Dual Near-Infrared-Emissive Luminescent Nanoprobes for Ratiometric

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Biological and Medical Applications of Materials and Interfaces

Dual Near-Infrared Emissive Luminescent Nanoprobe for Ratiometric Luminescent Monitoring of ClO in Living Organisms -

Cong Cao, Xiaobo Zhou, Meng Xue, Chunmiao Han, Wei Feng, and Fuyou Li ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.9b02008 • Publication Date (Web): 12 Apr 2019 Downloaded from http://pubs.acs.org on April 12, 2019

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ACS Applied Materials & Interfaces

Dual

Near-Infrared

Emissive

Luminescent

Nanoprobe for Ratiometric Luminescent Monitoring of ClO- in Living Organisms Cong Cao, Xiaobo Zhou, Meng Xue, Chunmiao Han, Wei Feng*, Fuyou Li* Department of Chemistry & State Key Laboratory of Molecular Engineering of Polymers & Institute of Biomedicine Sciences & Collaborative Innovation Center of Chemistry for Energy Materials, Fudan University, 2005 Songhu Road, Shanghai, P.R. China.

KEYWORDS Detection of ClO-, Lanthanide Doped Nanoparticles, Ratiometric Fluorescence Probe, NearInfrared, Inflammation Model, In vivo Bioimaging

ABSTRACT

The difficulty of near-infrared (NIR) ratiometric detection imaging lies in the lack of highefficiency NIR probes and the overlapping interference between two emission peaks. To achieve more accurate detecting in living organisms, dual near-infrared emissive luminescent nanoprobe 1

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was designed under the same excitation at 808 nm. The Er3+ ions doped nanoparticles were employed as reference with its fluorescence emission at 1525 nm. Meanwhile, a cyanine dye molecule (Cy925) was combined on the surface of nanoparticles as ClO- recognition site with its NIR emission at 925 nm. The ratiometric nanoprobe relied on the ratio of aforementioned two separated NIR peaks (I925 nm/I1525 nm), featuring deeper imaging penetration depth and low autofluorescence. This nanoprobe was verified to be sensitive and highly selective to ClO- through photoluminescence titration. The in vitro detection experiment developed reasonable work curves guarantee that we can detect the change in concentration of ClO- in mice limbs with arthritis through in vivo imaging experiment.

■

INTRODUCTION

Fluorescent probes are powerful tools for real time monitoring of bio-molecules at physiological levels in vitro and in vivo.1-3 The main difficulties of such detection probe using in living organisms include the limited tissue penetration depth of working light and the signal uncertainty caused by the variable concentration of probe.4,5 Actually, photons are absorbed less by biological tissues in the near-infrared region (NIR, 700-1700 nm) than that in the ultra violet and visible region.6-8 In addition, there is almost no auto-fluorescence in the NIR window, which is beneficial for acquiring high quality of imaging. With effective recognition sites, NIR fluorescent dyes are promised biological candidate for detection.9-14 Nevertheless, the detection mechanism of these dyes is generally based on the change of single emission peak.15,16 The signal change could not represent the actual concentration of the changed analyte. To solve this problem, constructing ratiometric fluorescent probe has been proposed as an effective method. It can be more reliable quantification 2


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for its self-calibration, meanwhile, two or more different emission bands were involved to generate the detection signal.17-19 Indeed, the feasibility has been proved to construct such ratiometric probe in cellular detection by binding nanocrystals with the fluorescent dye.5,19-22 However, the challenge is still severe for detection in living organisms. At first, aforementioned ratiometric probes are mostly based on the organic dyes, which usually have small Stokes-shift and broad absorption and NIR emission peaks, resulting in inevitably overlapping peak disturbances. After all, the synthesis of two separated NIR dyes is extremely difficult for now. If the reference signal has too close wavelength difference to the response signal, the sensitivity of detection will be decreased. To achieve bigger wavelength difference, it is also a great challenge for most phosphors to be excited at the same wavelength without reabsorption. On the other hand, differ from the narrow NIR-I window (700-950 nm), a more widely NIR-II window (950-1700 nm) attracts more attention.23-27 The ratiometric probe working in this window can easily achieve both separated emission peaks and deeper imaging penetration depth. Noteworthy, among plenty of lanthanide doped NIR nanocrystals, Er3+ ions doped nanoparticles have NIR emission at 1525 nm under 980/808 nm excitation.28-31 Thus the large Stokes-shift made it be favorable candidate for constructing dual NIR emissive ratiometric probes. Acted as activators, the doping concentration of Er3+ ions is usually at low level (99.999%) and Nd2O3 (>99.999%) were all bought from Shanghai Yuelong Rare Earth New Materials Co., Ltd. Oleic acid (OA, >90%), Oleylamine (OM, >90%) and 1-Octadecene (ODE; >90%) were obtained from Alfa Aesar Ltd. CF3COONa, trifluoroacetic acid (TFA) and NaClO were bought from Sinopharm Chemical Reagent Co.. Ethanol, CH2Cl2 and cyclohexane were bought from Adamas-beta® Co.. The methoxy polyethylene glycol phospholipids (DSPE-PEG2000) was bought from Shanghai Ponsure Biotechnology Co. RE(CF3COO)3 (RE3+=Nd3+, Er3+, Yb3+, Y3+) were obtained through oxides adding with trifluoroacetic acid. All chemical materials and reagents were bought from commercial sources. The XRD patterns of all nanocrystals were determined on a D4 advance diffractometer with the scanning rate of 0.5 ° minute-1 (λ= 1.5406 Å, Cu Kα radiation). All TEM, HRTEM, HAADFSTEM images and EDXA spectrum of the nanoparticles were obtained by a Tecnai G2 F20 STwin instrument operating at 200 kV. The absorption spectrum was measured by a Lambda 35 UV-Visible spectrophotometer. The 1H NMR spectra were characterized by an AVANCE III nuclear magnetic resonance spectrometer at 400 MHz. The NIR fluorescence spectra were recorded from the FLS920 luminescence spectrometer (Edinburgh Instruments) equipped with an InGaAs matrix near-infrared detector (Princeton), under an external adjustable 808 nm laser (Changchun Femtosecond Technology Co., Ltd., China). The power of the 808 nm laser was 16


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detected by the photodiode power probe (S175C, Thorlabs) and the optical power meter console (PM200, Thorlabs). And the power density (mW/cm2) is the ratio of the power (mW) and the effective area of the laser spot (cm2). The multi oxidants [O2-, 1O2, H2O2, HO·, BuOOH, NO, BuOO·, ONOO-] used in the responsive measurements were generated according to the previous report.46 And the NIR luminescence imaging system was constructed by our research group, as shown in the Figure 5. The NIR luminescence images were collected with an InGaAs-based NIR camera (Princeton) before corresponding bandpass filters (Thorlabs) under the external 808nm laser. Synthesis of NaYbF4:Er nanoparticles. NaYbF4:2%Er nanoparticles were synthesized by a thermolysis method. 0.98 mmol Yb(CF3COO)3, 0.02 mmol Er(CF3COO)3 and 1.00 mmol CF3COONa were added into a three-neck flask (100 mL) which contained with 10 mmol OA, 10 mmol OM and 20 mmol ODE. The whole solution was heated to 120 °C under vacuum until all the powder dissolved. Then the solution was heated up to 300 °C and maintained the temperature for 0.5 h at N2 atmosphere. The products were precipitated by adding excessive ethanol and centrifugation. Synthesis of NaYbF4:Er@NaYF4:Yb nanoparticles. The 0.50 mmol NaYbF4:Er nanoparticles, 0.45 mmol Y(CF3COO)3, 0.05 mmol Yb(CF3COO)3 and 0.50 mmol CF3COONa, were added into a three-neck flask (100 mL) containing with 20 mmol OA and 20 mmol ODE. The solution was heated to 105 °C under vacuum until formed a transparent solution. Then the solution was heated up to 300 °C and maintained the temperature for 0.5 h under N2 protecting. The NaYbF4:2%Er@NaYF4:10%Yb nanoparticles were precipitated by adding ethanol and centrifugation.

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Synthesis of OA coated NaYbF4:Er@NaYF4:Yb@NaYF4:Nd nanoparticles (Er-CSSNPs). The 0.50 mmol NaYbF4:Er@NaYF4:Yb nanoparticles, 0.50 mmol Nd(CF3COO)3, 0.50 mmol Y(CF3COO)3 and 0.50 mmol CF3COONa were added into a three-neck flask (100 mL) containing with 20 mmol OA and 20 mmol ODE. The solution was heated to 105 °C under vacuum until the powder dissolved. Then the solution was heated up to 300 °C and maintained the temperature for 0.5 h at N2 atmosphere. The NaYbF4:2%Er@NaYF4:10%Yb@NaYF4:50%Nd nanoparticles were precipitated by adding ethanol and centrifugation, dispersed into 5 mL of cyclohexane. Synthesis of Compound 1. The mixture of POCl3 (40 mL) and CH2Cl2 (45 mL) was added slowly into an ice-cooled solution of DMF (40 mL). Then the cyclohexanone (10 g) was dropwise added to the mixture. The whole solution was heated to 55 °C and refluxed for 2 h. The reaction was cooled in ice water and kept stirring for 0.5 h. Then the water layer was extracted with CH2Cl2. The CH2Cl2 solution was all collected and passed through anhydrous magnesium sulfate column, concentrated on a rotary evaporator, and treated with pentane (200 mL).The final products were yellow crystalline solid and 5.2 g (30%). 1H NMR (400 MHz, CDCl3, ): 2.46 (t, J= 6.2 Hz, 4H), 1.75-1.68 (m, 2H). MS (MALDI-TOF MS): calcd. For C8H9ClO2 172.03 [M]+; found, 172.00 [M]+. Synthesis of Compound 2. CH3CH2ONa (50 mg), 3-hydroxy-3-methyl-2-butanone (450 mg), malononitrile (600 mg) and EtOH (0.5 mL) were added into a 10 mL round-bottomed flask and kept stirring for 1 h at 25 °C. Then 1.5 mL ethanol was added into the mixed solution, slightly heated and refluxed for 2 h. Finally the mixture was cooled down and crystallized out slight yellow solid. After suction filtration and washed, 700 mg (80%) of the products were finally obtained. 1H NMR (400 MHz, CDCl3, ): 2.367 (s, 3H), 1.633 (s, 6H). MS (MALDI-TOF MS): calcd. For C11H9N3O+ 199.07 [M]+; found, 199.04 [M]+. 18


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Synthesis of Compound Cy925. Compound 1 (0.25 mmol) and 2 (0.5 mmol), 50 mg CH3COOK and 1 mL acetic anhydride were added to a 10 mL round-bottomed flask. The mixture was heated to 70 °C for reaction 0.5 h under nitrogen atmosphere. The mixture cooled down to 25 °C and with saturated NaHCO3 neutralization. The products were extracted with CH2Cl2 and concentrated on a rotavapor. Methanol and CH2Cl2 were used as eluant column chromatography to obtained Cy925 (113 mg, 85%). 1H NMR (400 MHz, MeOD, ): 8.1796 (d, J=14.0 Hz, 2H), 6.087 (t, J=14.8 Hz, 2H), 2.681-2.549 (m, 4H), 1.869 (m, 2H), 1.658 (s, 12H). MS (MALDI-TOF MS): calcd. For C30H22ClN6O2+ 533.15 [M]+; found, 533.06 [M]+. Synthesis of the composite probe Er-CSSNPs@Cy925. Er-CSSNPs@Cy925 was synthesized according to a previous reported method. The Er-CSSNPs (10 mg) and Cy925 (2 mg) were dispersed in chloroform (8 mL) with sonication for 10 min at 20 °C. The mixture was stirred for 1 h. Then the amphiphilic polymer (DSPE-PEG2000, 10 mg) was added to the solution. Furthermore, the whole solution kept stirring for 12 h at 20 °C meanwhile the solvent was gradually evaporated. The products were collected by centrifugation (24149 rcf, 10 min), dispersed in water. In vitro NIR luminescence imaging. The solution of Er-CSSNPs@Cy925 probe (0.1 mg/mL * 200 L) was added into the three wells of 96-well plate as parallel groups, and then dropped with ClO- separately. The signals of Cy925 were collected at 845-935 nm by using a band-pass filter (Thorlabs), meanwhile the signals from Er-CSSNPs were collected at 1490-1580 nm by using a band-pass filter (Thorlabs), both using an InGaAs-based NIR camera. The average signals of three well in titration process were analyzed by the Bruker imaging software. In vivo NIR luminescence imaging. All the animal experiments follow the guiding principles of the Institutional Animal Care and Use Committee, School of Pharmacy, Fudan University. Saline solution (10 mg/mL) of carrageen was injected into the ankle joint of the right hind limb of 19



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the 4-week old female Balb/c mice (n=3) to form an acute inflammation model. Meanwhile, 50 L of saline was injected as control group at the ankle joint of the left hind limb of the mouse. After different time points of 1 h, 2 h and 4 h, 50 L of the nanoprobe was injected into the left and right hind limbs of the parallel experimental mice (n=3), respectively. The NIR luminescence photos were obtained by the NIR camera, the same as in vitro titration imaging. Signals of luminescence photos were analyzed by Bruker Imaging software and Origin 8.0 software. ■

ASSOCIATED CONTENT

Supporting Information The Supporting Information is available free of charge on the ACS Publications website at DOI: XXX. (1) Additional characterization analysis of Er-CSSNPs and dye Cy925; (2) Quantum yield curve of NIR CCD camera; (3) Details for the proposed data model. ■ AUTHOR

INFORMATION

Corresponding Author *E-mail: [email protected]. (W. Feng). *E-mail: [email protected]. (F. Y. Li) Notes The authors declare no competing financial interest. ■ ACKNOWLEDGMENT

The authors acknowledge the financial supporting from the National Natural Science Foundation of China (21722101, 21671042, and 21874027). 20


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(46) Wei, P.; Yuan, W.; Xue, F.; Zhou, W.; Li, R.; Zhang, D.; Yi, T. Deformylation reactionbased probe for in vivo imaging of HOCl. Chem. Sci. 2018, 9, 495-501.

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Dual Near-Infrared-Emissive Luminescent Nanoprobes for Ratiometric

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