Yawei Suna,
Yaopeng Zhang*a,
Jingjing Liu*b and
Fuqiang Nie*b
aState Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai, 201620, China. E-mail: zyp@dhu.edu.cn
bSuzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Division of Nanobionic Research, Suzhou, 215123, China. E-mail: jjliu2015@sinano.ac.cn; fqnie2012@sinano.ac.cn
First published on 21st January 2016
In this work, hydrogel photonic crystal beads with inverse opal structure are generated on a well-controlled microfluidic chip device. An online droplet drying method and templating technique are integrated into the producing process. This process results in the silica nanoparticles in the droplets self-assembled into spherical photonic crystals with narrow stop bands and identical structural colours, which is the ideal template for fabricating inverse opal hydrogel beads. The effects of acrylic acid (AA) concentration, water dosage and buffer pH on the equilibrium swelling of inverse opal hydrogel are discussed. In the concentration of AA (3%) and water (31%), the inverse opal hydrogel beads show wide sensing range and rapid response (less than 30 s) to pH variation. Overall, the inverse opal hydrogels as pH sensors show homogeneous structural colour changes due to the spherical 3D structure. The present characterization of quite mechanically robust and good reproducibility for the spherical pH sensor may have promise application in advanced optical devices.
Since ordered macroporous polymer hydrogels exhibit large reversible volume changes in response to external stimuli, such as pH, ions, temperature or electric field,21–23 which leading to a readable change in optical diffraction accompanied by a visually perceptible colour change, it would be the best material to fabricate pH sensor. Some studies also used polymer hydrogel and photonic crystal to fabricate various types of sensors24–26 and bionic structural colour materials27 due to the regulatory photonic band gap. Lee and Braun21 first synthesized thin (∼23 μm) inverse opal hydrogels film through colloidal crystal templating method, which make a breakthrough on the pH sensor. However, since the colour change on the film varied when observed from different angle, this angle dependence limits the application of pH sensor. Compared to films, the inverse opal hydrogel beads have advantages of identical structural colour and stop-band gaps derived from PCBs. In addition, the uniform macrospores through the inverse opal hydrogel provide higher specific surface area, faster ion diffusion and more interaction sites, resulting in more sensitive to external stimulus. Thus, there is still a challenge to achieve a high pH sensitive and fast response of inverse opal hydrogel which could be identified by angle-independent colour.
In this study, we report a simple microfluidic chip equipped with on line collecting device to fabricate photonic crystal beads. Integrated digital control of fluids, on line direct droplet solidification and collection, the chip show advantages of fast generation and controllable operation. Monodisperse droplet templates and PCBs can be produced efficiently and reproducible. Furthermore, by using SiO2 PCBs as templates, we synthesized inverse opal hydrogel pH sensors based on photo-polymerization of 2-hydroxyethyl methacrylate and acrylic acid (HEMA/AA). Several different compositions of AA and water in hydrogel precursors are chosen to examine the pH sensitivities, and the high sensitive inverse opal hydrogels exhibit tunable colour changes which almost covering the entire wavelength of visible light. In addition, materials with these inverse opal hydrogel pH sensors show optical diffraction shift along with volume variation that could be useful for drug-delivery or other potential optical devices.
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Fig. 1 The schematic diagram for fabricating photonic crystal beads and the inverse opal hydrogel beads. |
Subsequently, the hydrogel precursor was thoroughly polymerized through the PCBs using a portable UV-lamp (Yuezhong) at 365 nm for 2 h with 15 mm distance between lamp and the samples. After immerged in the DI-water for 30 min, the hybrid PCBs in the hydrogel film were split readily, it could be explained that the hydrogel outside the PCBs exhibited a certain degree of swelling, while the hydrogel in the interstices of the PCBs did not swell because of the restriction of the close-packed template. After etching SiO2 colloidal templates with 10% hydrofluoric acid (caution the danger of the HF) for 24 h, the hydrogel beads with inverse opal structure were obtained eventually. The hydrogel beads were soaked in DI-water for further use. Using a pH meter (PHS-3E, INESA), the phosphate buffer solutions were prepared by mixing KH2PO4 (0.1 M, Enox) with different volumes of HCl (0.1 M, Enox) and NaOH (0.1 M, Enox).
Similar with classic T-junction microfluidic chip,18 the cross channel of the chip is designed to generate droplets efficiently in this study. As calculated in Fig. 2d, the size distribution of the droplets gives a polydispersity (σ/d, σ is the standard deviation of the droplet diameter, d is the average diameter of 200 droplets) of less than 0.3%. The low polydispersity of the droplets should be attributed to the stable generation process. High-quality droplets can be fast generated for further application. Compared to capillary microfluidic device,29 this microfluidic device show more convenience and stability for the fabrication of SiO2 PCBs because that all the procedures are integrated into the microfluidic chip.
In this experiment, the droplets are generated, collected and dried directly on the chip. Generally, the generated droplets are transport to the oven for drying. However, during the transportation, the droplets are readily to break and converge into larger droplets. With our microfluidic chip device, this variations could be eliminated. As long as SiO2 particles are stable in liquid and their size distribution is sufficiently narrow, they could crystallize into a face centred cubic (FCC) lattice30 by increasing their volume fraction through concentration process like controlled evaporation. When the oil in the outlet being constantly heated, the water in the droplets start to evaporate, the silica nanoparticles gradually self-assemble into ordered lattices and appear iridescent colour. Eventually, the beads show a characteristic opaline colour in water (Fig. 3a) and in air (Fig. 3b), which is a clear evidence of the formation of photonic crystal. The consolidation time and the size of the PCBs depend on the drying temperature, the concentration of the silica nanoparticles in latex, and the diameter of the droplets.
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Fig. 3 Images of PCBs: (a) in water and (b) in air; SEM images of PCBs: (c) low-magnification image, (d) high-magnification images of the surface structure and (e) the inner structure. |
The silica nanoparticles of the PCBs mainly formed a close-packed FCC structure in the sphere. It can be observed that the PCBs have excellent spherical structures and smooth surfaces (Fig. 3c). The enlarged SEM image shows that the nanoparticles on the PCBs surface arrange in predominantly hexagonal symmetry (Fig. 3d) which extend to the inside of the whole beads (Fig. 3e). This structure imparts photonic band-gaps (PBGs) and characteristic reflection peaks to PCBs. Characteristic reflection peaks are a remarkable property of the photonic crystals. Under normal incidence, the peak value can be estimated by Bragg's law:31
λ = 1.633Dparticleneff | (1) |
Besides, there are some disorder occurred in the inverse opal hydrogel beads and the disordered parts could give the hydrogel beads a variegated colour from its original homogeneous structural colour (Fig. 4a and S1, ESI†). As shown in Fig. 4b, the defects in the inverse opal hydrogel that may derive from drying cracks and crystal defects of the colloidal template,26 are filled with hydrogel and tend to swell more drastically than the rest of the porous hydrogel network which may cause the hydrogel to increasing disorder during swelling. Besides, the higher swelling in the defect sites may create local stress points that may buckle the surrounding structures, resulting in a large scatter in the normalized full width at half maximum (FWHM) values and inhomogeneous structural colour in some hydrogel beads. Some defects may be contributed by template etching process and needle prick operated by a needle. Despite that the defects may affect the pH response measurement in a way, the main colour change is clearly readable for naked-eye detection.
According to the Bragg's law (eqn (1)), the diameter of the silica nanoparticle is about 240 nm in the PCBs templates (Fig. 5a), and the average refractive index (neff) of the PCBs close-packed structure is approximately 1.35 (neff2 = nsilica2η + nbuffer2(1 − η), where nsilica = 1.45, nbuffer = 0.98, η = 0.74), the calculated reflection peak is 527 nm, which is close to the detected peak position value of 541 nm. With regard to the inverse opal hydrogel beads, the neff is about 1.14 (neff2 = nbuffer2η + nhydrogel2(1 − η), nbuffer = 0.98, nhydrogel = 1.51), the peak position is mainly attributed to the size of holes (Dparticle). For instance, in the buffer solution of pH 6, the detected peak position of the 1% AA, 19.2% H2O hydrogel beads is 560 nm. The diameter of this hydrogel beads is about 450 μm (Fig. 5b) which is much higher than the diameter of the PCBs template (260 μm, Fig. 5a), hence, the void size is far above the SiO2 particle size. The consistency of the peak position between estimated values and the experimental measurements show that the products are qualified in optical properties. Furthermore, the hydrogel beads exhibit well-ordered macroporous structure not only can be proved by Fig. 4d, but also can be detected by the value of FWHM as narrow as 40 nm at the reflection spectra.
As the acrylic acid (AA) concentration increasing in hydrogel beads (Fig. 5b–d), they show higher swelling with diameter 450 μm, 525 μm, 560 μm and their detected peak position red shift, which are 560 nm, 616 nm and 668 nm respectively. Besides, as the water dosage increasing (Fig. 5c, e and f), the optical reflection peak should also red shift as expected because their crosslinking density decrease. However, the detected peak position of (c), (e) and (f) are 616 nm, 687 nm and 626 nm respectively. The abnormality peak position of (f) may be caused by adding too much water content in hydrogel precursor which made the concentration of the crosslinking agent (EGDM) too low to form a perfect hydrogel network. Compare to other samples, the disorder structures through the beads made this hydrogel bead exhibit poor swelling behaviour, little red shift, wide FWHM, poor iridescent colour and low reflection intensity. In addition, as shown in the reflection spectra in Fig. 5, the decreased of diffraction peak intensity from (a) to (f) could be explained by a number of causes such as continuously emerge of disorder and partial pore close during hydrogel expansion.
To further evaluate the effect of the AA concentration, water dosage and buffer pH on the equilibrium swelling of inverse opal hydrogel, four kinds of hydrogel beads are tested under the stimulation of buffer solution with different pH value. Since the same diameter sacrificial SiO2 particles are used for all cases, the crosslinking density of the hydrogel is the only reason for the apparent λmax difference at the same pH buffer (Fig. 6a). The degree of pH sensitivity varies with the different composition of hydrogel. As shown in Fig. 6a, the hydrogel beads become more sensitive as the AA concentration increasing. Similarly, with the same composition of AA (3%), the best sensitive could be depended on the water dosage of the hydrogel, which show larger λmax variation of high percentage H2O (31%) in the hydrogel beads than lower percentage of H2O (18%).
As the pH value of buffer increasing, the swelling degree (D/D0) of the hydrogel beads significantly increase due to the ionization equilibrium between the carboxyl group in acrylic acid and the ion in buffer solution which result in perceptible colour change and reversible swelling (Fig. 6b). As shown in Fig. 6c, a larger unit lattice size (distance between pores) within the inverse opal structure resulted in a more red-shifted λmax corresponding to the Bragg's law (eqn (1)). When hydrogel beads swell, the buffer solution fill pores, the hydrogel network keep stay on the ordered porous lattice. Diffraction response kinetics could be modelled as a hindered diffusion-limited process,33 where H+ and OH− ions, diffusing from the bulk solution into the gel phase as a result of a concentration gradient, are eliminated when they come into contract with immobilized deprotonated/protonated acid moieties on the network.
The 0.1 M potassium phosphate (KH2PO4) buffer mix with 0.1 M HCl and/or 0.1 M NaOH are used since the buffering pH range exactly covers the most sensitive pH range of HEMA/AA hydrogel system (around pH 5–6) as illustrated in Fig. 6a. Since most of AA units are deprotonated by a pH of 8, as pH increase over 7, λmax red shift slightly, the corresponding colour change is not recognizable because red colour is located at the long wavelength edge of the visible spectrum. By applying pH buffer below 5, λmax further blue-shift and the hydrogel exhibit explicit colour change. The beads have fast response less than 30 s when pH varies from 5 to 6 (Fig. S2, ESI†). The rapid pH response may be mainly attributed to two factors: the small volume of the hydrogel beads (micrometre size); the well-ordered porous structure in which the molecules or ions could diffuse rapidly. Overall, as shown in Fig. 6, among the hydrogel beads, the mixed ratio with 3% AA, 31% H2O of hydrogel precursors has the relative high pH sensitivity (D/D0) and wide pH response region (pH 1–9).
Furthermore, during pH increases, the perceptible structural colour changes could be detected by optical spectra instruments (Fig. 7), the colour of hydrogel beads with 3% AA, 18.8% H2O concentration varies from initial blue to green then yellow and orange, finally red. The brilliant colours cover almost the whole wavelength of visible lights, which is perfect for naked-eye detection in further development.
Now that the hydrogel sensor selectively responds to the pH variation, there may exist complex ion equilibria in the mixed buffer system which could affect Donnan equilibrium exerted by proton. When the pH value of buffer solution is low, the hydrogel chains curl up because the high concentration of H+ restrain the dissociation of the carboxyl group (–COOH) in the hydrogel. As pH increasing, –COOH begin to dissociate, the hydrogen bonds between chains are destroyed while the crosslinking points are decayed, which give rise to the increase of electrostatic repulsion, the bonds stretching, eventually lead to expanding of the hydrogel network. Besides, the derived –COO− also make the hydrogel expand by its hydrophilic property. The inverse opal hydrogel beads exhibit pH-dependent shifts in optical diffraction. The general shape of the peaks remains unchanged, suggesting that the overall layered microstructure of the template hydrogel could maintain during swelling. The hydrogel sensor demonstrate the good repeatability, fast responsive to pH value without visible degradation of iridescence or mechanical robustness even after it is completely dried or multiple pH tests (Fig. S3, ESI†).
A series of pH distinctive inverse opal hydrogel beads could be achieved by using different composition of hydrogel precursor. The optical diffraction shift may rely on the concentration of AA and water varied, which make difference in the swelling and deswelling of hydrogel, and the size of holes. When the concentration of AA and water is 3% and 31% respectively, the hydrogel shows best pH response and widest pH sensing range. These hydrogel pH sensors possess a series of desirable features including angle-independence, high sensitivity and quick response, which could be better applied in drug delivery, catalysis, and film separations in the future.
Footnote |
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c5ra25893f |
This journal is © The Royal Society of Chemistry 2016 |