterial killing occurs through PDT, which damages DNA, enzymes, and proteins for bacterial eradication.²⁴⁹ While other materials experience temperature increases on their surface under light exposure, and the heat generated during this process can eliminate bacteria, leading to PTT.^250,251 Currently, achieving satisfactory therapeutic effects through single mode PTT or PDT is difficult to achieve while avoiding damaging normal tissues, either due to excessive heat or insufficient ROS.^252,253 In contrast, combined PDT and PTT treatment provides better outcomes than either modality alone.²⁵⁴ Therefore, there is a pressing need to design novel biomaterials with excellent PTT and PDT synergistic effects and ideal biocompatibility.

Not all types of MOFs exhibit photocatalytic properties, but MOFs can be modified to acquire photocatalytic as well as photothermal properties. Common Cu-based MOFs (HKUST-1) are not inherently photoreactive, but Yu et al.²¹⁴ embedded CuS NPs into HKUST-1 via in situ sulfurization to create a composite material that possessed synergistic PTT and PDT effects (Fig. 11A). This formulation exhibits great potential for biological applications. CuS NPs, as a p-type semiconductor, show significant LSPR in the NIR region.²⁵⁵ Under NIR exposure, Cu²⁺ undergoes endogenous d–d transitions, producing photothermal effects.²⁵⁶ Additionally, CuS NPs, as a self-doped material, contain internal copper defects in their lattice, resulting in a high concentration of free carriers (holes).^257,258 Thus, CuS NPs embedded in HKUST-1 maintained strong NIR absorption, and in CuS NPs the hole carriers could interact with H₂O, generating ·OH radicals. HKUST-1, as a suitable MOF carrier, provided an advantageous environment for these reactions, enabling ROS to diffuse with freedom inside or outside MOFs, and transferring photon energy to generate heat, thus rapidly sterilizing within a short time while improving biocompatibility. The synergistic antibacterial performance in CuS@HKUST-1 under NIR irradiation is shown in Fig. 11B. Under NIR illumination, CuS@HKUST-1 utilized its efficient NIR absorption to convert light into heat, causing membrane loosening and increased permeability, resulting in irreversible bacterial membrane damage,²⁵⁹ while also leading to protein denaturation.²⁶⁰ Moreover, the ROS generated under light exposure were more likely to oxidize DNA, certain enzymes, or proteins,²⁶¹ aided by the photothermal-induced destruction of bacterial cell membranes. In addition to PDT and PTT synergistic antibacterial effects, CuS@HKUST-1's decomposition under hyperthermic conditions released antibacterial Cu²⁺, which had great permeability of the bacterial membrane and capability of bacterial inactivation by disrupting the bacterial DNA structure, important enzymes and proteins, and causing leakage of intracellular substances.^262,263

Fig. 11 (A) The mechanism of synergistic PDT and PTT effect in CuS@HKUST-1 under NIR irradiation. (B) Illustration of synergistic antibacterial performance in CuS@HKUST-1 under NIR irradiation. Reproduced from ref. 214 with permission from Elsevier, Copyright 2020. (C) Illustration of the core–shell structure of PB@MOF. (D) The mechanism of antibacterial PB@MOF under dual light irradiation. (E) The charge transfer mechanism of PB@MOF heterojunction photocatalysts. (F–I) Bacterial colony and corresponding antibacterial rates after incubating with different materials of different concentrations under the irradiation of 808 nm light, 660 nm light and dual light respectively, compared with under dark conditions. Reproduced from ref. 212. Available under a CC BY 4.0 license. Copyright 2019.

Porphyrin MOFs,^264–266 which can produce ¹O₂, have been widely studied. Meanwhile, PB MOFs, as a kind of photothermal agent, have received broad attention, especially after being clinically approved by the FDA.²⁶⁷ PB MOFs offer advantages such as simple preparation, excellent photothermal effects, low biological toxicity, and biodegradability, making them widely used in PTT. Luo et al.²¹² designed a MOF heterojunction with a core–shell structure using PB MOF as the core and UiO-66@TCPP MOF as the shell, named as PB@MOF (Fig. 11C). Porphyrins, TCPP, were doped into UiO-66, due to the defects inside UiO-66.^268,269 TCPP significantly enhanced electron transfer in PB, suppressing h⁺–e⁻ recombination, and thus improving photocatalytic performance, leading to an increased production of ¹O₂ under the exposure of 660 nm light. Under the exposure of NIR (808 nm), PB@MOF exhibited enhanced photothermal conversion efficiency, reaching 29.9% at maximum. Through the synergistic PTT and PDT effects, the dual-layer PB@MOF under mixed light (dual-light) at 808 + 660 nm for 10 minutes achieved remarkable bacterial inactivation efficiency (Fig. 11F–I). The antibacterial mechanism of PB@MOF under dual light irradiation is illustrated in Fig. 11D. The charge transfer mechanism of PB@MOF heterojunction photocatalysts is illustrated in Fig. 11E.

Synergistic PTT–PDT antimicrobial surfaces provide a novel strategy to combat bacterial infections, and yet often need complex and laborious processes of chemical preparation. Gao et al.²¹³ enabled ZIF-8 particles' rapid assembly on the surfaces of different materials through a chelation reaction between metal ions and dopamine (Fig. 12A). In this facile assembly method, only neutral conditions and a short period of incubation time were required to obtain uniform MOF films. Upon incorporation of the photo-responsive nanoreagent indocyanine green (ICG),^270,271 the acquired PTT-PDT synergistic antimicrobial surfaces demonstrated strong antimicrobial effects under NIR irradiation. In addition, the synthesized PTT–PDT antimicrobial surfaces showed unnoticeable cytotoxicity under NIR irradiation and good hemocompatibility.

Fig. 12 (A) Synthetic routes and mechanism of antibacterial ZIF-8/DA-0.5/ICG. Reproduced from ref. 213 with permission from the Royal Society of Chemistry, Copyright 2022. (B) Synthetic routes and mechanism of antibacterial HMIL-ACF-Por with synergistic PDT–PTT effects. Reproduced from ref. 215 with permission from American Chemical Society, Copyright 2024. (C) Synthetic routes and mechanism of Cu-doped PCN-224 with enhanced photocatalytic and photothermal properties. (D and E) Bacterial colony incubated with different materials under light irradiation compared with under dark conditions. Reproduced from ref. 147 with permission from Elsevier, Copyright 2020.

In the fields of photothermal and photodynamic therapies, typical organic PSs and PTAs include tetrakis (4-aminophenyl) porphyrin (Por), acridine yellow (ACF),²⁷² BODIPY,^273,274 phthalocyanines,²⁷⁵ and diketopyrrolo-pyrrole.^276,277 These have become good candidates for applications in photothermal and photodynamic therapies. However, these macromolecules often possess extensive π-conjugation,²⁷⁸ resulting in poor water solubility and easy aggregation, which compromises their photothermal or photodynamic efficacy. Therefore, molecular-level dispersion of PSs and PTAs can prevent aggregation and exposure to active sites, thereby enhancing their PDT/PTT effect. MOFs, with their high porosity, provide space for guest molecules and improve loading efficiency.²⁷⁹ Moreover, MOFs' robust structure and abundant active groups enable them to maintain their topological structure while also modulating the dispersion of guest molecules, making them suitable for post-synthetic modifications.^280,281 Li et al.²¹⁵ reported a PDT–PTT synergistic antibacterial MOF formulation, HMIL-121-acridine yellow-tetrakis (4-aminophenyl) porphyrin (HMIL-ACF-Por), by post-synthetically modifying the aluminium-based MOF HMIL-121 with cationic acridine yellow and tetrakis (4-aminophenyl) porphyrin (Fig. 12B). The porous structure of HMIL-121 facilitated ROS transport. The resulting HMIL-ACF-Por addressed the common aggregation issues in photosensitizers and photothermal agents, as well as imparted both PDT and PTT properties to HMIL-121. Under the irradiation of NIR, HMIL-ACF-Por generated significant ROS, including O₂˙⁻ and ¹O₂, and also produced hyperthermia. In vitro experiments demonstrated that HMIL-ACF-Por exhibited excellent and broad-spectrum antibacterial performance. Furthermore, due to combined PTT–PDT, HMIL-ACF-Por effectively inhibited bacterial infection-induced inflammation under NIR irradiation and accelerated the healing of S. aureus-infected wounds. Hemolysis and cytotoxicity measurements indicated that HMIL-ACF-Por possessed excellent biocompatibility. Importantly, there was no obvious toxicity to major organs. A series of experimental results suggested that HMIL-ACF-Por was a potential PTT-PDT synergistic antibacterial MOF formulation, contributing to effective solutions for bacterial infection treatment and promoting the application of photo-responsive antibacterial MOFs in biomedicine.

With the growing concern over antibiotic resistance, antibiotic-free strategies have become an urgent priority in curing bacterial infections. Han et al.¹⁴⁷ doped Cu²⁺ into PCN-224's porphyrin ring to enhance the photocatalytic properties of PCN-224 (Fig. 12C). The doped Cu²⁺ could capture electrons, thereby inhibiting h⁺–e⁻ recombination and accelerating electron mobility under light irradiation, which increased ROS generation. Additionally, due to the d–d energy band transition, Cu²⁺ could absorb light, transfer photon energy into heat and therefore enhance the PTT effect of Cu-MOFs. However, excessive doping of Cu²⁺ might capture more photoelectrons and reduce the absorption of photon energy, thus weakening the PTT and PDT effects of Cu-MOFs. In this regard, the research group explored the PTT and PDT performance of PCN-224 with varying Cu²⁺ doping ratios and found that the MOF doped with 10% Cu²⁺ (Cu10MOF) exhibited optimal ROS and photothermal synergistic effects after 20 minutes of light exposure. In vitro experiments verified that Cu10MOF exhibited an excellent and broad-spectrum antibacterial efficacy (Fig. 12D and E).

Due to the multi-target antibacterial effects of PTT and PDT, researchers have recently developed a range of PTT-PDT synergistic antibacterial MOFs to address the limitations of single-mode treatments and enhance antibacterial efficacy. Certain photo-responsive MOFs exhibit strong light absorption, efficiently converting photon energy into heat, which not only facilitates bacterial eradication but also prevents biofilm formation. Consequently, the integration of PDT and PTT presents a promising, safe, and effective strategy for combating bacterial infections. However, despite their potential, current PTT–PDT synergistic antibacterial MOFs remain largely confined to laboratory research. Challenges such as suboptimal photothermal conversion efficiency, limited biodegradability, and potential cytotoxicity hinder their clinical translation, necessitating further advancements in material design and optimization.

2.4.4 Drugs/chemodynamic-photothermal-photodynamic synergistic antibacterial MOFs. The multiple synergistic antibacterial mode platform has emerged as a promising new antibacterial strategy in recent years. Nie et al.²¹⁶ constructed a hybrid material similar to “dew” (Ag-PCN@Ti₃C₂-BC) that integrates the triple effects of PTT, PDT, and Ag⁺ release for drugs–PTT–PDT synergistic antibacterial activity (Fig. 13A). The group grew PCN-224 NPs (Dew) in situ on Ti₃C₂ MXene nanosheets (PCN@Ti₃C₂), and subsequently fixed PCN@Ti₃C₂ nanocomposites onto bacterial cellulose (BC) nanofiber membranes (PCN@Ti₃C₂-BC). Afterward, Ag NPs were sputtered onto the nanocomposite's surface (Ag-PCN@Ti₃C₂-BC) (Fig. 13B). The unique structure of PCN@Ti₃C₂ in the material not only ensured the synergistic PDT–PTT effect through the absorption of photon energy but also avoided the aggregation and poor water solubility issues of PCN-224 nanoparticles. The ¹O₂ produced by the PDT effect of PCN-224 and the hyperthermia generated by the PTT effect of Ti₃C₂ synergistically enhanced antibacterial activity, while also promoting the degradation of the sputtered Ag NPs and the release of silver ions, therefore achieving rapid sterilization and sustained antibacterial effects. Antibacterial experiments revealed that Ag-PCN@Ti₃C₂-BC had an excellent and broad-spectrum sterilization rate even after being used twice for eliminating bacteria and long periods of indoor storage. In conclusion, this photo-responsive antibacterial MOF offers a novel approach for controlled, safe, and effective microbial inactivation, providing a preventive or therapeutic solution for bacterial infections.

Fig. 13 (A) The mechanism of antibacterial PCN@Ti₃C₂-BC with synergistic drugs–PDT–PTT effects. (B) Synthetic routes and morphology of PCN@Ti₃C₂-BC. Reproduced from ref. 216 with permission from Elsevier, Copyright 2021. (C) Synthetic routes of Au NCs@PCN. (D) The mechanism of antibacterial Au NCs@PCN with synergistic CDT–PDT–PTT effects. (E) The mechanism of bacterial inactivation involving the disruption of bacterial membrane structure and leakage of protein and the corresponding mechanism of wound healing involving angiogenesis promotion and epithelial cell repair through up-regulated expression of related growth factors. Reproduced from ref. 217 with permission from American Chemical Society, Copyright 2022.

Bacterial infections have long been a major challenge during the healing process of diabetic wounds, making the development of multifunctional MOF antibacterial formulations for diabetic wound infections highly attractive. Zhao et al.²¹⁷ employed an in situ growth method to reduce Au(III) precursors to Au nanoclusters (Au NCs), and then Au NCs were incorporated into a zirconium–porphyrin MOF (Au NCs@PCN). Afterward, the material was enclosed in a hydrogel to ensure homogeneous distribution and moisture retention at the wound site (Fig. 13C). The Au NCs exhibited Fenton-like catalytic activity, generating ·OH in the high endogenous H₂O₂ concentration at the wound site. Furthermore, Au NCs@PCN performed excellently in both PDT and PTT effects. The produced hyperthermia and generated ROS under the irradiation of NIR enabled CDT-PTT-PDT triple synergistic antibacterial activities, effectively killing bacteria (Fig. 13D). Antibacterial experiments showed that Au NCs@PCN disrupted bacterial membrane structures and thereby induced protein leakage (Fig. 13E). Western blot analysis results indicated that Au NCs@PCN promoted related growth factors' expression, facilitating angiogenesis and epithelial cell repair (Fig. 13E). In vivo experiments further demonstrated that Au NCs@PCN could accelerate diabetic wound healing.

Drugs/CDT–PTT–PDT synergistic antibacterial MOFs have demonstrated exceptional antibacterial efficacy and enhanced wound healing capabilities, offering a cutting-edge approach to multi-modal bacterial eradication in biomedical applications. By integrating antibacterial agents/CDT with PTT and PDT, these MOFs provide a highly effective and synergistic strategy for combating bacterial infections. However, despite their promising potential, the practical application of these synergistic photo-responsive antibacterial MOFs remains largely confined to academic research. For successful clinical translation, several critical factors must be addressed, including large-scale production feasibility, biosafety, cost-effectiveness, industrial reproducibility, and environmental sustainability. Overcoming these challenges is essential to advancing these multifunctional MOFs from laboratory research to real-world medical applications.

2.5 Large-scale synthesis of photo-responsive MOFs

Photo-responsive MOFs have emerged as promising materials for diverse applications, including sterilization, air cleaning, thermal regulation, and wound healing. Their superior properties over conventional porous materials have sparked commercial interest, highlighting the necessity of reducing production costs and enhancing scalability to facilitate widespread adoption.

Among the current synthesis approaches (such as hydrothermal, solvothermal, electrochemical, and mechanochemical etc.), batch processing remains the most commonly used method for large-scale production of photo-responsive MOFs. However, continuous flow synthesis is gaining attention as a viable alternative for future industrial applications due to its enhanced properties of mass and heat transport, the production of fine and homogeneous products, the formation of accurately controlled particle size, and high space-time yield (STY).²⁸² Additionally, advancements in artificial intelligence (AI)-driven methodologies could significantly accelerate process optimization by minimizing the consumption of solvent and additives, identifying environmentally friendly synthesis routes, and improving washing procedures.^283,284 These developments collectively contribute to making large-scale MOF production more sustainable and economically viable.

3. Conclusions and perspectives

In this review, we summarize the applications of photo-responsive antibacterial MOFs. Due to the diverse components of MOFs, their morphology, structure, size, and physicochemical properties can be flexibly designed and modified, endowing them with multifunctionality and responsive drug release under light irradiation or other endogenous/exogeneous stimuli.²⁸⁵ However, their structural and performance potentials have not been fully realized, and there are still many limitations to be addressed in the field of photo-responsive antibacterial MOFs (Fig. 14).

Fig. 14 Summary of the advantages, disadvantages and optimization strategies of photo-responsive antibacterial MOFs, particularly the antibacterial mechanisms and further perspectives. Created with https://BioRender.com.

(i) The colloidal instability of MOFs limits their biomedical applications.²⁸⁶ This instability arises from the fact that the coordination bonds between organic ligands and metal ions are relatively weak, particularly under humid conditions which are conducive to bacterial growth, making them prone to decomposition under physiological conditions. Additionally, once dried, MOF-based nanocarriers cannot be re-dispersed, and thus, they must remain suspended in solution. Nanosized MOFs loaded with drugs exhibit poor stability in solution due to the aggregation issues and uncontrollable drug release, which further limits their clinical application. Hence, there is a need to regulate MOFs' stability based on specific needs, and to improve their reusability during sterilization processes. Further research into their crystallinity, size, composition, structure, and synthesis methods is required.

(ii) Biosafety and biocompatibility are crucial for MOFs used as antibacterial agents in medical applications.²⁷⁹ The antibacterial effect of MOFs primarily derives from the decomposition of the frameworks and the resulting release of drugs, antibacterial metal ions or organic ligands. Although they show desirable antibacterial effects, the low biocompatibility and intrinsic toxicity issues of many organic ligands limit antibacterial MOFs' wide utilization. Through surface modification, many antibacterial MOFs can improve their biocompatibility, but biological safety concerns still persist, particularly with regard to the toxic side effects on surrounding normal tissues after long term use, the degradation modes of antibacterial MOFs, and their tissue accumulation. Therefore, it is necessary to explore biologically safe MOFs.

(iii) A major concern with NPs is their potential toxic effects on mammalian systems. Therefore, enhancing the specificity of antibacterial MOFs for targeting pathogenic microorganisms is critical for both biological safety and preclinical applications. Additionally, MOFs to effectively target, recognize, and kill pathogens without harming other beneficial bacteria or normal human cells have gradually become the research focus. To improve the targeting and selectivity of MOFs to bacterial infection sites, it is essential to design targeted and selective systems responsive to diverse stimuli that kill bacteria upon activation. After optimizing the targeting and sterilization efficiency of antibacterial MOFs, it is crucial to comprehensively evaluate and document their pharmacokinetics and the long-period efficiency in the body. Last but not the least, to explore the practical applicability of MOF materials in antibacterial applications, investigating new antibiotic resistance after long-term exposure to these materials is essential to determine their clinical suitability.

Above all, developing photo-responsive antibacterial MOFs has great promise due to their superior capacity for loading drugs, ease of functionalization, low toxicity and excellent biocompatibility. However, their clinical applications remain distant. Further research on their long-term toxicity and the relative in vivo studies are crucial for their clinical translation. This review outlines recent studies on photo-responsive antibacterial MOFs, including their underlying mechanisms of sterilization and specific in vivo applications, aiming to assist researchers in understanding their progresses as well as encouraging their further development.

Author contributions

Xiaojie Yan: conceptualization, writing – original draft preparation, and visualization. Zhengzheng Lin: validation and visualization. He Shen: validation and visualization. Yu Chen: supervision, project administration, and funding acquisition. Liang Chen: conceptualization, writing – review & editing, supervision, project administration, and funding acquisition.

Data availability

This narrative review does not present any new data. All the data discussed were derived from previously published studies, all of which are fully cited within the text. Software have been included, and no new data were analyzed or produced for the purpose of this review.

Conflicts of interest

No conflicts for declaration.

Acknowledgements

This work is financially supported by the National Natural Science Foundation of China (52102350), the Chenguang Program of Shanghai Education Development Foundation and Shanghai Municipal Education Commission, and the Wenzhou Basic Scientific Research Project (Grant No. Y20230135).

Notes and references

1. J. W. Costerton, P. S. Stewart and E. P. Greenberg, Science, 1999, 284, 1318–1322.
2. L. Hall-Stoodley, J. W. Costerton and P. Stoodley, Nat. Rev. Microbiol., 2004, 2, 95–108.
3. T. Wei, Q. Yu and H. Chen, Adv. Healthcare Mater., 2019, 8, 1801381.
4. R. Karimi Alavijeh, S. Beheshti, K. Akhbari and A. Morsali, Polyhedron, 2018, 156, 257–278.
5. P. Murugesan, J. A. Moses and C. Anandharamakrishnan, J. Mater. Sci., 2019, 54, 12206–12235.
6. M. Shen, F. Forghani, X. Kong, D. Liu, X. Ye, S. Chen and T. Ding, Compr. Rev. Food Sci. Food Saf., 2020, 19, 1397–1419.
7. C. J. Leaver and J. Edelman, Nature, 1965, 207, 1000–1001.
8. R. Bentley, Perspect. Biol. Med., 2005, 48, 444–452.
9. K. Kümmerer, Chemosphere, 2009, 75, 417–434.
10. B. Berger-Bächi, Int. J. Med. Microbiol., 2002, 292, 27–35.
11. A. W. Smith, Adv. Drug Delivery Rev., 2005, 57, 1539–1550.
12. A. M. Allahverdiyev, K. V. Kon, E. S. Abamor, M. Bagirova and M. Rafailovich, Expert Rev. Anti-Infect. Ther., 2011, 9, 1035–1052.
13. P. Grenni, V. Ancona and A. Barra Caracciolo, Microchem. J., 2018, 136, 25–39.
14. Q. Jia, Q. Song, P. Li and W. Huang, Adv. Healthcare Mater., 2019, 8, 1900608.
15. W. Wang, G. Huang, J. C. Yu and P. K. Wong, J. Environ. Sci., 2015, 34, 232–247.
16. W. Li, C. Wang, Y. Yao, C. Wu, W. Luo and Z. Zou, Trends Chem., 2020, 2, 1126–1140.
17. I. Levchuk, M. Kralova, J. J. Rueda-Márquez, J. Moreno-Andrés, S. Gutiérrez-Alfaro, P. Dzik, S. Parola, M. Sillanpää, R. Vahala and M. A. Manzano, Appl. Catal., B, 2018, 239, 609–618.
18. Q. H. Tran, V. Q. Nguyen and A.-T. Le, Adv. Nat. Sci.: Nanosci. Nanotechnol., 2013, 4, 033001.
19. Y. Zhu, J. Wu, M. Chen, X. Liu, Y. Xiong, Y. Wang, T. Feng, S. Kang and X. Wang, Chemosphere, 2019, 237, 124403.
20. M. Alavi, E. Jabari and E. Jabbari, Expert Rev. Anti-Infect. Ther., 2021, 19, 35–44.
21. M. Pelaez, N. T. Nolan, S. C. Pillai, M. K. Seery, P. Falaras, A. G. Kontos, P. S. M. Dunlop, J. W. J. Hamilton, J. A. Byrne, K. O'Shea, M. H. Entezari and D. D. Dionysiou, Appl. Catal., B, 2012, 125, 331–349.
22. A. Sirelkhatim, S. Mahmud, A. Seeni, N. H. M. Kaus, L. C. Ann, S. K. M. Bakhori, H. Hasan and D. Mohamad, Nano-Micro Lett., 2015, 7, 219–242.
23. W. Zhan, L. Sun and X. Han, Nano-Micro Lett., 2019, 11, 1.
24. H. Furukawa, K. E. Cordova, M. O’Keeffe and O. M. Yaghi, Science, 2013, 341, 1230444.
25. A. Dhakshinamoorthy, A. M. Asiri and H. García, Angew. Chem., Int. Ed., 2016, 55, 5414–5445.
26. A. Dhakshinamoorthy, A. M. Asiri and H. García, Angew. Chem., Int. Ed., 2016, 55, 5414–5445.
27. J. Li, Z. Cui, Y. Zheng, X. Liu, Z. Li, H. Jiang, S. Zhu, Y. Zhang, P. K. Chu and S. Wu, Appl. Catal., B, 2022, 317, 121701.
28. Y. Luo, X. Liu, L. Tan, Z. Li, K. W. K. Yeung, Y. Zheng, Z. Cui, Y. Liang, S. Zhu, C. Li, X. Wang and S. Wu, Chem. Eng. J., 2021, 405, 126730.
29. A. Bigham, N. Islami, A. Khosravi, A. Zarepour, S. Iravani and A. Zarrabi, Small, 2024, 20, 2311903.
30. S. Chen, Z. Huang, M. Yuan, G. Huang, H. Guo, G. Meng, Z. Feng and P. Zhang, J. Mater. Sci. Technol., 2022, 125, 67–80.
31. H. Huang, Z. Wang, L. Chen, H. Yu and Y. Chen, Adv. Healthcare Mater., 2023, 12, 2201607.
32. A. B. Cook and P. Decuzzi, ACS Nano, 2021, 15, 2068–2098.
33. C. Pettinari, R. Pettinari, C. Di Nicola, A. Tombesi, S. Scuri and F. Marchetti, Coord. Chem. Rev., 2021, 446, 214121.
34. H. Zhou, J. Han, J. Cuan and Y. Zhou, Chem. Eng. J., 2022, 431, 134170.
35. J. Son, G. Yi, J. Yoo, C. Park, H. Koo and H. S. Choi, Adv. Drug Delivery Rev., 2019, 138, 133–147.
36. H. Huang, A. Ali, Y. Liu, H. Xie, S. Ullah, S. Roy, Z. Song, B. Guo and J. Xu, Adv. Drug Delivery Rev., 2023, 192, 114634.
37. Y. Liu, J. Wu, W. Li, J. Li, H. Han and Z. Song, Coord. Chem. Rev., 2023, 496, 215431.
38. D.-B. Hao, J.-L. Li, X.-C. Zhou, Y. Y. Li, Z.-X. Zhao and R. Zhou, Small, 2024, 20, 2305943.
39. Y. Wu, G. Deng, K. Jiang, H. Wang, Z. Song and H. Han, Biomaterials, 2021, 268, 120588.
40. Y. He, X. Wang, C. Zhang, J. Sun, J. Xu and D. Li, Small, 2023, 19, 2300199.
41. X. Han, G. Boix, M. Balcerzak, O. H. Moriones, M. Cano-Sarabia, P. Cortés, N. Bastús, V. Puntes, M. Llagostera, I. Imaz and D. Maspoch, Adv. Funct. Mater., 2022, 32, 2112902.
42. Z. Song, Y. Wu, Q. Cao, H. Wang, X. Wang and H. Han, Adv. Funct. Mater., 2018, 28, 1800011.
43. W. Teng, Z. Zhang, Y. Wang, Y. Ye, E. Yinwang, A. Liu, X. Zhou, J. Xu, C. Zhou, H. Sun, F. Wang, L. Zhang, C. Cheng, P. Lin, Y. Wu, Z. Gou, X. Yu and Z. Ye, Small, 2021, 17, 2102315.
44. X. Nie, S. Wu, A. Mensah, Q. Wang, F. Huang and Q. Wei, Chem. Eng. J., 2020, 395, 125012.
45. M. Chen, Z. Long, R. Dong, L. Wang, J. Zhang, S. Li, X. Zhao, X. Hou, H. Shao and X. Jiang, Small, 2020, 16, 1906240.
46. W. Xie, J. Chen, X. Cheng, H. Feng, X. Zhang, Z. Zhu, S. Dong, Q. Wan, X. Pei and J. Wang, Small, 2023, 19, 2205941.
47. Y. Li, L. Liu, T. Meng, L. Wang and Z. Xie, ACS Nano, 2023, 17, 2932–2942.
48. J. Sun, Y. Fan, W. Ye, L. Tian, S. Niu, W. Ming, J. Zhao and L. Ren, Chem. Eng. J., 2021, 417, 128049.
49. J. Li, S. Song, J. Meng, L. Tan, X. Liu, Y. Zheng, Z. Li, K. W. K. Yeung, Z. Cui, Y. Liang, S. Zhu, X. Zhang and S. Wu, J. Am. Chem. Soc., 2021, 143, 15427–15439.
50. P. Li, J. Li, X. Feng, J. Li, Y. Hao, J. Zhang, H. Wang, A. Yin, J. Zhou, X. Ma and B. Wang, Nat. Commun., 2019, 10, 2177.
51. D. Ma, P. Li, X. Duan, J. Li, P. Shao, Z. Lang, L. Bao, Y. Zhang, Z. Lin and B. Wang, Angew. Chem., Int. Ed., 2020, 59, 3905–3909.
52. Q. Deng, P. Sun, L. Zhang, Z. Liu, H. Wang, J. Ren and X. Qu, Adv. Funct. Mater., 2019, 29, 1903018.
53. D. Han, Y. Li, X. Liu, B. Li, Y. Han, Y. Zheng, K. W. K. Yeung, C. Li, Z. Cui, Y. Liang, Z. Li, S. Zhu, X. Wang and S. Wu, Chem. Eng. J., 2020, 396, 125194.
54. J. Li, X. Liu, L. Tan, Z. Cui, X. Yang, Y. Liang, Z. Li, S. Zhu, Y. Zheng, K. W. K. Yeung, X. Wang and S. Wu, Nat. Commun., 2019, 10, 4490.
55. Z. Liu, L. Tan, X. Liu, Y. Liang, Y. Zheng, K. W. K. Yeung, Z. Cui, S. Zhu, Z. Li and S. Wu, Colloids Surf., B, 2020, 188, 110781.
56. L. Liu, Y. Li, L. Wang and Z. Xie, J. Mater. Chem. A, 2022, 10, 20794–20803.
57. Y. Yang, Y. Deng, J. Huang, X. Fan, C. Cheng, C. Nie, L. Ma, W. Zhao and C. Zhao, Adv. Funct. Mater., 2019, 29, 1900143.
58. K. O. Oduwole, A. A. Glynn, D. C. Molony, D. Murray, S. Rowe, L. M. Holland, D. J. McCormack and J. P. O'Gara, J. Orthop. Res., 2010, 28, 1252–1256.
59. M. J. Hoekstra, S. J. Westgate and S. Mueller, Int. Wound J., 2017, 14, 172–179.
60. W. Liu, J. Li, M. Cheng, Q. Wang, Y. Qian, K. W. K. Yeung, P. K. Chu and X. Zhang, Biomaterials, 2019, 208, 8–20.
61. D. P. Linklater, M. De Volder, V. A. Baulin, M. Werner, S. Jessl, M. Golozar, L. Maggini, S. Rubanov, E. Hanssen, S. Juodkazis and E. P. Ivanova, ACS Nano, 2018, 12, 6657–6667.
62. L. Děkanovský, R. Elashnikov, M. Kubiková, B. Vokatá, V. Švorčík and O. Lyutakov, Adv. Funct. Mater., 2019, 29, 1901880.
63. C. Peng, Y. Zhao, S. Jin, J. Wang, R. Liu, H. Liu, W. Shi, S. K. Kolawole, L. Ren, B. Yu and K. Yang, ACS Appl. Mater. Interfaces, 2019, 11, 125–136.
64. X. Wang, S. Liu, M. Li, P. Yu, X. Chu, L. Li, G. Tan, Y. Wang, X. Chen, Y. Zhang and C. Ning, J. Inorg. Biochem., 2016, 163, 214–220.
65. M. A. Wahab, C. M. Hasan, Z. A. Alothman and M. S. A. Hossain, J. Hazard. Mater., 2021, 408, 124919.
66. M. M. Yallapu, P. K. B. Nagesh, M. Jaggi and S. C. Chauhan, AAPS J., 2015, 17, 1341–1356.
67. K. Mahmood, K. M. Zia, M. Zuber, M. Salman and M. N. Anjum, Int. J. Biol. Macromol., 2015, 81, 877–890.
68. N. Thomas, D. D. Dionysiou and S. C. Pillai, J. Hazard. Mater., 2021, 404, 124082.
69. W. Zhao, J. Deng, Y. Ren, L. Xie, W. Li, Q. Wang, S. Li and S. Liu, Nanotoxicology, 2021, 15, 311–330.
70. J. Yang and Y.-W. Yang, Small, 2020, 16, 1906846.
71. Q. Xu and H. Kitagawa, Adv. Mater., 2018, 30, 1803613.
72. J. Chen, D. Sheng, T. Ying, H. Zhao, J. Zhang, Y. Li, H. Xu and S. Chen, Nano-Micro Lett., 2020, 13, 23.
73. Y. Duan, Y. Wang, X. Li, G. Zhang, G. Zhang and J. Hu, Chem. Sci., 2020, 11, 186–194.
74. W. Gong, C. Xia and Q. He, Wiley Interdiscip. Rev.: Nanomed. Nanobiotechnol., 2022, 14, e1744.
75. P. G. Wang, M. Xian, X. Tang, X. Wu, Z. Wen, T. Cai and A. J. Janczuk, Chem. Rev., 2002, 102, 1091–1134.
76. L. Gao, X. Qiao, L. Zhang, Y. Wang, Y. Wan and C. Chen, Nitric oxide, 2022, 128, 50–58.
77. S. Sortino, Chem. Soc. Rev., 2010, 39, 2903–2913.
78. J. Lee, L. Chen, A. H. West and G. B. Richter-Addo, Chem. Rev., 2002, 102, 1019–1066.
79. C. Parisi, M. Failla, A. Fraix, B. Rolando, E. Gianquinto, F. Spyrakis, E. Gazzano, C. Riganti, L. Lazzarato, R. Fruttero, A. Gasco and S. Sortino, Chem. – Eur. J., 2019, 25, 11080–11084.
80. N. Ieda, Y. Hotta, N. Miyata, K. Kimura and H. Nakagawa, J. Am. Chem. Soc., 2014, 136, 7085–7091.
81. K. Zhao, Z. Zhang, Y. Feng, S. Lin, H. Li and X. Gao, Appl. Catal., B, 2020, 268, 118740.
82. H. Liu, C. Xu, D. Li and H.-L. Jiang, Angew. Chem., Int. Ed., 2018, 57, 5379–5383.
83. A. C. McKinlay, J. F. Eubank, S. Wuttke, B. Xiao, P. S. Wheatley, P. Bazin, J. C. Lavalley, M. Daturi, A. Vimont, G. De Weireld, P. Horcajada, C. Serre and R. E. Morris, Chem. Mater., 2013, 25, 1592–1599.
84. Y.-H. Hong, M. Narwane, L. Y.-M. Liu, Y.-D. Huang, C.-W. Chung, Y.-H. Chen, B.-W. Liao, Y.-H. Chang, C.-R. Wu, H.-C. Huang, I. J. Hsu, L.-Y. Cheng, L.-Y. Wu, Y.-L. Chueh, Y. Chen, C.-H. Lin and T.-T. Lu, ACS Appl. Mater. Interfaces, 2022, 14, 3849–3863.
85. I. Roy and J. F. Stoddart, Acc. Chem. Res., 2021, 54, 1440–1453.
86. S. He, L. Wu, X. Li, H. Sun, T. Xiong, J. Liu, C. Huang, H. Xu, H. Sun, W. Chen, R. Gref and J. Zhang, Acta Pharm. Sin. B, 2021, 11, 2362–2395.
87. Y. He, T. Xiong, S. He, H. Sun, C. Huang, X. Ren, L. Wu, L. H. Patterson and J. Zhang, Adv. Funct. Mater., 2021, 31, 2004550.
88. V. Singh, T. Guo, H. Xu, L. Wu, J. Gu, C. Wu, R. Gref and J. Zhang, Chem. Commun., 2017, 53, 9246–9249.
89. Q. Xue, C. Ye, M. Zhang, X. Hu and T. Cai, J. Colloid Interface Sci., 2019, 551, 39–46.
90. Y. Furukawa, T. Ishiwata, K. Sugikawa, K. Kokado and K. Sada, Angew. Chem., Int. Ed., 2012, 51, 10566–10569.
91. H. Li, M. R. Hill, R. Huang, C. Doblin, S. Lim, A. J. Hill, R. Babarao and P. Falcaro, Chem. Commun., 2016, 52, 5973–5976.
92. S. Lin, X. Liu, L. Tan, Z. Cui, X. Yang, K. W. K. Yeung, H. Pan and S. Wu, ACS Appl. Mater. Interfaces, 2017, 9, 19248–19257.
93. S. Quaresma, V. André, A. M. M. Antunes, S. M. F. Vilela, G. Amariei, A. Arenas-Vivo, R. Rosal, P. Horcajada and M. T. Duarte, Cryst. Growth Des., 2020, 20, 370–382.
94. B. P. Lazzaro, M. Zasloff and J. Rolff, Science, 2020, 368, eaau5480.
95. J. Wang, X. Dou, J. Song, Y. Lyu, X. Zhu, L. Xu, W. Li and A. Shan, Med. Res. Rev., 2019, 39, 831–859.
96. Z. Karimzadeh, S. Javanbakht and H. Namazi, Bioimpacts, 2019, 9, 5–13.
97. K. Suresh and A. J. Matzger, Angew. Chem., Int. Ed., 2019, 58, 16790–16794.
98. F. Duan, X. Feng, Y. Jin, D. Liu, X. Yang, G. Zhou, D. Liu, Z. Li, X.-J. Liang and J. Zhang, Biomaterials, 2017, 144, 155–165.
99. F. Xiong, Z. Qin, H. Chen, Q. Lan, Z. Wang, N. Lan, Y. Yang, L. Zheng, J. Zhao and D. Kai, J. Nanobiotechnol., 2020, 18, 139.
100. Q. Sun, H. Bi, Z. Wang, C. Li, X. Wang, J. Xu, H. Zhu, R. Zhao, F. He, S. Gai and P. Yang, Biomaterials, 2019, 223, 119473.
101. A. Maleki, M.-A. Shahbazi, V. Alinezhad and H. A. Santos, Adv. Healthcare Mater., 2020, 9, 2000248.
102. M. Kermanian, S. Nadri, P. Mohammadi, S. Iravani, N. Ahmadi, V. Alinezhad, M.-A. Shokrgozar, M. Haddad, E. Mostafavi and A. Maleki, J. Controlled Release, 2023, 359, 326–346.
103. N. Nasihat Sheno, S. Farhadi, A. Maleki and M. Hamidi, New J. Chem., 2019, 43, 1956–1963.
104. R. J. Ferguson, A. J. R. Palmer, A. Taylor, M. L. Porter, H. Malchau and S. Glyn-Jones, Lancet, 2018, 392, 1662–1671.
105. M. Morgenstern, R. Kühl, H. Eckardt, Y. Acklin, B. Stanic, M. Garcia, D. Baumhoer and W.-J. Metsemakers, Injury, 2018, 49, S83–S90.
106. W.-J. Metsemakers, J. Onsea, E. Neutjens, E. Steffens, A. Schuermans, M. McNally and S. Nijs, Int. Orthop., 2017, 41, 2457–2469.
107. P. A. Anderson, J. W. Savage, A. R. Vaccaro, K. Radcliff, P. M. Arnold, B. D. Lawrence and M. F. Shamji, Neurosurgery, 2017, 80, S114–S123.
108. L. Urish Kenneth and E. Cassat James, Infect. Immun., 2020, 88, e00932-19.
109. X. Zhu, K. Zhang, K. Lu, T. Shi, S. Shen, X. Chen, J. Dong, W. Gong, Z. Bao, Y. Shi, Y. Ma, H. Teng and Q. Jiang, Ann. Transl. Med., 2019, 7, 170.
110. T. Shirai, T. Shimizu, K. Ohtani, Y. Zen, M. Takaya and H. Tsuchiya, Acta Biomater., 2011, 7, 1928–1933.
111. Y. Yan, Y. Zhang, Q. Wang, H. Du and L. Qiao, Appl. Surf. Sci., 2016, 363, 432–438.
112. Z. Wang, X. Tang, X. Wang, D. Yang, C. Yang, Y. Lou, J. Chen and N. He, Chem. Commun., 2016, 52, 12210–12213.
113. H. Sun, F. He and W. Choi, Environ. Sci. Technol., 2020, 54, 6427–6437.
114. E. Bigot, R. Bataille and T. Patrice, J. Photochem. Photobiol., B, 2012, 107, 14–19.
115. A. Blázquez-Castro, T. Breitenbach and P. R. Ogilby, Photochem. Photobiol. Sci., 2014, 13, 1235–1240.
116. J.-C. Yang, Y. Chen, Y.-H. Li and X.-B. Yin, ACS Appl. Mater. Interfaces, 2017, 9, 22278–22288.
117. C. M. Courtney, S. M. Goodman, J. A. McDaniel, N. E. Madinger, A. Chatterjee and P. Nagpal, Nat. Mater., 2016, 15, 529–534.
118. W. C. M. A. de Melo, P. Avci, M. N. de Oliveira, A. Gupta, D. Vecchio, M. Sadasivam, R. Chandran, Y.-Y. Huang, R. Yin, L. R. Perussi, G. P. Tegos, J. R. Perussi, T. Dai and M. R. Hamblin, Expert Rev. Anti-Infect. Ther., 2013, 11, 669–693.
119. M. R. Hamblin, Curr. Opin. Microbiol., 2016, 33, 67–73.
120. M. R. Hamblin and T. Hasan, Photochem. Photobiol. Sci., 2004, 3, 436–450.
121. M. Wainwright, T. Maisch, S. Nonell, K. Plaetzer, A. Almeida, G. P. Tegos and M. R. Hamblin, Lancet Infect. Dis., 2017, 17, e49–e55.
122. M. Wang, L. Nian, Y. Cheng, B. Yuan, S. Cheng and C. Cao, Chem. Eng. J., 2021, 426, 130832.
123. Y. Yang, H. Liu, M. Han, B. Sun and J. Li, Angew. Chem., Int. Ed., 2016, 55, 13538–13543.
124. Z.-Y. Chu, W.-N. Wang, C.-Y. Zhang, J. Ruan, B.-J. Chen, H.-M. Xu and H.-S. Qian, Chem. Eng. J., 2019, 375, 121927.
125. P. Gong, L. Sun, F. Wang, X. Liu, Z. Yan, M. Wang, L. Zhang, Z. Tian, Z. Liu and J. You, Chem. Eng. J., 2019, 356, 994–1002.
126. N. Niu, Z. Zhang, X. Gao, Z. Chen, S. Li and J. Li, Chem. Eng. J., 2018, 352, 818–827.
127. C. Chen, L. Ao, Y.-T. Wu, V. Cifliku, M. Cardoso Dos Santos, E. Bourrier, M. Delbianco, D. Parker, J. M. Zwier, L. Huang and N. Hildebrandt, Angew. Chem., Int. Ed., 2018, 57, 13686–13690.
128. K. E. Sapsford, L. Berti and I. L. Medintz, Angew. Chem., Int. Ed., 2006, 45, 4562–4589.
129. M. Chen, J. Zhang, J. Qi, R. Dong, H. Liu, D. Wu, H. Shao and X. Jiang, ACS Nano, 2022, 16, 7732–7744.
130. E. Lee, X. Li, J. Oh, N. Kwon, G. Kim, D. Kim and J. Yoon, Chem. Sci., 2020, 11, 5735–5739.
131. S. Rojas and P. Horcajada, Chem. Rev., 2020, 120, 8378–8415.
132. Z. Wu, X. Yuan, J. Zhang, H. Wang, L. Jiang and G. Zeng, ChemCatChem, 2017, 9, 41–64.
133. V. K. Sharma and M. Feng, J. Hazard. Mater., 2019, 372, 3–16.
134. K. Liu, Y. Gao, J. Liu, Y. Wen, Y. Zhao, K. Zhang and G. Yu, Environ. Sci. Technol., 2016, 50, 3634–3640.
135. A. Galstyan, R. Schiller and U. Dobrindt, Angew. Chem., Int. Ed., 2017, 56, 10362–10366.
136. Y. Liu, H. C. van der Mei, B. Zhao, Y. Zhai, T. Cheng, Y. Li, Z. Zhang, H. J. Busscher, Y. Ren and L. Shi, Adv. Funct. Mater., 2017, 27, 1701974.
137. M. Chen, J. Wei, S. Xie, X. Tao, Z. Zhang, P. Ran and X. Li, Nanoscale, 2019, 11, 1410–1422.
138. Y. Liu, H. J. Busscher, B. Zhao, Y. Li, Z. Zhang, H. C. van der Mei, Y. Ren and L. Shi, ACS Nano, 2016, 10, 4779–4789.
139. H.-C. Flemming and J. Wingender, Nat. Rev. Microbiol., 2010, 8, 623–633.
140. S. Fuchs, J. Pané-Farré, C. Kohler, M. Hecker and S. Engelmann, J. Bacteriol., 2007, 189, 4275–4289.
141. A. F. Radovic-Moreno, T. K. Lu, V. A. Puscasu, C. J. Yoon, R. Langer and O. C. Farokhzad, ACS Nano, 2012, 6, 4279–4287.
142. D. Hu, H. Li, B. Wang, Z. Ye, W. Lei, F. Jia, Q. Jin, K.-F. Ren and J. Ji, ACS Nano, 2017, 11, 9330–9339.
143. L. Zhao, X. Zhang, X. Wang, X. Guan, W. Zhang and J. Ma, J. Nanobiotechnol., 2021, 19, 335.
144. J.-W. Xu, K. Yao and Z.-K. Xu, Nanoscale, 2019, 11, 8680–8691.
145. G. Liu, J. Zou, Q. Tang, X. Yang, Y. Zhang, Q. Zhang, W. Huang, P. Chen, J. Shao and X. Dong, ACS Appl. Mater. Interfaces, 2017, 9, 40077–40086.
146. R. Zhang, F. Yan and Y. Chen, Adv. Sci., 2018, 5, 1801175.
147. D. Han, Y. Han, J. Li, X. Liu, K. W. K. Yeung, Y. Zheng, Z. Cui, X. Yang, Y. Liang, Z. Li, S. Zhu, X. Yuan, X. Feng, C. Yang and S. Wu, Appl. Catal., B, 2020, 261, 118248.
148. Z. Tang, P. Zhao, D. Ni, Y. Liu, M. Zhang, H. Wang, H. Zhang, H. Gao, Z. Yao and W. Bu, Mater. Horiz., 2018, 5, 946–952.
149. Y. Qu, T. Wei, J. Zhao, S. Jiang, P. Yang, Q. Yu and H. Chen, J. Mater. Chem. B, 2018, 6, 3946–3955.
150. Y. Feng, L. Liu, J. Zhang, H. Aslan and M. Dong, J. Mater. Chem. B, 2017, 5, 8631–8652.
151. M. A. Huergo, L. J. Giovanetti, A. A. Rubert, C. A. Grillo, M. S. Moreno, F. G. Requejo, R. C. Salvarezza and C. Vericat, Appl. Surf. Sci., 2019, 464, 131–139.
152. Y. Qiao, F. Ma, C. Liu, B. Zhou, Q. Wei, W. Li, D. Zhong, Y. Li and M. Zhou, ACS Appl. Mater. Interfaces, 2018, 10, 193–206.
153. X. Ran, Y. Du, Z. Wang, H. Wang, F. Pu, J. Ren and X. Qu, ACS Appl. Mater. Interfaces, 2017, 9, 19717–19724.
154. S. Cai, J. Qian, S. Yang, L. Kuang and D. Hua, Colloids Surf., B, 2019, 181, 31–38.
155. Z.-H. Miao, K. Li, P.-Y. Liu, Z. Li, H. Yang, Q. Zhao, M. Chang, Q. Yang, L. Zhen and C.-Y. Xu, Adv. Healthcare Mater., 2018, 7, 1701202.
156. M. Hou, R. Yang, L. Zhang, L. Zhang, G. Liu, Z. Xu, Y. Kang and P. Xue, ACS Biomater. Sci. Eng., 2018, 4, 4266–4277.
157. J. Hu, J. Lin, Y. Zhang, Z. Lin, Z. Qiao, Z. Liu, W. Yang, X. Liu, M. Dong and Z. Guo, J. Mater. Chem. A, 2019, 7, 26039–26052.
158. C. Jiang, G. Wang, R. Hein, N. Liu, X. Luo and J. J. Davis, Chem. Rev., 2020, 120, 3852–3889.
159. H. Zhou, H. Wang, H. Niu, Y. Zhao, Z. Xu and T. Lin, Adv. Funct. Mater., 2017, 27, 1604261.
160. X. Yin, W. Liang, Y. Wang, Y. Xiao, Y. Zhou and M. Lang, Mater. Chem. Phys., 2021, 261, 124102.
161. J. Lv and Y. Cheng, Chem. Soc. Rev., 2021, 50, 5435–5467.
162. D. Feng, Z.-Y. Gu, J.-R. Li, H.-L. Jiang, Z. Wei and H.-C. Zhou, Angew. Chem., Int. Ed., 2012, 51, 10307–10310.
163. M. Liu, L. Wang, X. Zheng and Z. Xie, ACS Appl. Mater. Interfaces, 2017, 9, 41512–41520.
164. M. Shen, X. Liao, Y. Xianyu, D. Liu and T. Ding, ACS Appl. Mater. Interfaces, 2022, 14, 12662–12673.
165. M. Cao, W. Zhao, L. Wang, R. Li, H. Gong, Y. Zhang, H. Xu and J. R. Lu, ACS Appl. Mater. Interfaces, 2018, 10, 24937–24946.
166. X. Fan, F. Yang, C. Nie, Y. Yang, H. Ji, C. He, C. Cheng and C. Zhao, ACS Appl. Mater. Interfaces, 2018, 10, 296–307.
167. H. E. Karahan, C. Wiraja, C. Xu, J. Wei, Y. Wang, L. Wang, F. Liu and Y. Chen, Adv. Healthcare Mater., 2018, 7, 1701406.
168. C. Nie, Y. Yang, C. Cheng, L. Ma, J. Deng, L. Wang and C. Zhao, Acta Biomater., 2017, 51, 479–494.
169. S. Li, C. Cheng and A. Thomas, Adv. Mater., 2017, 29, 1602547.
170. C. Cheng, S. Li, A. Thomas, N. A. Kotov and R. Haag, Chem. Rev., 2017, 117, 1826–1914.
171. C. Cheng, J. Zhang, S. Li, Y. Xia, C. Nie, Z. Shi, J. L. Cuellar-Camacho, N. Ma and R. Haag, Adv. Mater., 2018, 30, 1705452.
172. M. Zhao, Y. Huang, Y. Peng, Z. Huang, Q. Ma and H. Zhang, Chem. Soc. Rev., 2018, 47, 6267–6295.
173. D. Mao, F. Hu, Kenry, S. Ji, W. Wu, D. Ding, D. Kong and B. Liu, Adv. Mater., 2018, 30, 1706831.
174. Y. Li, J. Tang, L. He, Y. Liu, Y. Liu, C. Chen and Z. Tang, Adv. Mater., 2015, 27, 4075–4080.
175. J. Xiao, Y. Zhu, S. Huddleston, P. Li, B. Xiao, O. K. Farha and G. A. Ameer, ACS Nano, 2018, 12, 1023–1032.
176. R. R. Salunkhe, Y. V. Kaneti and Y. Yamauchi, ACS Nano, 2017, 11, 5293–5308.
177. Y. Zhang, F. Wang, E. Ju, Z. Liu, Z. Chen, J. Ren and X. Qu, Adv. Funct. Mater., 2016, 26, 6454–6461.
178. Y. Wang, N. Zhang, E. Zhang, Y. Han, Z. Qi, M. B. Ansorge-Schumacher, Y. Ge and C. Wu, Chem. – Eur. J., 2019, 25, 1716–1721.
179. C. Cheng, S. Li, Y. Xia, L. Ma, C. Nie, C. Roth, A. Thomas and R. Haag, Adv. Mater., 2018, 30, 1802669.
180. S. Li, C. Cheng, A. Sagaltchik, P. Pachfule, C. Zhao and A. Thomas, Adv. Funct. Mater., 2019, 29, 1807419.
181. S. Li, S. Dong, W. Xu, S. Tu, L. Yan, C. Zhao, J. Ding and X. Chen, Adv. Sci., 2018, 5, 1700527.
182. K. Herget, P. Hubach, S. Pusch, P. Deglmann, H. Götz, T. E. Gorelik, I. Y. A. Gural'skiy, F. Pfitzner, T. Link, S. Schenk, M. Panthöfer, V. Ksenofontov, U. Kolb, T. Opatz, R. André and W. Tremel, Adv. Mater., 2017, 29, 1603823.
183. R. F. Landis, C.-H. Li, A. Gupta, Y.-W. Lee, M. Yazdani, N. Ngernyuang, I. Altinbasak, S. Mansoor, M. A. S. Khichi, A. Sanyal and V. M. Rotello, J. Am. Chem. Soc., 2018, 140, 6176–6182.
184. L. Gao, M. Li, S. Ehrmann, Z. Tu and R. Haag, Angew. Chem., Int. Ed., 2019, 58, 3645–3649.
185. Y. Yang, P. He, Y. Wang, H. Bai, S. Wang, J.-F. Xu and X. Zhang, Angew. Chem., Int. Ed., 2017, 56, 16239–16242.
186. H. Xu, Z. Fang, W. Tian, Y. Wang, Q. Ye, L. Zhang and J. Cai, Adv. Mater., 2018, 30, 1801100.
187. R. Joseph, A. Naugolny, M. Feldman, I. M. Herzog, M. Fridman and Y. Cohen, J. Am. Chem. Soc., 2016, 138, 754–757.
188. S. J. Lam, N. M. O'Brien-Simpson, N. Pantarat, A. Sulistio, E. H. H. Wong, Y.-Y. Chen, J. C. Lenzo, J. A. Holden, A. Blencowe, E. C. Reynolds and G. G. Qiao, Nat. Microbiol., 2016, 1, 16162.
189. S.-H. Cha, J. Hong, M. McGuffie, B. Yeom, J. S. VanEpps and N. A. Kotov, ACS Nano, 2015, 9, 9097–9105.
190. K. Usha, A. K. Nicholas and J. S. VanEpps, Curr. Pharm. Des., 2018, 24, 896–903.
191. C. Zhan, W. Wang, C. Santamaria, B. Wang, A. Rwei, B. P. Timko and D. S. Kohane, Nano Lett., 2017, 17, 660–665.
192. L. Zhang, S.-S. Wan, C.-X. Li, L. Xu, H. Cheng and X.-Z. Zhang, Nano Lett., 2018, 18, 7609–7618.
193. N. Yan, X. Wang, L. Lin, T. Song, P. Sun, H. Tian, H. Liang and X. Chen, Adv. Funct. Mater., 2018, 28, 1800490.
194. H. Wang, P. Li, D. Yu, Y. Zhang, Z. Wang, C. Liu, H. Qiu, Z. Liu, J. Ren and X. Qu, Nano Lett., 2018, 18, 3344–3351.
195. Z. Xu, Z. Qiu, Q. Liu, Y. Huang, D. Li, X. Shen, K. Fan, J. Xi, Y. Gu, Y. Tang, J. Jiang, J. Xu, J. He, X. Gao, Y. Liu, H. Koo, X. Yan and L. Gao, Nat. Commun., 2018, 9, 3713.
196. C. Mao, Y. Xiang, X. Liu, Z. Cui, X. Yang, Z. Li, S. Zhu, Y. Zheng, K. W. K. Yeung and S. Wu, ACS Nano, 2018, 12, 1747–1759.
197. J. Shao, C. Ruan, H. Xie, Z. Li, H. Wang, P. K. Chu and X.-F. Yu, Adv. Sci., 2018, 5, 1700848.
198. F. Yang, A. Skripka, M. S. Tabatabaei, S. H. Hong, F. Ren, A. Benayas, J. K. Oh, S. Martel, X. Liu, F. Vetrone and D. Ma, ACS Nano, 2019, 13, 408–420.
199. A. Panáček, L. Kvítek, M. Smékalová, R. Večeřová, M. Kolář, M. Röderová, F. Dyčka, M. Šebela, R. Prucek, O. Tomanec and R. Zbořil, Nat. Nanotechnol., 2018, 13, 65–71.
200. X. Xie, C. Mao, X. Liu, L. Tan, Z. Cui, X. Yang, S. Zhu, Z. Li, X. Yuan, Y. Zheng, K. W. K. Yeung, P. K. Chu and S. Wu, ACS Cent. Sci., 2018, 4, 724–738.
201. L. Tan, J. Li, X. Liu, Z. Cui, X. Yang, S. Zhu, Z. Li, X. Yuan, Y. Zheng, K. W. K. Yeung, H. Pan, X. Wang and S. Wu, Adv. Mater., 2018, 30, 1801808.
202. H. Bagheri, S. Bochani, M. Seyedhamzeh, Z. Shokri, A. Kalantari-Hesari, R. J. Turner, M. Kharaziha, K. Esmaeilzadeh, M. Golami, H. Zeighami and A. Maleki, Adv. Ther., 2024, 7, 2400099.
203. S. Bochani, A. Kalantari-Hesari, F. Haghi, V. Alinezhad, H. Bagheri, P. Makvandi, M.-A. Shahbazi, A. Salimi, I. Hirata, V. Mattoli, A. Maleki and B. Guo, ACS Appl. Bio Mater., 2022, 5, 4435–4453.
204. Y. Zhang, P. Sun, L. Zhang, Z. Wang, F. Wang, K. Dong, Z. Liu, J. Ren and X. Qu, Adv. Funct. Mater., 2019, 29, 1808594.
205. H. Qiu, F. Pu, Z. Liu, Q. Deng, P. Sun, J. Ren and X. Qu, Small, 2019, 15, 1902522.
206. Y. Zeng, C. Wang, K. Lei, C. Xiao, X. Jiang, W. Zhang, L. Wu, J. Huang and W. Li, Adv. Healthcare Mater., 2023, 12, 2300250.
207. Q.-T. He, P. Qian, X.-Y. Yang, Q. Kuang, Y.-T. Lin, W. Yi, T. Tian, Y.-P. Cai and X.-J. Hong, Chem. Eng. J., 2024, 493, 152760.
208. Y. Xiao, M. Xu, N. Lv, C. Cheng, P. Huang, J. Li, Y. Hu and M. Sun, Acta Biomater., 2021, 122, 291–305.
209. Y. Yang, X. Wu, C. He, J. Huang, S. Yin, M. Zhou, L. Ma, W. Zhao, L. Qiu, C. Cheng and C. Zhao, ACS Appl. Mater. Interfaces, 2020, 12, 13698–13708.
210. D. Kim, K. W. Park, J. T. Park and I. Choi, ACS Appl. Mater. Interfaces, 2023, 15, 22903–22914.
211. X. Fan, F. Yang, J. Huang, Y. Yang, C. Nie, W. Zhao, L. Ma, C. Cheng, C. Zhao and R. Haag, Nano Lett., 2019, 19, 5885–5896.
212. Y. Luo, J. Li, X. Liu, L. Tan, Z. Cui, X. Feng, X. Yang, Y. Liang, Z. Li, S. Zhu, Y. Zheng, K. W. K. Yeung, C. Yang, X. Wang and S. Wu, ACS Cent. Sci., 2019, 5, 1591–1601.
213. J. Gao, L. Hao, R. Jiang, Z. Liu, L. Tian, J. Zhao, W. Ming and L. Ren, Green Chem., 2022, 24, 5930–5940.
214. P. Yu, Y. Han, D. Han, X. Liu, Y. Liang, Z. Li, S. Zhu and S. Wu, J. Hazard. Mater., 2020, 390, 122126.
215. J. Li, Q. Zhang, Z. Chen, S. Guo, J. Guo and F. Yan, ACS Appl. Mater. Interfaces, 2024, 16, 8459–8473.
216. X. Nie, S. Wu, F. Huang, W. Li, H. Qiao, Q. Wang and Q. Wei, Chem. Eng. J., 2021, 416, 129072.
217. X. Zhao, L. Chang, Y. Hu, S. Xu, Z. Liang, X. Ren, X. Mei and Z. Chen, ACS Appl. Mater. Interfaces, 2022, 14, 18194–18208.
218. S. Jahangir, S. Hosseini, F. Mostafaei, F. A. Sayahpour and M. Baghaban Eslaminejad, J. Mater. Sci.: Mater. Med., 2018, 30, 1.
219. X. Ren, Y. Han, J. Wang, Y. Jiang, Z. Yi, H. Xu and Q. Ke, Acta Biomater., 2018, 70, 140–153.
220. Q. Zhang, J.-H. Oh, C. H. Park, J.-H. Baek, H.-M. Ryoo and K. M. Woo, ACS Appl. Mater. Interfaces, 2017, 9, 7950–7963.
221. J. Tian, X. Zeng, X. Xie, S. Han, O.-W. Liew, Y.-T. Chen, L. Wang and X. Liu, J. Am. Chem. Soc., 2015, 137, 6550–6558.
222. E.-J. Lee and E. A. Groisman, Nature, 2012, 486, 271–275.
223. R. Mempin, H. Tran, C. Chen, H. Gong, K. Kim Ho and S. Lu, BMC Microbiol., 2013, 13, 301.
224. C. Xu, Z. Liu, L. Wu, J. Ren and X. Qu, Adv. Funct. Mater., 2014, 24, 1624–1630.
225. S. P. Deshmukh, S. M. Patil, S. B. Mullani and S. D. Delekar, Mater. Sci. Eng. C, 2019, 97, 954–965.
226. K. S. Siddiqi, A. Husen and R. A. K. Rao, J. Nanobiotechnol., 2018, 16, 14.
227. S. Shakya, Y. He, X. Ren, T. Guo, A. Maharjan, T. Luo, T. Wang, R. Dhakhwa, B. Regmi, H. Li, R. Gref and J. Zhang, Small, 2019, 15, 1901065.
228. Z. Liu, Y. Wang, Y. Zu, Y. Fu, N. Li, N. Guo, R. Liu and Y. Zhang, Mater. Sci. Eng. C, 2014, 42, 31–37.
229. O. Choi and Z. Hu, Environ. Sci. Technol., 2008, 42, 4583–4588.
230. M. Xu, Y. Hu, W. Ding, F. Li, J. Lin, M. Wu, J. Wu, L.-P. Wen, B. Qiu, P.-F. Wei and P. Li, Biomaterials, 2020, 258, 120308.
231. D. F. Sava Gallis, K. S. Butler, J. O. Agola, C. J. Pearce and A. A. McBride, ACS Appl. Mater. Interfaces, 2019, 11, 7782–7791.
232. A. R. Chowdhuri, B. Das, A. Kumar, S. Tripathy, S. Roy and S. K. Sahu, Nanotechnology, 2017, 28, 095102.
233. H. Nabipour, M. H. Sadr and G. R. Bardajee, New J. Chem., 2017, 41, 7364–7370.
234. M. Zhang, L. Zhang, Y. Chen, L. Li, Z. Su and C. Wang, Chem. Sci., 2017, 8, 8067–8077.
235. Y. Liu, K. Ai and L. Lu, Chem. Rev., 2014, 114, 5057–5115.
236. T. Zhou, Y. Zhu, X. Li, X. Liu, K. W. K. Yeung, S. Wu, X. Wang, Z. Cui, X. Yang and P. K. Chu, Prog. Mater. Sci., 2016, 83, 191–235.
237. Q. Wu, M. Niu, X. Chen, L. Tan, C. Fu, X. Ren, J. Ren, L. Li, K. Xu, H. Zhong and X. Meng, Biomaterials, 2018, 162, 132–143.
238. Z. Tu, G. Guday, M. Adeli and R. Haag, Adv. Mater., 2018, 30, 1706709.
239. R. Walczak, B. Kurpil, A. Savateev, T. Heil, J. Schmidt, Q. Qin, M. Antonietti and M. Oschatz, Angew. Chem., Int. Ed., 2018, 57, 10765–10770.
240. Z. Zhang, L. H. Klausen, M. Chen and M. Dong, Small, 2018, 14, 1801983.
241. X. Zou, L. Zhang, Z. Wang and Y. Luo, J. Am. Chem. Soc., 2016, 138, 2064–2077.
242. Y. Tu, M. Lv, P. Xiu, T. Huynh, M. Zhang, M. Castelli, Z. Liu, Q. Huang, C. Fan, H. Fang and R. Zhou, Nat. Nanotechnol., 2013, 8, 594–601.
243. Z. Qi, P. Bharate, C.-H. Lai, B. Ziem, C. Böttcher, A. Schulz, F. Beckert, B. Hatting, R. Mülhaupt, P. H. Seeberger and R. Haag, Nano Lett., 2015, 15, 6051–6057.
244. K. H. Tan, S. Sattari, I. S. Donskyi, J. L. Cuellar-Camacho, C. Cheng, K. Schwibbert, A. Lippitz, W. E. S. Unger, A. Gorbushina, M. Adeli and R. Haag, Nanoscale, 2018, 10, 9525–9537.
245. F. Perreault, A. F. de Faria, S. Nejati and M. Elimelech, ACS Nano, 2015, 9, 7226–7236.
246. C. Korupalli, C.-C. Huang, W.-C. Lin, W.-Y. Pan, P.-Y. Lin, W.-L. Wan, M.-J. Li, Y. Chang and H.-W. Sung, Biomaterials, 2017, 116, 1–9.
247. C.-W. Hsiao, H.-L. Chen, Z.-X. Liao, R. Sureshbabu, H.-C. Hsiao, S.-J. Lin, Y. Chang and H.-W. Sung, Adv. Funct. Mater., 2015, 25, 721–728.
248. S. Wang, K. Li, Y. Chen, H. Chen, M. Ma, J. Feng, Q. Zhao and J. Shi, Biomaterials, 2015, 39, 206–217.
249. T. Maisch, J. Baier, B. Franz, M. Maier, M. Landthaler, R.-M. Szeimies and W. Bäumler, Proc. Natl. Acad. Sci. U. S. A., 2007, 104, 7223–7228.
250. Q. Tang, W. Xiao, C. Huang, W. Si, J. Shao, W. Huang, P. Chen, Q. Zhang and X. Dong, Chem. Mater., 2017, 29, 5216–5224.
251. P. Liang, Y. Wang, P. Wang, J. Zou, H. Xu, Y. Zhang, W. Si and X. Dong, Nanoscale, 2017, 9, 18890–18896.
252. V. A. J. Kempf, M. Lebiedziejewski, K. Alitalo, J.-H. Wälzlein, U. Ehehalt, J. Fiebig, S. Huber, B. Schütt, C. A. Sander, S. Müller, G. Grassl, A. S. Yazdi, B. Brehm and I. B. Autenrieth, Circulation, 2005, 111, 1054–1062.
253. J. Borovička, W. J. Metheringham, L. A. Madden, C. D. Walton, S. D. Stoyanov and V. N. Paunov, J. Am. Chem. Soc., 2013, 135, 5282–5285.
254. Y. Li, X. Liu, L. Tan, Z. Cui, X. Yang, Y. Zheng, K. W. K. Yeung, P. K. Chu and S. Wu, Adv. Funct. Mater., 2018, 28, 1800299.
255. M. Liu, X. Xue, C. Ghosh, X. Liu, Y. Liu, E. P. Furlani, M. T. Swihart and P. N. Prasad, Chem. Mater., 2015, 27, 2584–2590.
256. J. Chen, C. Ning, Z. Zhou, P. Yu, Y. Zhu, G. Tan and C. Mao, Prog. Mater. Sci., 2019, 99, 1–26.
257. X. Liu and M. T. Swihart, Chem. Soc. Rev., 2014, 43, 3908–3920.
258. A. Comin and L. Manna, Chem. Soc. Rev., 2014, 43, 3957–3975.
259. S. Sortino, J. Mater. Chem., 2012, 22, 301–318.
260. L. O. Svaasand, C. J. Gomer and E. Morinelli, Lasers Med. Sci., 1990, 5, 121–128.
261. Z. Xu, Y. Gao, S. Meng, B. Yang, L. Pang, C. Wang and T. Liu, Front. Microbiol., 2016, 7, 242.
262. G. Wyszogrodzka, B. Marszałek, B. Gil and P. Dorożyński, Drug Discovery Today, 2016, 21, 1009–1018.
263. I. Burghardt, F. Lüthen, C. Prinz, B. Kreikemeyer, C. Zietz, H.-G. Neumann and J. Rychly, Biomaterials, 2015, 44, 36–44.
264. D. Wang, L. Niu, Z.-Y. Qiao, D.-B. Cheng, J. Wang, Y. Zhong, F. Bai, H. Wang and H. Fan, ACS Nano, 2018, 12, 3796–3803.
265. J. Park, Q. Jiang, D. Feng, L. Mao and H.-C. Zhou, J. Am. Chem. Soc., 2016, 138, 3518–3525.
266. S. M. Yoon, J. H. Park and B. A. Grzybowski, Angew. Chem., Int. Ed., 2017, 56, 127–132.
267. D. Wang, J. Zhou, R. Chen, R. Shi, G. Zhao, G. Xia, R. Li, Z. Liu, J. Tian, H. Wang, Z. Guo, H. Wang and Q. Chen, Biomaterials, 2016, 100, 27–40.
268. M. J. Cliffe, W. Wan, X. Zou, P. A. Chater, A. K. Kleppe, M. G. Tucker, H. Wilhelm, N. P. Funnell, F.-X. Coudert and A. L. Goodwin, Nat. Commun., 2014, 5, 4176.
269. H. Wu, Y. S. Chua, V. Krungleviciute, M. Tyagi, P. Chen, T. Yildirim and W. Zhou, J. Am. Chem. Soc., 2013, 135, 10525–10532.
270. K. Bilici, N. Atac, A. Muti, I. Baylam, O. Dogan, A. Sennaroglu, F. Can and H. Yagci Acar, Biomater. Sci., 2020, 8, 4616–4625.
271. C. Fang, D. Cen, Y. Wang, Y. Wu, X. Cai, X. Li and G. Han, Theranostics, 2020, 10, 7671–7682.
272. C. Zhang, J. Guo, X. Zou, S. Guo, Y. Guo, R. Shi and F. Yan, Adv. Healthcare Mater., 2021, 10, 2100775.
273. J. Zhu, J. Zou, Z. Zhang, J. Zhang, Y. Sun, X. Dong and Q. Zhang, Mater. Chem. Front., 2019, 3, 1523–1531.
274. W. Zhang, W. Lin, X. Wang, C. Li, S. Liu and Z. Xie, ACS Appl. Mater. Interfaces, 2019, 11, 278–287.
275. M. Broekgaarden, R. Weijer, M. Krekorian, B. van den Ijssel, M. Kos, L. K. Alles, A. C. van Wijk, Z. Bikadi, E. Hazai, T. M. van Gulik and M. Heger, Nano Res., 2016, 9, 1639–1662.
276. W. Deng, Q. Wu, P. Sun, P. Yuan, X. Lu, Q. Fan and W. Huang, Polym. Chem., 2018, 9, 2805–2812.
277. Q. Wang, B. Xia, J. Xu, X. Niu, J. Cai, Q. Shen, W. Wang, W. Huang and Q. Fan, Mater. Chem. Front., 2019, 3, 650–655.
278. Q. Guan, L.-L. Zhou, Y.-A. Li, W.-Y. Li, S. Wang, C. Song and Y.-B. Dong, ACS Nano, 2019, 13, 13304–13316.
279. T. Simon-Yarza, A. Mielcarek, P. Couvreur and C. Serre, Adv. Mater., 2018, 30, 1707365.
280. J. Jiang, Y. Zhao and O. M. Yaghi, J. Am. Chem. Soc., 2016, 138, 3255–3265.
281. S. M. Cohen, J. Am. Chem. Soc., 2017, 139, 2855–2863.
282. D. Chakraborty, A. Yurdusen, G. Mouchaham, F. Nouar and C. Serre, Adv. Funct. Mater., 2024, 34, 2309089.
283. S. M. Moosavi, A. Nandy, K. M. Jablonka, D. Ongari, J. P. Janet, P. G. Boyd, Y. Lee, B. Smit and H. J. Kulik, Nat. Commun., 2020, 11, 4068.
284. S. M. Moosavi, A. Chidambaram, L. Talirz, M. Haranczyk, K. C. Stylianou and B. Smit, Nat. Commun., 2019, 10, 539.
285. B. Xu, Z. Huang, Y. Liu, S. Li and H. Liu, Nano Today, 2023, 48, 101690.
286. X. Chen, Y. Zhuang, N. Rampal, R. Hewitt, G. Divitini, C. A. O’Keefe, X. Liu, D. J. Whitaker, J. W. Wills, R. Jugdaohsingh, J. J. Powell, H. Yu, C. P. Grey, O. A. Scherman and D. Fairen-Jimenez, J. Am. Chem. Soc., 2021, 143, 13557–13572.

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