Deming
Liu
abc,
Xiaoxue
Xu
*abc,
Fan
Wang
abc,
Jiajia
Zhou
cd,
Chao
Mi
bc,
Lixin
Zhang
a,
Yiqing
Lu
a,
Chenshuo
Ma
a,
Ewa
Goldys
a,
Jun
Lin
ce and
Dayong
Jin
*abc
aAdvanced Cytometry Labs, ARC Centre of Excellence for Nanoscale BioPhotonics, Macquarie University, Sydney, NSW 2109, Australia. E-mail: xiaoxue.xu@mq.edu.au; dayong.jin@uts.edu.au
bInstitute for Biomedical Materials and Devices, Faculty of Science, University of Technology Sydney, NSW 2007, Australia
cAustralian Research Council Research Hub for Integrated Device for End-user Analysis at Low-levels (IDEAL), Faculty of Science, University of Technology Sydney, NSW 2007, Australia
dCollege of Optical Science and Engineering, State Key Laboratory of Modern Optical Instrumentation, Zhejiang University, Hangzhou, 310027, P. R. China
eState Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, P. R. China
First published on 5th September 2016
Rare-earth doped upconversion nanocrystals have emerged as a novel class of luminescent probes for biomedical applications. The knowledge about their optical stability in aqueous solution under different pH and temperature conditions has not been comprehensively explored. Here we conduct a systematic investigation and report the emission stability and reversibility of typical NaYF4:Yb3+,Er3+ nanocrystals and their core–shell nanostructures in aqueous solution at different temperatures and with different pH values. These nanocrystals show reversible luminescence response to temperature changes, while low pH permanently quenches their luminescence. With the addition of inert shells, with thicknesses ranging from 1.5 nm to 8 nm, the emission stability and reversibility change significantly. Thicker inert shells not only lead to a significant enhancement in the emission intensity but also stabilize its optical responses which become less affected by temperature variations and pH conditions. This study suggests that upconversion nanocrystal-based sensitive temperature and pH sensors do not generally benefit from the core–shell structure usually recommended for enhanced upconversion luminescence.
Several groups reported that UCNPs can serve as accurate nanoscale sensors for intracellular monitoring of temperature24 or pH.25 They can also be applied as photoresponsive carriers for controlled delivery and release of drugs in vivo,26–31 where high temperature and/or lower pH conditions trigger drug release. The ratio-metric green emissions of Er3+ doped UCNPs are sensitive to cellular temperature with a resolution of 0.5 °C in the biological range of 25 °C to 45 °C.32 The red emission of the Er3+ UCNPs was found to be responsive to pH variations and to increase at low pH.32 Li and co-workers recently reported a hybrid design of carbon@ inert shell @UCNPs for real-time monitoring of the localized temperature increase during photodynamic therapy.33 We demonstrated a drug release sensing scheme by using the luminescence intensity of UCNPs. In this scheme we monitored the drug release process in the low pH environment (around pH = 5), as the drug on the surface of UCNPs was designed to quench the luminescence increase upon drug release.34
The understanding of luminescence responses to the varied temperature and pH environment35–37 require more detailed consideration of the stability and reversibility of UCNP luminescence under different pH and temperature conditions. The literature reports on the subject remain scattered. Wei et al. reported the stable emission of the UC nanocrystals with different surface ligands, but it was only tested at neutral pH in aqueous solutions.38 Li et al. reported the thermal stability of UCNPs and an anomalous relationship between temperature and the upconversion luminescence.39,40 Xu et al. reported that α-NaYb(Mn)F4:Er3+@NaYF4 UCNPs can be applied as luminescent nano-thermometers over a wide temperature range. But these tests were done only for the dry powder.
Coating inert shells onto the core UCNPs is a well-established and effective solution to minimize the surface quenching effect and therefore to enhance the upconversion luminescence by a factor of several to hundreds, depending on the core size and shell thickness.41–44 However, the role of the inert shells in influencing the stability and reversibility of luminescence at varied pH and temperature in aqueous solution has not yet been investigated.
In this work, we systematically investigated and compared the luminescence response of Er3+ doped UCNPs to different pH and temperature values in aqueous solution for both core-only and core–shell UCNPs. Using a modified hot-injection method, we prepared a systematic series of UCNPs by epitaxial growth of the homogeneous NaYF4:Yb3+,Er3+ UCNPs with different shell thicknesses from 1.5 to 8 nm. To characterize these nanoparticles in aqueous solution, we removed the surface organic ligand of oleic acids and transfer the hydrophilic UCNPs into the aqueous phase using an acid-based ligand removal method reported by Capobianco et al.45 We chose this approach to reduce the influence of surface ligands38 on UCNP upconversion luminescence. Our results show that the luminescence intensity of UCNPs decreases in either an acid or an alkali pH environment. In an acidic environment this luminescence decrease is not reversible. Conversely, higher temperature significantly reduces the luminescence intensity in a reversible way. The inert shell also reduces the sensitivity and resolution of the ratiometric response of green emissions (524 nm/545 nm) of Er3+ doped UCNPs for temperature sensing below 60 °C. This work compliments the current knowledge underpinning the rapid development of upconversion nanosensors for emerging biomedical applications and further suggests that new careful designs are necessary to accurately sense temperature and pH in specific applications.
Fig. 2(a) illustrates the major four emissions' energy transfer processes between energy levels of Yb3+ and Er3+ under 980 nm light excitation. The three-dimensional time resolved luminescence spectrum of UCNPs was obtained by high-throughput time-resolved luminescence spectroscopy that simultaneously provides the emission spectrum and the lifetime decay curve, as shown in Fig. 2(b). The luminescence enhancement and increased lifetimes due to coating of the UCNPs with the inert shells (as shown in Fig. S3 and S4, ESI†) was consistent with other reports in the literature.43,46,49–51Fig. 2(c) shows that the enhancement of emissions increased with increased thickness of the shells, while enhancement factors at varied emission positions were also different. The emission peaks at 408 nm, 540 nm, and 655 nm were only enhanced by about 3 times by coating a 1.5 nm inert NaYF4 shell, and the enhancement factors of 30, 12 and 15 were achieved for these peaks when a 8 nm shell was coated. Similar exceptional enhancement of violet emissions was also observed for the NaYF4:Yb3+,Tm3+@CaF2 core–shell nanocrystals.52 This suggested that higher order energy transfer processes benefited more from the inert shell protection. The luminescence lifetime data, shown in Fig. 2(d), further confirmed that the uniform shells were coated onto the core UCNPs. The luminescence lifetimes from the three emission bands (violet, green and red) increased with thicker shells. Both these strongly enhanced emission intensities and significantly longer lifetimes confirmed the successful growth of a series of homogeneous core–shell UCNPs.
Fig. 3 and Fig. S5 (ESI†) show the impact of the shell on the luminescence stability and reversibility against pH changes. The luminescence spectra of core-only and core–shell UCNPs were tested in aqueous solution under varying pH values. Fig. S5 (ESI†) shows that the acidic solution had a strong quenching effect on the UCNPs' luminescence and the inert shells were able to alleviate the quenching to some degree. Both the green and red emissions displayed similar emission quenching trends with the pH decrease (Fig. 3(a)). The green emission from the core UCNPs decreased to 28% of its initial intensity with the pH decreasing from 7 to 3, while the green emission from the core–shell UCNPs only decreased to about 65% of its original intensity. The alkaline conditions have been found to have less influence on the emissions. The emission from the core UCNPs was reduced only by 20% with the pH increasing from 7 to 12, while the emission from core–shell UCNPs only experienced a slight decrease under alkaline conditions. These data showed that the inert shells help in improving the luminescence stability against pH changes.
Fig. 3(b) shows the luminescence reversibility of luminescence of the core and core–shell UCNPs when repeatedly varying the pH conditions between pH = 4 and pH = 7. The quenching effect by the acidic aqueous solution was not reversible regardless of the presence of thick inert shells. Once the pH of the samples was decreased to pH = 4 for less than ten minutes, irreversible luminescence quenching occurred. Luminescence in these samples did not recover even by bringing the pH back to 7. The irreversible luminescence quenching of the UNCPs in the acidic environment suggested that the crystal surface may experience chemical damage under low pH conditions. To prove this, we carefully compared the TEM images of ligand free UCNPs before (Fig. 3(c)) and after (Fig. 3(d)) treatment with the pH = 3 acid solution for 1 hour. Interestingly, we observed an obvious decrease in size from 24 nm to 21 nm and a rough surface morphology, showing that the nanocrystals were chemically etched. This chemical damage from weak acid was also found in other rare earth fluoride nanocrystals, such as NaEuF453 and Lu6O5F8.54 We attributed this to the dissociation of Ln–F bonds of the NaYF4 nanocrystals in the solution with low pH (≤3).
We further measured the spectra of NaYF4:Yb3+,Er3+ core-only and core–shell UCNPs in Milli-Q water at various temperatures from 10 °C to 80 °C (shown in Fig. 4 and Fig. S6, ESI†). Fig. S6a and b (ESI†) shows the luminescence intensities of both core-only and core–shell nanocrystals decreased at a higher temperature with the core UCNPs being more strongly affected. The green emission of the core-only UCNPs decreased quickly to 78% of its original intensity even when the temperature was increased only from 10 °C to 30 °C. With a further temperature increase from 30 °C to 80 °C, the green emission decreased to nearly half of its original intensity at 10 °C. The shell protection again was found to alleviate the temperature-induced quenching, with the green emission from the core–shell UCNPs decreasing by only 27% at 80 °C. The quenching of the red emission was similar to the green emission, when it occurred at lower temperatures from 10 °C to 40 °C. However, the red emission has slightly higher stability than the green emission in the higher temperature range from 40 °C to 80 °C. We think that the reason for red emission receiving a lower quenching effect than the green emission at the higher temperature range is due to an increase of population transition from 4S3/2 to 4F9/2. According to Xiaogang Liu group's investigation55 on the relationship between relative emission intensity and nanocrystal surface defects that the higher energy level excited state would receive multiphonon nonradioactive relaxation from surface quenchers. The relative low energy level of 4F9/2 would receive some population from the higher energy levels (e.g.4S3/2), and therefore the red emission presents relatively higher stability than the green emission at a higher temperature.
Fig. 4(b) demonstrates the reversibility of the luminescence emission against temperature, and it shows that the emission intensities of both the core-only and core–shell nanocrystals followed the temperature change between 10 °C and 40 °C, and these changes were fully reversible. The degree of intensity variations for the core–shell nanocrystals was lower than that of the core nanocrystals. These results suggested that the core–shell structure of NaYF4:Yb3+,Er3+/NaYF4 has a less pronounced response to temperature variations, especially in the range from 10 °C to 40 °C, relevant for in vivo biomedical applications. The observed improvement in emission stability by coating the passivation shell suggested that the inert shell can effectively reduce the quenching effect from the vibrational energies and optical traps arising from the particle surface. The water molecule is known as a surface oscillator that significantly quenches the luminescence of lanthanide dopant ions, because of the high energy (ca. 3500 cm−1) of the stretching vibration. As the temperature increases, the water molecular on the crystal surface could be more intensely vibrating, which may affect the Ln–F bond on the crystal surface and create more phonons. By coating the inert shell structure, forming a gap between the emitters and the quenchers can effectively reduce the quenching effect caused by a temperature increase.
The ratiometric emissions (I524/I540) from the NaYF4:Yb3+,Er3+ UCNPs have been broadly used in nanoscale thermometry56 because the population distributions on 2H11/2 and 4S3/2 are dominated by Boltzmann's thermal distribution and elevated temperature leads to rapid population of the 2H11/2 state.57Fig. 5 shows the intensity ratios of 524 nm to 540 nm (I524/I540) and 540 nm to 655 nm (I540/I655) emissions for the core-only and core–shell nanocrystals. The ratio of I524/I540 in Fig. 5(a) for the core nanocrystals shows a linear increase with temperature in the range from 10 °C to 80 °C, which is consistent with previously reported results.57,58 The ratio of I524/I540 of core–shell nanocrystals is slightly higher than that of core-only nanocrystals at 10 °C, which suggests that the inert shell effectively saved some population on 2H11/2 from nonradioactive relaxation. As the temperature was increased from 10 °C to 60 °C, the ratio of I524/I540 of core–shell nanocrystals slightly increases; however, the ratio increases quickly when the temperature was increased from 60 °C to 75 °C. This anomalous temperature-dependent phenomenon was also found and reported by other groups for small sized upconversion nanocrystals.59 The population distribution changes on 2H11/2 and 4S3/2 could be caused by surface defects and surface molecular quenchers (e.g. water molecular vibration) and temperature. Higher temperature helps to increase the population distribution on 2H11/2. On the other hand, stronger surface quenchers would decrease the population on 2H11/2 compared to that on 4S3/2 because the higher level excited state of 2H11/2 could receive more quenching effects.55 At elevated temperatures, not only the thermal factor of nanocrystals would become larger but also the surface quenching effect would be stronger. The slow increase rate of I524/I540 of core–shell nanocrystals in the low temperature range is due to the competition of the two different effects. Due to the inert shell which effectively blocks the quenching effect at high temperatures, the fast increasing rate of I524/I540 can attribute to the sole thermal factor. These data suggested that the core–shell UCNPs may not be sensitive for temperature measurements in the temperature range from 10 °C to 60 °C.
Fig. 5 Emission intensity ratio (a) of 524 nm/540 nm from core and core–shell UCNPs and (b) emission intensity ratio of 540 nm/655 nm from core and core–shell UCNPs as a function of temperature. |
Fig. 5(b) further shows that the ratios of I540/I655 emissions for the core and core–shell nanocrystals linearly decreased with temperature between 10 °C to 80 °C, which was consistent with the results reported by other authors.57 Higher temperature increases the comparative influence of the non-radiative relaxation channels, from 4I11/2 to 4I13/2 and from 4S3/2, 2H11/2 to 4F9/2, leading to an increase of the ratio of I540/I655 emission.
Footnote |
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c6tc02990f |
This journal is © The Royal Society of Chemistry 2016 |