Smart All-in-one Thermometer-heater Nanoprobe Based on Post

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Smart All-in-one Thermometer-heater Nanoprobe Based on Postsynthetical Functionalization of a Eu(#)-metal-organic Framework Hui-Cheng Yan, Hongyuhang Ni, Jian-Guo Jia, Changfu Shan, Tong Zhang, Yu-Xin Gong, Xiangkai Li, Jing Cao, Wenyu Wu, Weisheng Liu, and Yu Tang Anal. Chem., Just Accepted Manuscript • Publication Date (Web): 25 Mar 2019 Downloaded from http://pubs.acs.org on March 25, 2019

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Analytical Chemistry

Smart All-in-one Thermometer-heater Nanoprobe Based on Post-synthetical Functionalization of a Eu(Ⅲ)-metal-organic Framework Huicheng Yan,† Hongyuhang Ni,‡ Jianguo Jia,† Changfu Shan,† Tong Zhang,† Yuxin Gong,‡ Xiangkai Li,‡ Jing Cao,*† Wenyu Wu,† Weisheng Liu,† and Yu Tang*† † State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, P. R. China ‡ Ministry of Education Key Laboratory of Cell Activities and Stress Adaptations, School of Life Sciences, Lanzhou University, Lanzhou 730000, P. R. China Email: [email protected], [email protected]. Fax: 86-931-8912582.

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Abstract: Real-time temperature feedback in tissue based on photothermal therapy is an urgent problem to be solved in the cancer treatment. Herein, a smart all-in-one nanoprobe

THA@Eu-NMOF@Fe/TA

was

designed

and

assembled

by

post-synthetical functionalization of an Eu(Ⅲ)-based nanoscale metal-organic framework

(Eu-NMOF)

with

a

two-photon-absorbing

β-diketonate

ligand

4,4,4-trifluoro-1-(9-hexylcarbazol-3-yl)-1,3-butanedione (HTHA) and Fe(Ⅲ)/tannic acid assembly (Fe/TA). Such a functionalized material can simultaneously achieve the temperature-sensing and optical heating under a single beam of near-infrared (NIR) light. Under 808 nm laser excitation, real-time feedback of temperature by monitoring thermo-responsive fluorescence emission ratio (I616/I590) and fluorescence lifetime of Eu(Ⅲ) ions were realized. Meantime, Fe/TA served as the photothermal agent and antibacterial agent to implement photothermal therapy (PTT) and antibacteria simultaneously. The functions of the nanoprobe were proved with ex vivo experiments, and the antibacterial activity against gram-positive and gram-negative bacteria of the probe was also elaborately evaluated. Our work paves a new avenue for engineering new cancer treatment probe which can achieve real-time temperature sensing feedback during PTT and antibacterial process.

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INTRODUCTION Conventional strategies including surgery, radiation therapy, and chemotherapy have been widely used in cancer clinic therapy which may result in tumor metastases and severe toxic side effects to the patients. Cancer therapy based on nanoparticles1-3 (NPs) has attracted many researchers’ interests due to the high payload incorporation and multimodal loading capability.4 As a new treatment for cancer cells and bacterial infection, photothermal therapy (PTT)1,5 can cause thermal ablation of tumor cells and the death of bacterial with photo-absorbing agents to generate heat from light activation. It has been recognized as a safe method to reduce the normal tissue damage and system side effects. Also it is found that inflammation increases the potential of cancer cell recurrence and metastasis, and adding bacteriostatic materials during PTT to effectively inhibit cancer cell recurrence and metastasis.6 Iron(Ⅲ)/tannic acid assemblies (Fe/TA) is a newly discovered photothermal reagent with excellently photothermal conversion capability to efficiently ablate tumor cells.7-8 And tannic acid was reported to have the ability to inactivate proteins.9-10 Therefore, Fe/TA can synergistically enhance the antibacterial effect by utilizing the bacteriostatic effect and photothermal inactivation effects. The therapeutic effect of PTT depends largely on the amount of heat produced by photothermal conversion agent. Insufficient heating or intracellular hyperthermia can result in ineffective treatment of cancer cells or collateral damages to surrounding tissue during the PTT. Thus, the precise sensing of temperature is an important factor to promote the efficacy of PTT. However, the current method to monitor the 3



temperature during PTT is to use a thermographic imaging method which is generally reflected by the temperature of the surface of the objects, different from the temperature of the injection site, thus resulting in poor therapeutic effects.11 Consequently, developing a new method of real-time monitor intracellular temperature during the process of PTT deserves much research. Nanothermometer based on fluorescence intensity ratio or fluorescence lifetime is a new detection method to feedback temperature.12-13 This method could accurately feedback temperature under sub-tissue to achieve accurately cancer treatment during the process of PTT. Li’s group had proved this possibility by using a carbon-coated core-shell up-conversion nanocomposite with a fluorescent temperature sensitive core and a photothermal carbon shell.14 In recent reports, the realization of temperature sensing and photothermal treatment under a single beam of light had been reported,15 which was mainly achieved by using up-conversion NPs. Metal-organic frameworks (MOFs) is assembled with metal ions/metal clusters and organic bridging ligands.16 The unlimited selection of metal ions and ligands allows the crystal structures and fluorescent properties of MOFs to be controlled and tuned relatively easily. In addition, post-synthetic modification of the MOFs including derivatization of the linkers or introduction of metals by way of complexation or ion swap allows further modulation of luminescence.17 Because of the inherent narrow-band luminescence, long lifetime and large Stokes shift, lanthanide metal-organic frameworks (Ln-MOFs) possessing advantages of MOFs and lanthanide ions have aroused widespread research interests.18 Thus, contact 4


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thermometers based on Ln-MOFs can provide a bright future for the development of various types of temperature sensors. In the past few years, the use of Ln-MOFs to achieve temperature sensing has already been adopted for developing molecular thermometer.19-20 However, so far, most of the Ln-MOFs based thermometers reported previously were excited by ultraviolet or visible light (λex < 500 nm). Self-fluorescence and tissue damage caused by excitation light limits its application in biological neighborhoods.21 In general, in the biological windows of 800-1800 nm, light absorption and scattered by tissues is minimal and generally gets a high penetration depth exceeding 1 cm,22 further reducing

non-selectivity and

light-induced damage to the normal tissue. Two-photon-absorption MOFs (TPA-MOFs) is a potential method that allows deep tissue to penetrate (light in the 700-1000 nm range) by simultaneously stimulating two low-energy near-infrared (NIR) photons.23-24 Moreover, up to now, no data has been reported that TPA-MOFs based thermometers can achieve both temperature sensing and photothermal therapy under NIR excitation using single beam of light. Therefore, it is urgent to design an intelligent Ln-MOFs based all-in-one thermometer−heater platforms capable of remote thermometry and efficient heating under single-beam NIR light excitation. In

our

work,

a

smart

all-in-one

thermometer−heater

nanoprobe

(THA@Eu-NMOF@Fe/TA) was designed and synthesized, which can achieve precisely temperature sensing and antibacterial effect during PTT under single-beam 808 nm NIR light excitation (Scheme 1). A versatile methodology for introducing functionality into Eu-NMOF (designated as THA@Eu-NMOF) assembled by Eu3+ 5



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with trimesic acid,25 known as post-synthetic modification, was achieved on Eu-NMOF

with

the

TPA

(4,4,4-trifluoro-1-(9-hexylcarbazol-3-yl)-1,3-butanedione)

ligand by

HTHA coordination

interaction. HTHA was introduced to sensitize Eu3+, which can absorb 808 nm NIR light excitation to reduce light-induced damage to tissues and increase the depth of light penetrating tissue. Particularly, the long emission lifetime and ultra-sensitive transition of the Eu3+ endowed THA@Eu-NMOF probe the ability for sensing temperature. Photothermal agent Fe/TA7-8 could be subsequently deposited on the surface of THA@Eu-NMOF by adjusting the pH of the solution, which can generate photothermal effect by 808 nm laser irradiation. Tannic acid (TA) is a resin polyphenol consisting of central glucose linked to five diacetyl ester groups. It can be used as a multidentate ligand to rapidly coordinate with metal ions into a three-dimensional network within minutes,25 and also had the ability to precipitate proteins affecting the life activities of bacteria.9-10 Because of the inherent antibacterial activity of TA and the photothermal conversion capability of Fe/TA, it gave the nanoprobe THA@Eu-NMOF@Fe/TA the ability for photothermal ablation of cancer cells and photothermal synergy enhanced bacteriostatic effect. Therefore, the all-in-one THA@Eu-NMOF@Fe/TA nanoprobe can be achieved, possessing temperature sensing and photothermal therapy under single-beam NIR light excitation, which also can synergy enhance bacteriostatic effect. This work offers a new strategy for engineering all-in-one multifunctional nanoprobes in biological and other applications. 6


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Scheme 1. Schematic representation of the synthetic procedure, HTHA coordination, Fe/TA loading and the application of THA@Eu-NMOF@Fe/TA nanoprobe.

EXPERIMENTAL Synthesis of Nanoscale [Eu(BTC)(H2O)·DMF] (Eu-NMOF). Eu(NO3)3·6H2O (0.008 g), H3BTC (0.007 g), and DMF (80 mL) was mixed in a beaker. Then the mixture was heated to 150 °C (5 min) in a microwave. The solution was cooled to room temperature, centrifuged to obtain the product, and then rinsed several times using DMF and ethanol to get rid of extra reactants. Elemental analyses showed the text upshot (C, 31.49; H, 2.79; N, 3.08; Eu, 32.90), which are same with the previously report numerical value (C, 31.28; H, 2.63; N, 3.04; Eu, 33.76). Synthesis of THA@Eu-NMOF. An ethanol solution of HTHA (4.2 mg) in ethanol 7



(15 mL) was adjusted to pH 7 (NaOH solution) with stirring. Then the ethanol solution of Eu-NMOF (10 mg) was dropped into the above mixture solution. After stirring at 80 °C for 24 hours, the white product was obtained by centrifugation, followed by washing with ethanol several times to remove extra HTHA. The product is then dried at room temperature. Synthesis of THA@Eu-NMOF@Fe/TA. 10 mg of THA@Eu-NMOF was dispersed in 5 mL of ethanol, and then 40 μL of tannic acid (40 mg/mL) solution was added to the solution. The pH of the solution was adjusted to 7.0 with 0.1 mol/L NaOH solution under vortex. Then 300 μL of FeCl3 (10 mg/mL) was added to the solution. After reacting for 30 minutes, the outcome was collected by centrifugation and cleaned with ethanol repeatedly and dried at room temperature. In Vitro Antibacterial Activity of THA@Eu-NMOF@Fe/TA. Enterococcus faecalis (ATCC 29212), and Escherichia coli (ATCC 8739) were cultured in lysogeny broth (LB) medium to the log phase (6-12 h). Both bacteria were collected by centrifugation at 6000 × g, resuspended in sterilized water after centrifuging and resuspending for 3 more times and diluted to ∼107 CFU/mL by using sterilized water. Five milliliters of bacterium solution were stored at room temperature as the control group. Then, the antibacterial activities of the THA@Eu-NMOF@Fe/TA against Escherichia coli (E. coli) and Enterococcus faecalis (E. faecalis) were tested. With respect to E. coli, the solution of THA@Eu-NMOF@Fe/TA was diluted with five milliliters of bacterium solution to different concentrations (10, 50, 100, 200, 300, 400, 500 μg/ml) and cultivate for 15 minutes as different experimental groups. 8


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Bacterial contents in both groups were measured by Colony-Forming Units (CFU) method. Each bacterial solution was gradient diluted. Each dilution was plated in triplicate and incubated at LB medium for 12 h. Control group and materials treated groups were compared to evaluate the effect of inactivation. Nest, we tested the antimicrobial activity against E. faecalis. Sterilized water or sterilized water containing THA@Eu-NMOF@Fe/TA was mingled adequately with 3 mL E. faecalis solution. The above two control groups were irradiated with an 808 nm laser for 15 minutes (2 W / cm2), abbreviated as water + 808 nm, water + sample + 808 nm. The same two groups without any illumination were set as controls, respectively, and indicated blank and water + samples, respectively. Bacterial contents in both groups were measured by Colony-Forming Units (CFU) method. Each bacterial solution was gradient diluted. Each dilution was plated in triplicate and incubated at LB medium for 12 h. Control group and materials treated groups were compared to evaluate the effect of inactivation. Thermometric and Heating Difunctions of THA@Eu-NMOF@Fe/TA in Sub-tissues. Chicken breasts were used to simulate in vitro experiments, and an aqueous solution of THA @ Eu-NMOF @ Fe / TA (1 mg / mL) was sprayed into the chicken tissue. The signal at the injection site was recorded with a spectrophotometer under excitation of 808 nm at different power densities, and the surface temperature was recorded with a thermal imager.

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RESULTS AND DISCUSSION Preparation and characterization of THA@Eu-NMOF@Fe/TA nanoprobe According to the previously reported literature,26 the white powder-like Eu-NMOF was obtained. As shown in Figures 1a and 1b, the synthesized Eu-NMOF and THA@Eu-NMOF both displayed spherical morphologies in transmission electron microscope (TEM) figures, and there was no significant change in particle shape after modification with HTHA. After treatment in ethanol with 40 mg/mL TA and 10 mg/mL FeCl3, the achieved THA@Eu-NMOF@Fe/TA NPs displayed a rougher surface with “massif-like” humps (Figure 1c), and the color changed from white to black was observed. This indicated clearly that Fe/TA was deposited on the Eu-NMOF NPs. the energy dispersive X-ray (EDX) spectrum (Figure 1d) and elemental mapping images (Figure S3) illustrated the existence and even distribution of carbon, oxygen, iron and europium in the THA@Eu-NMOF@Fe/TA NPs, consistent

with

the

TEM

results

of

THA@Eu-NMOF@Fe/TA.

Dynamic light scattering technique (DLS) measurement (Figure 1e) showed the diameters of the nanoprobe THA@Eu-NMOF@Fe/TA around 80 ~ 112 nm with the average diameter of 98 nm which was same with the TEM results of THA@Eu-NMOF@Fe/TA. In order to identify the crystal structure and composition of the samples, powder X-ray diffraction (PXRD) of the materials before and after modification was tested. Figure 1f presented the PXRD pattern of the Eu-NMOF NPs before and after the modification of HTHA and Fe/TA. All the diffraction peaks in the 10


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PXRD patterns of Eu-NMOF NPs was consistent with previous reports,25 suggesting that there was no significant change in structure of the Eu-NMOF NPs before and after the modification of HTHA and Fe/TA. Additionally, the surface properties of Eu-NMOF, THA@Eu-NMOF, and THA@Eu-NMOF@Fe/TA were measured by zeta potential measurements. The results demonstrated that the HTHA coordination and Fe/TA loading could affect the zeta potential (Table S1). Due to the loading of HTHA on Eu-NMOF nanoparticles, the zeta potential of THA@Eu-NMOF NPs decreased from ˗2.38 to ˗13.2 mV, and then the zeta potential dropped to ˗20.9 mV after Fe/TA deposition on the surface of THA@Eu-NMOF nanoparticles. These results also illustrated the successful post-synthetic modification of the Eu-NMOF NPs.

Figure 1. The morphologies of (a) Eu-NMOF, (b) THA@Eu-NMOF, (c) THA@Eu-NMOF@Fe/TA. (d) EDX spectrum of THA@Eu-NMOF@Fe/TA. (e) DLS particle-size distribution of THA@Eu-NMOF@Fe/TA. (f) PXRD patterns of Eu-NMOF and THA@Eu-NMOF@Fe/TA. 11



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FT-IR, X-ray photoelectron spectroscopy (XPS), thermo-gravimetric analysis (TGA), and inductively coupled plasma mass spectrometer (ICP-MS) were used to further

illustrate

the

composition

and

structure

of

the

nanoprobe

THA@Eu-NMOF@Fe/TA. In the FT-IR spectrum (Figure S4), three peaks at 3664−2997, 1714−1598 cm−1 were belong to the absorption peaks of ν(O-H), δ(O−H) and ν(C=O) in trimesic acid,27 respectively. The bands at 1182 and 769 cm−1 was detected in the IR spectrum of THA@Eu-NMOF, attributed to the C−F and −CF3 stretching vibrations of the HTHA ligand, which implied successful modification of HTHA to Eu-NMOF. To further investigate the interaction between ligand HTHA, Fe/TA and Eu3+ ion in Eu-NMOF, we examined XPS of Eu-NMOF, THA@Eu-NMOF and THA@Eu-NMOF@Fe/TA. The C 1s (284.8 eV) photoelectron peak was used to correct the binding energy of all the research elements in the XPS spectrum. Figure 2a showed that C 1s, O 1s, and Eu 3d all existed in three samples before and after modification. The Eu3+ 3d5/2 peak in Eu-NMOF was moved to 1135.15 eV after addition of the HTHA ligand (Figure 2b), inferring the successful coordination of the β-diketone moiety of the HTHA ligand with Eu3+ ions. Owing to the versatile adhesion capability of TA, the obtained TA/Fe complex was tendency to form a homogeneous coating layer on the THA@Eu-NMOF. Therefore, after adding TA/Fe complex, the peak of Eu3+ at 1135.15 eV in THA@Eu-NMOF was moved to 1135.45 eV. In the Fe 2p spectrum (Figure 2c), two peaks located at 725.5 and 711.2 eV were considered to be the peak of Fe 2p1/2 and Fe 2p3/2, respectively. The 12


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difference of binding energy between the two peaks was 14.3 eV, indicating the presence of Fe3+ without the valence change of Fe3+.

Figure

2.

(a)

The

XPS

spectra

of

Eu-NMOF,

THA@Eu-NMOF

and

THA@Eu-NMOF@Fe/TA. (b) High-resolution XPS spectra of Eu in different materials. (c) High-resolution XPS spectrum of Fe in THA@Eu-NMOF@Fe/TA. (d) Two-photon emission peak intensities of THA@Eu-NMOF under different excitation wavelengths. In order to further verify the loading of HTHA and TA/Fe complex on Eu-NMOF, the TGA cures were also measured. From Figure S5a, it can be inferred that the loading amount of HTHA on Eu-NMOF was 2.75%. As displayed in Figure

13



S5b, the weight loss values of THA@Eu-NMOF and THA@Eu-NMOF@Fe/TA were 53.2 and 64.1%, respectively. A higher weight loss of THA@Eu-NMOF@Fe/TA indicated that TA/Fe composite was successfully immobilized onto the surface of the THA@Eu-NMOF NPs. According to the ICP-MS test (Table S2), we noticed that the content of FeIII was 2.19%. According to the results of TGA and ICP-MS, the loading capacity of TA/Fe complex was estimated to be 13.09%.

Two-photon property of THA@Eu-NMOF@Fe/TA The excitation light with the wavelength of 700 ~ 1000 nm has a high transmittance to the medium, which can effectively reduce the absorption of excitation light by the medium. In order to analyze the TPA property of HTHA, UV-vis absorption and fluorescence spectra of HTHA in ethanol were executed (Figure S6). In UV-vis absorption spectrum, HTHA had a wide ultraviolet absorption peak at 400 nm and a small absorption peak at 325 nm. Under 808 nm excitation the two-photon-excited luminescence (TPL) peak of HTHA was mainly concentrated at 500 nm. In order to have a deep insight of the two-photon feature of THA@Eu-NMOF composite, a TPA cross-sectional area of THA@Eu-NMOF was measured (Rhodamine B was used as a calibration material). Two-photon emission performance of THA@Eu-NMOF was verified by two-photon emission spectroscopy intensities under different excitation wavelengths (Figure 2d). Using different excitation wavelengths, the wavelengths at 760 nm displayed the maximum two-photon excitation intensity for THA@Eu-NMOF. Besides, THA@Eu-NMOF displayed a 14


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TPA cross-sectional area of 33.08 GM under 808 nm excitation (the detailed calculation procedure was listed in the Supporting Information). Although it was not the largest two-photon absorption cross section of THA@Eu-NMOF under 808 nm excitation, in order to achieve photothermal therapy and temperature sensing under a single beam of light, we choose 808 nm as the excitation source. The coordination of HTHA not only endowed THA@Eu-NMOF NPs the function of two-photon sensitized Eu3+ emission under 808 nm NIR light excitation, but also ensured higher tissue penetration and avoids tissue burn caused by water (water has maximum absorption at 980 wavelength).

Temperature-dependent absorption and steady-state photoluminescence The infrared thermography obtains an infrared thermal image by receiving the infrared radiation energy of the target, and the thermal image corresponds to the heat distribution field on the surface of the object.28 It causes low spatial resolution due to the inherent imaging principle of thermal imagers. However, even a few degrees of temperature change in a biological system may mean a difference in cell life and death. In order to get more accurate temperature feedback, it need to find a more accurate temperature detection method. In general, the change of temperature affects the fluorescent properties of the material. The reason is that based on the classical Mott-Seitz model,29-30 the fluorescence intensity (I1 or I2) can be expressed by equation 1:

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𝐼0

𝐼= 𝑖

(1)

( )

𝐼 + ∑𝑎 𝑒𝑥𝑝

―∆𝐸1𝑖 𝐾𝐵𝑇

In this equation, ai is the ratio between the non-radiation and radiation probability of the i-deactivated channel, I0 is the beam intensity at T = 0 K, ∆Ei is the activation energy of the i-thermal quenching process, and kB is the Boltzmann constant, T is the absolute temperature. So I2/I1 can be expressed by equation 2: 𝐼1 𝐼2

( ―∆𝐸2 𝐾𝐵𝑇) = ∆0 ―∆𝐸1 1 + 𝑎 𝑒𝑥𝑝( 𝐾𝐵𝑇) 1 + 𝑎2𝑒𝑥𝑝

(2)

2

Where ∆0 = 𝐼01 𝐼02. From the equation of (1) and (2), we conclude that the change in fluorescence intensity is temperature dependent. And the lifetime can be expressed by the following equation 3:31 1

𝜏 = 𝑊𝑟 + 𝑊𝑛𝑟(𝑇) =

1 𝜏0―1

(

∆𝐸 𝐵𝑇

+ 𝐾𝑒𝑥𝑝 ― 𝐾

(3)

)

where Wr and Wnr are the radiative and non-radiative probability, respectively, ∆E is the energy gap between the emitting level and the higher excited state, 𝜏0 is the radiative lifetime (T = 0 K), k is a pre-exponential factor, and kB is the Boltzmann constant. Therefore, lifetime is also temperature dependent. The luminescence of Eu3+ in THA@Eu-NMOF@Fe/TA nanoprobe was sensitized by the HTHA, which can be verified by the excitation spectrum collected for

THA@Eu-NMOF@Fe/TA.

Upon

excitation

at

808

nm,

THA@Eu-NMOF@Fe/TA exhibited characteristic sharp emissions of Eu3+ ions (Figure

S7a).

To

evaluate

the

temperature

sensing

performance

of

THA@Eu-NMOF@Fe/TA, the luminescence spectra of THA@Eu-NMOF@Fe/TA 16


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was recorded at different temperature. In order to excavate the potential efficiency as molecular thermometer of THA@Eu-NMOF@Fe/TA, the intensity ratio I615/I590 is used as the thermometric parameter. Ratiometric thermometers are not affected by the concentration of the sensor in the medium during temperature measurement and can be self-calibrated measurement of the temperature from the emission spectra.28 The transition of Eu3+ at 5D0-7F2 (616 nm) is particularly ultrasensitive to change in external conditions. The thermal activation of nonradiative-decay pathways can be enhanced as the temperature increases.32 Therefore, the plot (Figure S7b) showed the luminescence intensity at 616 nm gradually decreased when the temperature increases from 20 °C to 60 °C. However, the intensity of 5D0-7F1 of Eu3+ (590 nm) was almost unchanged. The dependence of I615/I590 on temperature was plotted in Figure 3a which revealed a good linear relationship between I615/I590 and temperature within the range of 20 to 60 °C. The linear relationship can be fitted as a function of eqn. (4) with a correlation

coefficient

(R2)

of

0.993,

inferring

that

the

nanoprobe

THA@Eu-NMOF@Fe/TA was an excellent ratiometric nanothermometer in the range from 20 to 60 °C (biological range). I615/I590 = 4.86 - 0.021T

(4)

And the thermal sensitivity of THA@Eu-NMOF@Fe/TA can be calculated using eqn. (5).33 As show in Figure 3b, the maximal sensitivity of the THA@Eu-NMOF@Fe/TA nanoprobe is 0.59% at 60 °C.

(5)

17



Figure 3. (a) Intensity ratio I615/I590 of THA@Eu-NMOF@Fe/TA and the fitted curve. (b) The relative sensitivity (Sr) for THA@Eu-NMOF@Fe/TA. (c) Temperature-dependent lifetime data of THA@Eu-NMOF@Fe/TA and the fitted curve. (d) The relative sensitivity (Sr) of temperature-dependent lifetime for THA@Eu-NMOF@Fe/TA. The experimental details: the sample solution was placed in a fluorescence detector equipped with a temperature control device (warming procedure: heat for 5 minutes, keep for 10 minutes) to collect fluorescence or lifetime signals per 5 ̊Ϲ.

Temperature-dependent transient photoluminescence 18


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The lifetime value was not affected by the probe concentration, size or geometry, and was not affected by light scattering, reflection or intensity fluctuations of the excitation source.34 Thus, we studied the response of lifetime of the nanoprobe THA@Eu-NMOF@Fe/TA to the temperature. Figure 3c showed the influence of temperature on the lifetime of Eu3+ in the nanoprobe THA@Eu-NMOF@Fe/TA. It had been observed that as the temperature increases from 20 °C to 60 °C, the average lifetime of THA@Eu-NMOF@Fe/TA drops rapidly. Equation (6) is a function fit of the test results with a correlation coefficient (R2) of 0.986. τ615 = 788.40 - 1.57T

(6)

The sensitivity was calculated in the same way using eqn. (5) except that the fluorescence intensity ratio was replaced with the fluorescence lifetime. Figure 3d displayed the maximum temperature sensitivity is 0.23% at 60 °C (from 20 to 60°C). Compared with the Ln-MOFs-based temperature probes that have been reported (listed in Table 1), the nanoprobe THA@Eu-NMOF@Fe/TA has a more suitable excitation source (ex = 808 nm), which can reduce the damage of the excitation light to the biological tissue and have deeper penetration. Also, another advantage of the synthesized nanoprobe THA@Eu-NMOF@Fe/TA is that the lifetime signals can also be used in the temperature sensing. Therefore, it is more suitable for temperature monitoring in the biological systems which possess the complex biological background interferences.

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Table 1. Comparing the performance of the reported Ln-MOFs based temperature probes in terms of maximum relative sensitivity, excitation wavelength, temperature range. Ln-MOF

Range (K)

Ex (nm)

Sensitivity (%/K)

Ref.

Tb0.95Eu0.05HL

4 - 490

325

31 (4K)

35

Tb0.95Eu0.05HL

298 - 318

323

1.19 (313K)

36

Tb0.80Eu0.20BPDA

300 - 320

320

0.31 (318K)

32

Tb0.99Eu0.01(BDC)1.5(H2O)2

100 - 400

UV irradiation

0.079

37

Eu0.0878Tb0.9122L

75 - 250

325

4.9 (250K)

38

ZJU-88 ∋ perylene

293 - 353

388

1.28 (293K)

19

Tb0.9Eu0.1PIA

100 - 300

365

3.53

39

Photothermal effect of THA@Eu-NMOF@Fe/TA nanoprobe in vitro It can be seen from the UV-visible absorption spectrum (Figure S8) that the nanoprobe THA@Eu-NMOF@Fe/TA with strong NIR absorbance had strong potential to be used as a new theranostic nanoplatform for PTT. We next investigated the photothermal properties of the material. THA@Eu-NMOF@Fe/TA suspension was irradiated with an 808 nm NIR laser at a power density of 2 W/cm2. As the concentration of nanoprobe increased, the temperatures of THA@Eu-NMOF@Fe/TA solutions increased accordingly (Figure 4a). After 600 seconds of irradiation, the temperature of the THA@Eu-NMOF@Fe/TA solutions (600 μg/mL) ascended from 20


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24.3 to 56.7 °C. However, in the same conditions, the temperature of deionized water was almost constant. From the previously reported article,40 when the temperature reached to 50 °C, it can effectively kill cancer cells. As shown in Figure S9, as the power

density

change

from

0.5

to

2

W/cm2,

the

temperatures

of

THA@Eu-NMOF@Fe/TA solutions at the same concentration increased. However, when

the

power

density

was

0.5

W/cm2,

the

temperature

of

THA@Eu-NMOF@Fe/TA NPs did not change significantly. This illustrated that the power intensity had a great influence on the photothermal effect. As displayed in Figure 4b, the heat-generating ability of THA@Eu-NMOF@Fe/TA was hardly changed during repeated cycles, indicating that it has good photothermal steadiness. Therefore, THA@Eu-NMOF@Fe/TA nanoprobe can be reused during PTT. Next, the photothermal conversion efficiency (η) of THA@Eu-NMOF@Fe/TA was calculated as 16.28% from the fitting data obtained in the cooling phase (Figure S10 and the calculation formula of the photothermal conversion effect supporting the information recording listed in the Supporting Information).

21



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Figure 4. (a) Optical heating capacity of THA@Eu-NMOF@Fe/TA solutions at different concentrations under 808nm laser irradiation (2W/cm2). (b) Temperature curve of THA@Eu-NMOF@Fe/TA (300 μg/mL) under repeated illumination (808 nm, 2W/cm2) on/off cycles.

Antibacterial activities of the THA@Eu-NMOF@Fe/TA nanoprobe Due to the photothermal effect of the THA@Eu-NMOF@Fe/TA nanoprobe, photothermal inactivation effects against bacteria was be tested under 808 nm light illumination. Then, to demonstrate 808 nm light-induced photothermal inactivation effects against bacteria, the antibacterial activity of THA@Eu-NMOF@Fe/TA was assessed using Enterococcus faecalis (E. Faecalis) bacteria as a bacterial mold, as presented in Figure 5a. The simple experiment scheme, E. Faecalis bacteria were cultivated

with

sterilized

water

solution

or

sterilized

water

containing

THA@Eu-NMOF@Fe/TA samples. Next, the above two groups with 808 nm irradiation for 15 min were entitled water + 808 nm and water + sample + 808 nm. Meanwhile the control groups without laser irradiation were shorthand for blank and 22


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water + sample (Figure 5a). As described in Figure 5b, compared with the blank group, the bacterial strain had a higher survival rate (98%) in water + 808 nm, indicating that lighting was useless when THA@Eu-NMOF@Fe/TA NPs were not added. However, the viability of bacteria in the sterilized water solution containing THA@Eu-NMOF@Fe/TA without 808 nm irradiation decreased to 19.51%. In addition, compared with water + sample, water + sample + 808 nm groups had a higher mortality rate up to 93.43%. This upshot suggested that THA@Eu-NMOF@Fe/TA can enhance the antimicrobial effect by photothermal inactivation effects under 808 nm laser excitation. After irradiation with 808 nm light for 15 min, the sterilized water solution containing THA@Eu-NMOF@Fe/TA produced large amounts of heat, inducing the degeneration of the enzyme and then inhibiting the necessary intracellular response.41 In high temperatures, proteins and lipids on the membrane can be damaged, and some of the small molecules inside the cells such as DNA and RNA leak from the twisted membrane,42 severely interfering with normal cellular function. TA is a water-soluble polyphenol, commonly found in herbs and woody plants, and accepted by the FDA. It is widely used in foods and pharmaceuticals.43-44 According to the reports, TA has a bactericidal effect on a variety of bacteria such as Escherichia coli (E. coil), Staphylococcus aureus, Helicobacter pylori.10 This property suggested a potential utilization of THA@Eu-NMOF@Fe/TA nanoprobe in antibacterial field. Therefore,

we

tested

the

antibacterial

activity

of

the

nanoprobe

THA@Eu-NMOF@Fe/TA. The antibacterial activity was measured using E. coli 23



bacteria. The antibacterial activity of THA@Eu-NMOF@Fe/TA against E. coli was evaluated by measuring the cell mortality after cultivate of the bacteria with increasing concentrations of THA@Eu-NMOF@Fe/TA colloidal solutions. As show in Figure 5c, the bacterial cells were exposed to THA@Eu-NMOF@Fe/TA concentrations in the range of 10−500 μg/mL for 15 minutes. The bacterial cell loss gradually ascended with the increasing concentration of THA@Eu-NMOF@Fe/TA NPs. E. coli showed 45.74% mortality rate, at the lowest THA@Eu-NMOF@Fe/TA concentration of 10 μg/mL. Upon increasing the THA@Eu-NMOF@Fe/TA concentration from 10 μg/mL to 50 μg/mL, the mortality rate of E. coli was increased from 45.74 to 78.70%. More than 95.87% bacterial viability loss was observed at 100 μg/mL of THA@Eu-NMOF@Fe/TA NPs and bacterial inhibition was increased to more than 98% at 300 μg/mL of THA@Eu-NMOF@Fe/TA. Additionally, when the concentration was greater than 300 μg/mL, the concentration increase had no obvious enhancement on the antibacterial activities of E. coil. The above results showed that the THA@Eu-NMOF@Fe/TA NPs could be used as ideal antimicrobial agents and had excellent photothermal inactivation effect against E. Faecalis.

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Figure 5. (a) Digital images of photothermal inactivation effects against E. faecalis under 808 nm laser excitation. (b) Relative mortality of bacterial colonies formed by E. faecalis (500 µg/mL) under different concentration. (c) Relative viability of bacterial colonies formed by E. coli under different incubation condition.

Thermometry and heating in sub-tissues The power density evolution of both sub-tissues and surface temperature were obtained by the spectrophotometer and infrared thermal camera. As shown in Figure 6a, the aqueous solution containing the material (0.1 mL) was squirted into the chicken tissue about 1 cm. Under the illumination of 808 nm for 5 minutes with different power densities, the temperature at the injection site was calculated by the fluorescence spectroscopy, and at the same time the surface temperature was recorded by the thermal imager. The difference between sub-tissue and surface temperature 25



were recorded in Figure 6b. The important conclusion was that both sub-tissues and surface temperatures showed the same increasing trend with the increasing of power density, but their actual values were remarkable different. This result was consistent with the previous reports during PTT.45 When the laser density raised from 0.5 to 3 W/cm2, temperatures increased from 18 to 30 °C on the surface and 24 to 35 °C at the injected site. Therefore, it noticed that the obtained sub-tissues temperature was higher than that measured surface temperature. Due to the difference in the rate of transfer between the tissue's efficient heat transfer to the air and through the tissue's thermal diffusion, the temperature at the injection site and surface is different. The experimental result revealed the importance of monitoring temperature at injection sites, indicating that the fluorescence thermometer supplied more precise thermal sensing results in the subcutaneous injection site compared with infrared thermometry. Therefore, the dual performances of simultaneous heating with 808nm laser and temperature induction could minimally damage to surrounding normal tissue during the PTT. It means that THA@Eu-NMOF@Fe/TA NPs can be a great integrated thermometer-heater platform with real-time temperature feedback and optical heating capacity.

26


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Figure 6. (a) Experiment diagram for monitoring temperatures of fresh chicken breast and (b) Temperatures measurement in chicken breast with and without THA@Eu-NMOF@Fe/TA injection under 800 nm excitation with different power density.

CONCLUSIONS In summary, we have successfully developed a smart all-in-one nanoprobe THA@Eu-NMOF@Fe/TA by post-synthetically functionalization of a Eu(Ⅲ)-NMOF which can achieve temperature-sensing and optical heating at the same time under NIR light excitation. As an excellent photothermal reagent and bacteriostatic agent, Fe/TA can increase the temperature under 808 nm laser irradiation and had the corresponding ability to kill bacteria. By analyzing the fluorescence intensity ratio and fluorescence lifetime of the Eu-NMOF, it was found that the nanoprobe THA@Eu-NMOF@Fe/TA had excellent real-time temperature sensing property. When power density raised from 0.5 W/cm2 to 3 W/cm2 for 5 minutes, the subcutaneous maximum temperature monitored by fluorescence spectrum was higher than the indication temperature of infrared thermometry. In addition, under the 27



excitation of 808 nm light, the excellent light-induced photothermal inactivation effects against E. faecalis was also achieved for the nanoprobe. By integrating sensitive, moderate thermometry and efficient photothermal conversion agent into a MOF platform, THA@Eu-NMOF@Fe/TA nanoprobe can be considered as an ideal candidate for real-time temperature response during PTT with high therapeutic accuracy and bacteriostatic activity.

Supporting Information More experimental details, synthesis process, FTIR spectrum, 1H spectrum, UV-Vis spectra, Zeta-potential, ICP-MS, PL spectra and the determination of two-photon absorption cross-sectional area. This material is available free of charge via the Internet at http://pubs.acs.org.

ASSOCIATED CONTENT AUTHOR INFORMATION Corresponding Author *E-mails: [email protected] and [email protected] ORCID Yu Tang: 0000-0003-3933-043X Jing Cao: 0000-0003-3978-911X

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Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT We acknowledge the National Natural Science Foundation of China (Projects 21871121, 21801104, 21601074 and 21431002) and Fundamental Research Funds for the Central Universities Grants (Project Lzujbky-2018-ot01).

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Smart All-in-one Thermometer-heater Nanoprobe Based on Post

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