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Biological and Medical Applications of Materials and Interfaces

Adjusting the linear range of Au-MOF fluorescent probes for real-time analyzing intracellular GSH in living cells Tianyu Du, Hang Zhang, Jun Ruan, Hui Jiang, Hong-Yuan Chen, and Xuemei Wang ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b19356 • Publication Date (Web): 29 Mar 2018 Downloaded from http://pubs.acs.org on March 29, 2018

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ACS Applied Materials & Interfaces

Adjusting the linear range of Au-MOF fluorescent probes for real-time analyzing intracellular GSH in living cells Tianyu Du1, Hang Zhang1, Jun Ruan1, Hui Jiang1, Hong-Yuan Chen2, Xuemei Wang1,* 1 State Key Laboratory of Bioelectronics (Chien-Shiung Wu Lab), School of Biological Science and Medical Engineering, Southeast University, Nanjing 210096, China 2 State Key Laboratory of Analytical Chemistry for Life Science, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China *E-mail: [email protected]

Abstract A series of Au loaded MOFs were synthesized in this study and further employed for real-time quantitative analysis of intracellular GSH level. Different linear range can be acquired by altering the size of gold and MOF particles, or adjusting the proportion of 2-aminoterephthalic acid / 1,4-benzenedicarboxylate linkers, which is also observed on fluorescein isothiocyanate attached Au-MOFs. Further study reveals that the flexible molecular chain of GSH with the -COOH / -NH2 and -SH terminal may readily tie on relevant gold nanoparticles (Au NPs) through its -NH2 / -COOH groups, which then restricts the intra-molecular motions of fluorescence probes and thus induces marked fluorescence enhancement. Based on these observations, the intracellular GSH level of different cells including L02 cells, Hela and U87 as well as HepG2 cancer cells can be rapidly evaluated by these Au-MOF probes. Keywords: metal-organic frameworks, gold nanoparticles, glutathione, cell imaging, restriction of intramolecular rotation

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1. Introduction Thiols (e.g. cysteine, glutathione) play essential roles in biological systems.1 There levels involve in a numbers of diseases such as diabetes, AIDS, cancer and Alzheimer’s diseases.2-4 Since glutathione (GSH) is the most abundant thiol among them, its detection in psychological fluids or cells attracts a lot of attentions. A fatal defect of traditional approaches, such as electrochemical detection, mass spectroscopic and high performance liquid chromatography (HPLC), is their inability to reflect the intracellular information. On the contrary, fluorescent detection overcomes this shortcoming and received more and more attentions.5-8 A large number of fluorescent probes, organic and inorganic, have been designed and applied for a series of specifically conditions.9-14 Despite the advantages reported in these works, to meet the requirements of real time monitoring, there are still some serious problems to be urgently resolved. First is the selectivity, most chemodosimeters rely on their interaction with -SH, essentially, they do not have the recognition to specifically thiol specie. Secondly, the detection range is also a thorny problem, as we know, the GSH concentration of cancerous cells always range from 1 to 10 mM15,16 for which most fluorescent probes cannot match. Although many probes show excellent sensitivity and low detection limit, a consequent problem is the aggregation caused quenching (ACQ).17 With the developing of metal-organic frameworks (MOFs), some efforts have turned interests from catalysis to chemical sensor and biomedical imaging.18,19 Meanwhile, the nature of its fluorescence property was gradually revealed with its booming 2


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application.20,21 In this work, gold nanoparticles-attached MOFs were designed as potential fluorescent probes for GSH. We found that the GSH can act as a string to tie the gold particles and -NH2 groups on MOFs, by its -SH terminal and -COOH terminal, which induces significant fluorescence enhancement via RIR (restriction of intramolecular rotation) mechanism. The linear response of GSH can be adjusted in a wide range (0 - 10 mM) by simply changing the combination of gold and MOF specie. What’s more, the Au-MOF probes also behave good selectivity toward GSH. After a detailed exploration we further applied the Au-MOF for real-time monitoring of intracellular GSH level.

2. Results and discussion 2.1 Morphological Properties, detection linear range and selectivity Initially, NH2-MIL-53(Al) (denoted as N53), larger size NH2-MIL-53(Al) (denoted as N53(DMF)), smaller size NH2-MIL-53(Al) (prepared in the solution of 25% H2O and 75% DMF, denoted as N53(25%W)), MIL-53(Al) without amino group (denoted as MIL-53), NH2-MIL-53(Al) with mixed linkers (20% NH2-BDC and 80% BDC linkers, denoted as N53(20%)) and NH2-UiO-66 (denoted as N66) were prepared in this study, and their morphologies, structures and fluorescence were further characterized, as shown in Figure 1 A-F and Figures S1-S6. The fluorescent emission peak of MIL-53 is at ca. 328 nm (excited under 308 nm) while others' are all located at 440 nm (excited at about 345 nm). Fluorescein isothiocyanate (FITC) can conjugate to -NH2 via isothiocyano,22,23 then generate the second emission peak at about 517 nm 3



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(Figures S7 and S8), the FITC labeled N53 and N66 were denoted as F53 and F66 in further work. Three types of gold nanoparticles (prepared by using trisodium citrate, polyvinyl pyrrolidone, sodium borohydride and named as C-Au, P-Au, S-Au respectively, see in supporting information) were loaded onto these MOFs, and the particle size of them were characterized by TEM (Figures 1G-I) and illustrated in histograms (Figures 1J-L). The loading amount of Au NPs for each sample was estimated by UV-Vis absorption spectra (Figures S9-S16 in supporting information) and the results are listed in Table S1. In this work, we selected the MOFs with about 3.5 wt % loading of gold nanoparticles for further studies (if no extra illustration). By investigating their FTIR and UV-vis DRS (Figures S17-S24 in supporting information) we can find that the gold nanoparticles still maintain good dispersity and their loading does not impact the structure of MOFs.

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Figure 1. SEM or TEM images of (A) N53, (B) N53(DMF), (C) N53(25%W), (D) MIL-53, (E) N53(20%) and (F) N66. TEM images of (G) N66C, (H) N66P, (I) N66S and the corresponding particle size distribution of Au nanoparticles (J-L). Scale bars: 200 nm (A), 2 µm (B), 50 nm (C), 2 µm (D), 500 nm (E), 50 nm (F) and 20 nm (G-I). Table 1. Fluorescent response of Au-MOFs for GSH C-Au P-Au MOF or Linear range Coefficie Linear Coefficien Au species (mM) nt range t -1 (mM ) (mM) (mM-1) (I) 0 - 1 2.93 N53 1-9 0.77 (II) 1 - 5 0.62 N53(DMF) 0-1 0.93 0-1 0.64 (I) 0 - 1 0.63 N53(25% 0-1 0.15 W) (II) 1 - 9 0.13 N53(20%) 1-9 0.11 1-9 0.14 N66 1-9 0.71 0-9 0.85 F53 0-3 0.58 0-9 0.27 F66 0-3 0.59 0-9 0.39

Linear range (mM)

S-Au Coefficient (mM-1)

0-1

3.40

0-1 (I) 0 - 3 (II) 3 - 9 3-7 1-9 0-9 0-9

1.34 0.34 0.092 0.062 0.38 0.69 0.36

Table 1 and Figures S25-S32 (supporting information) show the fluorescent responses of Au-MOF for detecting GSH (in 7 mM PBS with pH of 7). The detection limit of 5



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-NH2 contained MOFs are all below 100 nM and the fluorescence generally increases with the concentration of GSH. It is found that different linear range of detection for GSH can be acquired by simply changing the MOF particles and the loaded gold species. FTIC-conjugated MOFs (F53C/P/S and F66C/P/S) exhibit similarly fluorescent response for GSH but inferior to N53C/P/S and N66C/P/S. In Table 1 we note N53P, N66P, F53S and F66S samples show good linear response of fluorescence for GSH, which implies these Au-MOFs can be explored as the probes to evaluate the GSH level in living cells. Figure 2 shows the selectivity of N53P, N66P, F53S and F66S towards some common amino acid (9 mM, pH = 7, in 7 mM PBS). It can be seen that only GSH and Cys can trigger the fluorescent response obviously. Comparing to conventional probes,3 Cys affect little on Au-MOF probes (less than 1/3 compared to GSH). While considering the GSH concentrations in cancerous cells (1 to 10 mM) and normal cells (less than 200 µM),3,15 the error caused by Cys can be effectively suppressed in living cell detection (Figure S33).

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Figure 2. Fluorescence response of (A) N53P, (B) N66P, (C) F53S and (D) F66S toward various amino acids. From left to right, L-Arginine, L-Glutamate, L-Histidine, L-Phenylalanin, GSH(control), L-Cysteine, L-Tyrosine and glutathione. GSH(control) means the fluorescent response of N53, N66, F53 and F66 for 9 mM GSH. 2.2 Possible mechanism of the Au-MOF probes To our knowledge, the organic linkers in most MOFs contain π electrons structure (e.g. aromatic rings) are luminescent under UV excitation.24,25 The fluorescent enhancement effect of MOF systems on these organic chromophores can be classified as follows. Firstly, by altering the space distance between ligands by introducing the metal ions center, constructing the ligand to metal charge transfer (LMCT) or metal to ligand charge transfer (MLCT),26-29 these processes are always accompanied with the obvious shift of excitation / emission peaks.30 Secondly, the formation of MOF restricting the intramolecular rotation by anchoring rotor chromophores within a rigid matrix (RIR mechanism),29-31 that suppresses the radiationless decay.32 Finally, for rotation-forbidden systems, the existence of MOF structure will restrict the energy decay from low-frequency motion (twisting or torsion) to some extent.33 In this work, the carboxyl of BDC and NH2-BDC are in the para positions, thus the phenyl rings can rotate freely, though restricted by MOF matrix, and the existence of apertures still allow the phenyl rings to rotate to a great degree.30 So it is not surprising that their fluorescence has considerable room for improvement (for instance, if we restrict the intermolecular motion by reducing the temperature from 293 K to 159 K, a 6 folds enhancement of fluorescence will induce for N66, Figure S34A. This also works for F66 sample, with an enhancement of 4 folds (Figure S34C).

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In general, gold nanoparticles on the MOFs have particularly high affinity for Cys and GSH via bonding the thiol groups,34-36 by checking the fluorescence response of N53, MIL-53C/P/S, N53(20%)C/P/S and N53C/P/S (Figures 2, S28, S29 and S25) it is found that the gold particles and -NH2 group play critical roles for GSH/Cys detection. This result inspires us to propose such a pathway, that is, the carboxyl groups of gold-adsorbed GSH/Cys interact with the -NH2 groups on NH2-BDC ligands to form the COO-···NH3+ units, then restrict the intramolecular rotation of phenyl rings and induce the fluorescence enhancement (as illustrated in Figure 3A).37 XPS analysis was conducted and the N1s spectra are shown in Figure 3A. The deconvolved peaks from low to high field are assigned to -NH2 groups on NH2-BDC (399.4 eV), GSH/Cys (400.1 eV) and protonated amine (NH3+, 401.6 eV), respectively, for F66 sample, the peak at 401.6 eV is also contributed by C-N bond between FITC and -NH2 groups.38,39 By comparing the fraction of protonated NH3+ in GSH adsorbed MIL-53P (3.6%), Cys adsorbed N53P (15.7%), GSH adsorbed N53P (27.2%) and GSH adsorbed F53P (22.6%) we find the fluorescent response associate with the COO-···NH3+ closely. The presence of acid amides is also indicated by IR spectra, as shown in Figure S35.40 The lower bonding proportion of Cys adsorbed sample could be attributed to the shorter carbon chain, which limits the attachment of COO- to NH3+ and leads to inferior fluorescent response. For F53S and F66S samples, we notice the -NH2 groups that should have to interact with the COO- of GSH are consumed by isothiocyano in FTIC. However, while using ninhydrin hydrate to check the primary amine of adsorbed GSH/Cys upon F53S/F66S, it is found that the amount of residual primary 8


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amine is much lower than that upon N53P and N66P (Figure S36 in supporting information). This result suggests that GSH/Cys has provided NH3+ to interact with the COO- on FITC and then form the COO-···NH3+ unit. Actually, we have also checked the fluorescence response of λ = 440 nm, the characteristic emission band of 2-aminoterephthalic acid MOFs, is much weaker (as shown in Fig. S37 in supporting information) than pure N66 MOF, which is due to the reaction between FITC and amino groups competes with that of GSH then weaken the interaction, this result also confirms the propose of RIR mechanism. In addition, although the rigid units account for a small fraction, their excellent dispersion on the surface of MOFs greatly enhances the fluorescence efficiency, and even leads to a higher global effect.

Figure 3. (A) From left up to right bottom, illustrations of the fluorescent response of MIL-53P, N53P, F53S, GSH functionalized MIL-53P, GSH functionalized N53P, Cys functionalized MIL-53P and GSH functionalized F53S (the red spheres present Au particles, cyan tetrahedrons present Al atoms), and their corresponding N1s XPS spectra are shown beside. (B) A scheme to reveal the effect of particle size on detection linear range. Under a higher concentration of GSH, larger particles reach adsorption saturation due to their lower surface exposure ratio, the smaller particles tend to aggregate then quench the fluorescence.

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Another concern is the linear range of fluorescence response for different materials. Firstly we discuss the sensitivity of gold nanoparticles for GSH and Cys. Thiol groups tend to deposit on (110) facet of gold particles, however, XRD result indicates the similar fraction of it in each sample (Figure S38), and thus, the large specific surface area should be considered as the dominated effect to expose more facets and increase the adsorption quantity.41,42 In Figures S39-S42 we find that decreasing the particle size results in higher capacity of -SH and better linear response, which also reveal why C-Au loaded samples show inferior linearity. On the other hand, the MOF specie is also a crucial factor, either larger or smaller particle size (N53(DMF), 5 µm or N53(25%W), 50 nm) leads to poor effect. The reason for N53(DMF) sample is its low surface exposure ratio limits the sufficient contact between COO- and NH3+ under higher concentration, while the fluorescence decay for N53(25%W) sample most probably results from the aggregation-caused quenching (ACQ) associates with the adsorbed GSH self-assemble into networks (this issue is discussed and further confirmed by Figures S43-S48 in supporting information). On this basis we can conclude that the fluorescent response of Au-MOFs is the result of RIR versus ACQ (as illustrated in Figure 3B). In addition, the FITC-labeled MOFs seem to suffer more from ACQ effect that easier to lose the linearity under high concentration of GSH (Figures S31 and S32 in supporting information). This result is also in consistent with the fact that the FITC-labeled MOFs need an insensitive gold particle (e.g. S-Au) to attemper its higher sensitivity for concentration.

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Figure 4. (A) Fluorescence confocal images of single F66S particle in 0, 1, 3, 5, 7 and 9 mM GSH PBS solution. Fluorescence confocal images of F66S cultured (B) L02, (C) Hela, (D) U87, (E) HepG2 cells, (F) HepG2 cells cultured with 0.1 mM HAuCl4 for 5 hours and (G) cultured with F66S for another 0.5 hour in PBS. The excited wavelength is 488 nm and the laser power and sensitivity of panel (F) is higher than others to get a good contrast. (H) The linear relationship between fluorescence intensity and GSH concentration in panel (A). (I) and (J), the GSH concentration level of cells derived from fluorescence confocal images. 2.3 In vitro sensing for different cells Undergoing a primary screening (i.e., fluorescent response, particle size, dispersity and biocompatibility, as illustrated in Figures S49-S51 in supporting information), F66S sample was employed as the probe to evaluate the GSH concentration in living cells. The linear relationship between fluorescence and the concentration of GSH is 11



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investigated and the result is shown in Figure 4A and 4H. Thereafter we calculated the GSH concentration of L02, Hela, U87 and HepG2 cells by combining the fluorescence intensity (Figures 4B-4E) and the formula in Figure 4H and the results for these cells are 1.55 mM, 8.1 mM, 5.8 mM and 9.1 mM, respectively (Figures 4I-4J). Our previous work indicated that culturing the cancerous cells with AuCl4ions can induce self-imaging by forming the fluorescent gold nanoclusters (Figure 4F).43,44 We wonder the intracellular GSH plays a significant role in this process, for this sake we have also checked the GSH concentration of HepG2 cells after culturing with 400 µM AuCl4- for 5 hours. It can be found that the GSH concentration decreases to 3.9 mM at last (Figure 4J), which confirms the formation of such a fluorescent gold nanoclusters indeed costs GSH. 3. Conclusion In conclusion, gold attached MOFs were prepared as a florescence probe for real-time monitoring of intracellular GSH. By changing the combination of gold and MOF species, the linear range can be fine adjusted to meet various standards for different cells. In contrast with the conventional probes, the Au-MOF overcomes the shortcoming of narrow detection limit, which can be further used to distinguish normal or cancerous cell and estimate the change of GSH concentration. To illustrate such a fluorescence response, a hypothesis based on RIR mechanism was proposed and confirmed. Furthermore, it is evident that in this process, the string-like effect of GSH and resistance of ACQ also played significant roles.

4. Experimental Section 12


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The synthesis of MOFs, Au nanoparticles, Au-MOFs and detection details are shown in section 2 of supporting information.

Acknowledgements This work was supported by National High Technology Research & Development Program of China (2017YFA0205300), National Natural Science Foundation of China (91753106, 21327902, 81325011 and 21675023) and Fundamental Research Funds for the Central Universities.

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