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Red fluorescent BODIPY molecular rotor for high microviscosity environments 用于高微粘度环境的红色荧光BODIPY分子转子
IF 3.2 3区 化学 Q3 CHEMISTRY, ANALYTICAL Pub Date : 2022-06-15 DOI: 10.1088/2050-6120/ac7943
Karolina Maleckaitė, Jelena Dodonova-Vaitkūnienė, Rugilė Žilėnaitė, S. Tumkevičius, Aurimas Vyšniauskas
Microviscosity has a strong impact for diffusion-controlled processes in biological environments. BODIPY molecular rotors are viscosity-sensitive fluorophores that provide a simple and non-invasive way to visualise microviscosity. Although green fluorescent probes are already well developed for imaging, thick biological samples require longer wavelengths for investigation. This work focuses on the examination of novel β-substituted meso-phenyl-BODIPYs possessing a red emission. We report a new red fluorescent BODIPY-based probe BP-Vinyl-NO2 suitable for sensing microviscosity in rigid environments of over 100 000 cP viscosities. Furthermore, we demonstrate that changing the methyl position from ortho to meta on the β-phenyl-substituted conjugate BP-PH-m2M-NO2 redshifts absorbance and fluorescence spectra while maintaining viscosity sensitivity. Finally, we show that nitro-substitution of meso-phenyl is a versatile approach to improve the sensitivity to viscosity while suppressing sensitivity to polarity and temperature of such derivatives. In summary, we present two nitro-substituted red fluorescent probes that could be used as lifetime-based microviscosity sensors.
微粘度对生物环境中的扩散控制过程具有重要影响。BODIPY分子转子是粘度敏感的荧光团,提供了一种简单而非侵入性的方法来观察微粘度。虽然绿色荧光探针已经很好地用于成像,但厚的生物样品需要更长的波长进行研究。这项工作的重点是研究具有红色发射的新型β-取代中苯基bodipys。我们报道了一种新的基于bodipy的红色荧光探针BP-Vinyl-NO2,适用于在超过100,000 cP粘度的刚性环境中检测微粘度。此外,我们证明了将β-苯基取代的共轭物BP-PH-m2M-NO2的甲基位置从邻位改变为间位,可以在保持粘度敏感性的同时使吸光度和荧光光谱发生红移。最后,我们表明硝基取代中苯基是一种通用的方法,可以提高对粘度的敏感性,同时抑制对此类衍生物的极性和温度的敏感性。总之,我们提出了两种硝基取代的红色荧光探针,可以用作基于寿命的微粘度传感器。
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引用次数: 0
Facile synthesis of sulfur and oxygen co-doped graphitic carbon nitride quantum dots for on-off detection of Cu2+ in real samples and living cells 硫氧共掺杂石墨氮化碳量子点的简单合成,用于实际样品和活细胞中Cu2+的开关检测
IF 3.2 3区 化学 Q3 CHEMISTRY, ANALYTICAL Pub Date : 2022-06-15 DOI: 10.1088/2050-6120/ac7944
Mengting Zhang, Yulu Zhang, Mingyu Gan, Liping Xie, Jing Wang, Wei‐Hua Jia, W. Bian, S. Shuang, Martin M. F. Choi
A fluorescent sulfur and oxygen co-doped graphitic carbon nitride quantum dots (S,O-CNQDs) were prepared from ethylenediaminetetraacetic acid disodium salt dihydrate and thiourea as the carbon and sulfur sources. The morphology and surface functional groups of S,O-CNQDs were characterized by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. The fluorescence of S,O-CNQDs could be quenched efficiently by Cu2+ under the optimum conditions. The S,O-CNQDs could function as an excellent fluorescent probe for Cu2+ detection with a wide linear range of 0.50–15 μM and a low detection limit of 0.58 nM. In addition, this fluorescent probe was employed for monitoring Cu2+ in samples of tap water, lake water, human serum and urine with good recoveries from 99.0% to 110.0%. Moreover, the S,O-CNQDs with high cell penetration and low cytotoxicity were utilized for Cu2+ detection in living cells. Owing to the excellent properties of S,O-CNQDs, the as-prepared S,O-CNQDs can be a potential candidate for biological applications.
以二水乙二胺四乙酸二钠盐和硫脲为碳源和硫源制备了硫氧共掺杂的荧光石墨氮化碳量子点(S,O-CNQDs)。采用x射线衍射、透射电子显微镜、x射线光电子能谱和傅里叶变换红外光谱对S,O-CNQDs的形貌和表面官能团进行了表征。在最佳条件下,Cu2+能有效猝灭S,O-CNQDs的荧光。S,O-CNQDs具有较宽的线性范围(0.50 ~ 15 μM)和较低的检测限(0.58 nM),是检测Cu2+的优良探针。该荧光探针可用于自来水、湖水、人血清和尿液中Cu2+的检测,回收率为99.0% ~ 110.0%。此外,具有高细胞穿透性和低细胞毒性的S,O-CNQDs被用于活细胞中Cu2+的检测。由于S,O-CNQDs的优异性能,制备的S,O-CNQDs具有潜在的生物学应用前景。
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引用次数: 5
3-aminoquinoline: a turn-on fluorescent probe for preferential solvation in binary solvent mixtures 3-氨基喹啉:一种用于二元溶剂混合物中优先溶剂化的开启荧光探针
IF 3.2 3区 化学 Q3 CHEMISTRY, ANALYTICAL Pub Date : 2022-06-13 DOI: 10.1088/2050-6120/ac784d
Sharmistha Das, Shirsendu Das, A. Singh, A. Datta
3-Aminoquinoline (3AQ) has been used as a fluorescent probe for preferential solvation in hexane-ethanol solvent mixtures. Results of the present experiment have been put into context by comparison with prior observations with 5-aminoquinoline (5AQ) as the probe. 3AQ exhibits a relatively small change of dipole moment (Δμ = 2.2 D) upon photoexcitation, compared to 5AQ (Δμ = 6.1D), which might appear to be a hindrance in the way of its use as a solvation probe. Indeed, the values of parameters like spectral shifts are smaller for the present experiment with 3AQ. At the smallest concentration of alcohol used, its local mole fraction around the probe is significantly lower than in the previous experiments with 5AQ. However, these apparent disadvantages are outweighed by the significant increase in fluorescence intensity and lifetime observed with increasing concentration of ethanol in the solvent mixture, as opposed to the drastic fluorescence quenching that occurs for 5AQ. This is a marked advantage in the use of 3AQ in studies like the present one. The local mole fraction of ethanol and preferential solvation index experienced by 3AQ are in line with those reported for 5AQ. The disadvantage of the smaller magnitude of Δμ persists in the time resolved fluorescence experiments, for solvent mixtures with very low ethanol content. Negligible wavelength dependence of fluorescence transients of 3AQ is observed for x p = 0.002,. However, this effect is outweighed at higher alcohol concentrations, for which nanosecond dynamics of preferential solvation is observed.
用3-氨基喹啉(3AQ)作为荧光探针,在己烷-乙醇混合溶剂中优先溶剂化。将实验结果与先前以5-氨基喹啉(5AQ)为探针的观察结果进行了比较。与5AQ (Δμ = 6.1D)相比,3AQ在光激发下的偶极矩变化相对较小(Δμ = 2.2 D),这可能会阻碍其作为溶剂化探针的使用。事实上,在目前的3AQ实验中,谱移等参数的值更小。在最小酒精浓度下,其在探针周围的局部摩尔分数明显低于先前使用5AQ的实验。然而,随着溶剂混合物中乙醇浓度的增加,荧光强度和寿命显著增加,而不是发生在5AQ中的剧烈荧光猝灭,这些明显的缺点被抵消了。在像现在这样的研究中使用3AQ是一个明显的优势。3AQ的局部乙醇摩尔分数和优先溶剂化指数与5AQ一致。在时间分辨荧光实验中,对于乙醇含量非常低的溶剂混合物,仍然存在Δμ量级较小的缺点。在x p = 0.002时,观察到3AQ荧光瞬态的波长依赖性可以忽略不计。然而,在较高的酒精浓度下,这种效应被抵消了,因为可以观察到纳秒级的优先溶剂化动力学。
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引用次数: 0
Two near-infrared fluorescent probes based on dicyanoisfluorone for rapid monitoring of Zn2+ and Pb2+ 基于二氰芴酮的两种近红外荧光探针快速监测Zn2+和Pb2+
IF 3.2 3区 化学 Q3 CHEMISTRY, ANALYTICAL Pub Date : 2022-05-19 DOI: 10.1088/2050-6120/ac7199
Jia Li, Cuiping Zhou, Hong Yang, Xiongzhi Wu, Liqiang Yan
Zinc (Zn2+) and lead (Pb2+) ions in the environment have important effects on human health and environmental safety. Therefore, it is necessary to effectively detect them by a convenient and reliable analysis method. In this study, two near-infrared fluorescent probes for the fast determination of Zn2+ and Pb2+ were synthesized by a simple Schiff base reaction between the dicyanoisophorone skeleton and carbohydrazide derivatives. Among them, the probe with the thiophene-2-carbohydrazide group showed a selective fluorescence response to Zn2+ and Pb2+ with a maximum emission wavelength of 670 nm. And the detection limits of the probe for Zn2+ and Pb2+ were 1.59 nM and 1.65 nM, respectively. In contrast the probe modified by the furan-2-carbohydrazide group achieved quantitative detection of Zn2+, with a detection limit of 2.7 nM. These results were attributed to the fact that the probes bind to Zn2+ and Pb2+ in stoichiometric ratios of 1:1, blocking the intramolecular PET effect. Furthermore, these two probes can be recycled through the action of EDTA and have been successfully used to detect Zn2+ and Pb2+ in real water samples.
环境中的锌(Zn2+)和铅(Pb2+)离子对人类健康和环境安全具有重要影响。因此,有必要通过一种方便可靠的分析方法来有效地检测它们。本研究通过二氰基槐酮骨架与碳酰肼衍生物之间的简单席夫碱反应,合成了两种用于快速测定Zn2+和Pb2+的近红外荧光探针。其中,具有噻吩-2-碳酰肼基团的探针对Zn2+和Pb2+表现出选择性荧光响应,最大发射波长为670nm。探针对Zn2+和Pb2+的检测限分别为1.59nM和1.65nM。相反,由呋喃-2-碳酰肼基团修饰的探针实现了Zn2+的定量检测,检测极限为2.7nM。这些结果归因于探针以1:1的化学计量比与Zn2+和Pb2+结合,阻断了分子内PET效应。此外,这两种探针可以通过EDTA的作用回收,并已成功用于检测真实水样中的Zn2+和Pb2+。
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引用次数: 4
A novel reversible fluorescent probe for Cu2+ and S2− ions and imaging in living cells 一种新型可逆的Cu2+和S2−离子荧光探针及其在活细胞中的成像
IF 3.2 3区 化学 Q3 CHEMISTRY, ANALYTICAL Pub Date : 2022-05-19 DOI: 10.1088/2050-6120/ac719a
Shuaici Cheng, Ran Sun, Zhuo-Hui Wu, Huihui Mei, Haocheng Yang, Qingqing Kong, Kuoxi Xu
A novel fluorescent probe TSOC (thiazole salicylaldehyde oxazole chlorinated) was synthesized based on benzothiazole conjugated olefinic bonds with salicylicaldehyde unit as fluorophore and a phenyl oxazole unit as bonding unit. The probe could reversibly detect of Cu2+ and S2− over other common ions with longer emission and large stokes shift in an aqueous solution at pH 7.3 (DMSO-Hepes, v/v, 5:1, 10 mM). The bonding mechanism was supported through the titration experiment of fluorescence and absorption spectroscopy, 1H-NMR titration, HR-MS and DFT calculations. Moreover, the probe further exhibited good cell permeability and were successfully used to visualize Cu2+ and S2− in living cells.
以水杨醛为荧光基团,苯基恶唑为成键单元的苯并噻唑共轭烯烃键为基础,合成了新型荧光探针噻唑水杨醛氯代恶唑。在pH为7.3 (DMSO-Hepes, v/v, 5:1, 10 mM)的水溶液中,该探针比其他发射时间长、斯托克斯位移大的常见离子更能可逆地探测Cu2+和S2−。通过荧光和吸收光谱滴定实验、1H-NMR滴定、HR-MS和DFT计算支持了键合机理。此外,该探针还表现出良好的细胞渗透性,并成功地用于观察活细胞中的Cu2+和S2−。
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引用次数: 3
Construction of fluorescent logic gates for the detection of mercury(II) and ciprofloxacin based on phycocyanin 基于藻蓝蛋白的汞和环丙沙星荧光逻辑门的构建
IF 3.2 3区 化学 Q3 CHEMISTRY, ANALYTICAL Pub Date : 2022-05-18 DOI: 10.1088/2050-6120/ac7123
Han Dong, Mogos Girmatsion, Ruoyu Wang, Gang Lu, Yunfei Xie, Yahui Guo, H. Qian, Weirong Yao
Chemical pollutants such as heavy metals and antibiotics in the environment pose a huge threat to humans and animals. Our studies have demonstrated that the fluorescence of phycocyanin showed quenching responses towards both mercury (Hg2+) and ciprofloxacin (CIP), which acted in accordance with the ‘OR’ molecular logic gate. In order to discriminate Hg2+ and CIP in application scenarios, cysteine (Cys) was utilized to design another ‘INHIBIT’ logic gate, in which Hg2+ and Cys were the two inputs. Thus, an intelligent biosensor with dual-target identification capacity was successfully developed by using a fluorescent natural protein in an ingenious logic gate system.
环境中的重金属和抗生素等化学污染物对人类和动物构成了巨大威胁。我们的研究表明,藻蓝蛋白的荧光对汞(Hg2+)和环丙沙星(CIP)都表现出猝灭反应,这符合“OR”分子逻辑门。为了在应用场景中区分Hg2+和CIP,利用半胱氨酸(Cys)设计了另一个“INHIBIT”逻辑门,其中Hg2+与Cys是两个输入。因此,在一个巧妙的逻辑门系统中,利用荧光天然蛋白质成功开发了一种具有双靶识别能力的智能生物传感器。
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引用次数: 0
Fluorescence intensity ratio technique and its reliability 荧光强度比技术及其可靠性
IF 3.2 3区 化学 Q3 CHEMISTRY, ANALYTICAL Pub Date : 2022-05-17 DOI: 10.1088/2050-6120/ac70ab
Vishab Kesarwani, V. K. Rai
The present article reports the optical absorption and upconversion (UC) studies of 1.0 mol% Er3+/2.0 mol% Yb3+ doped/codoped glasses prepared by melt-quenching technique. The elements present and the composition of the prepared glass have been confirmed from XPS and XRF analysis respectively. Judd-Ofelt intensity parameters have been calculated using the absorption spectrum which is further utilized to predict the nature of Er_O bond, the transition probabilities, branching ratios and radiative lifetimes. The CIE study shows non-colour tunable and highly pure green emission (94.2%). The temperature-dependent UC emission spectra of the 2.0 mol% Yb3+ sensitized glass have been recorded at three different pump power densities to establish a reliable FIR based temperature scale. Furthermore, the Arrhenius fitting of the temperature-dependent spectra reveals low thermal quenching of green luminescence in the codoped glass.
本文报道了熔融淬火法制备1.0 mol% Er3+/2.0 mol% Yb3+掺杂/共掺杂玻璃的光吸收和上转换(UC)研究。用XPS和XRF分析分别确定了所制玻璃的元素和组成。利用吸收光谱计算了Judd-Ofelt强度参数,并利用该参数预测了Er_O键的性质、跃迁概率、分支比和辐射寿命。CIE的研究显示出非颜色可调和高纯度的绿色发光(94.2%)。在三种不同的泵浦功率密度下,记录了2.0 mol% Yb3+敏化玻璃的温度依赖性UC发射光谱,以建立可靠的基于FIR的温标。此外,温度相关光谱的Arrhenius拟合表明,共掺杂玻璃中绿色发光的热猝灭程度较低。
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引用次数: 9
Vacuum ultraviolet photoluminescence of NaMgF3:Sm and NaMgF3:Sm,Ce: energy levels of the lanthanides in NaMgF3:Ln compounds NaMgF3:Ln化合物中镧系元素的真空紫外光致发光研究
IF 3.2 3区 化学 Q3 CHEMISTRY, ANALYTICAL Pub Date : 2022-05-17 DOI: 10.1088/2050-6120/ac70aa
J. Schuyt, G. Williams, K. Shinohara, T. Shimizu, K. Yamanoi, M. Cadatal-Raduban
The luminescence properties of NaMgF3:Sm and NaMgF3:Ce,Sm were studied in the vacuum ultraviolet spectral region. Excitation bands corresponding to the charge transfer processes F− → Sm3+, O2− → Sm3+, and O2− → Ce3+, and the energy transfer processes Ce3+ → Sm3+ and O2− → Sm3+, were observed. The energies of the Sm3+ charge transfer transitions and the crystal field split Ce3+ 4f 05d 1 transitions were used to construct a complete host referred binding energy diagram for the series of lanthanide-doped NaMgF3:Ln compounds. We demonstrate that the optical and luminescence properties predicted by the binding energy diagram are in good agreement with those predicted by the binding energy diagram constructed via the alternative impurity-informed method, and all available experimental data regarding the NaMgF3:Ln compounds. We demonstrate that NaMgF3:Ln compounds are model systems for the study of charge trapping phenomena and divalent lanthanide luminescence. Ultimately, we validate that the impurity-informed method can be used to establish the energy levels of lanthanides in fluoride systems.
研究了NaMgF3:Sm和NaMgF3:Ce,Sm在真空紫外光谱区的发光特性。与电荷转移过程F−相对应的激发带→ Sm3+、O2−→ Sm3+和O2−→ Ce3+和能量转移过程Ce3+→ Sm3+和O2−→ Sm3+。利用Sm3+电荷转移跃迁和晶体场分裂Ce3+4f05d1跃迁的能量,构建了一系列镧系掺杂NaMgF3:Ln化合物的完整的主体结合能图。我们证明了结合能图预测的光学和发光性质与通过替代杂质知情方法构建的结合能图以及关于NaMgF3:Ln化合物的所有可用实验数据预测的光学性质和发光性质非常一致。我们证明了NaMgF3:Ln化合物是研究电荷捕获现象和二价镧系元素发光的模型体系。最终,我们验证了杂质知情方法可以用于确定氟化物系统中镧系元素的能级。
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引用次数: 4
A cuvette-compatible Zn2+ sensing tool for conventional spectrofluorometers prepared by copolymerization of macrocyclic fluoroionophores on quartz glass surface 石英玻璃表面大环氟离子载体共聚制备的用于常规荧光光谱仪的比色杯兼容Zn2+传感工具
IF 3.2 3区 化学 Q3 CHEMISTRY, ANALYTICAL Pub Date : 2022-05-11 DOI: 10.1088/2050-6120/ac6ecb
Ádám Golcs, Korinna Kovács, Panna Vezse, L. Bezúr, P. Huszthy, T. Tóth
We report here the development of a surface-modified quartz glass sheet, which affords an opportunity for converting conventional spectrofluorometers to ion-selective optochemical sensors by placing it diagonally into a photometric cuvette. Moreover, we describe a generalizable technique, which allows the usage of any polymerizable ionophores for developing multiple-use fluorescent chemosensors of various selectivity. A fluorescent bis(acridino)-crown ether containing allyl groups was photocatalytically copolymerized with a methacrylate-acrylamide-based monomer mixture to obtain an ion-selective sensor membrane layer on the surface of the cuvette-compatible glass sheet. This glass membrane-based direct optode enabled the analysis of Zn2+ above a lower limit of detection of 2.2 × 10–7 mol·l−1 with an excellent reusability. Limiting factors, like pH and competing ionic or organic agents were thoroughly investigated. Moreover, spiked river-water samples were measured to demonstrate applicability. The proposed sensor placed in any conventional spectrofluorometer provides an innovative method for perturbation-free analysis of Zn2+ for all the chemists in need of a fast, easy-to-use, portable and regenerable analyzer without the requirement of an analyte-specific instrumentation.
我们在这里报告了一种表面改性石英玻璃片的发展,它提供了一个机会,将传统的荧光光谱仪转换为离子选择性光化学传感器,通过对角线放置在光度比色皿中。此外,我们描述了一种可推广的技术,该技术允许使用任何可聚合的离子载体来开发各种选择性的多用途荧光化学传感器。将一种含烯丙基的荧光双(吖啶酮)冠醚与甲基丙烯酸酯-丙烯酰胺基单体混合物进行光催化共聚,得到了一层离子选择性传感膜层。这种基于玻璃膜的直接光电器件使Zn2+的检测下限超过2.2 × 10-7 mol·l−1,具有良好的可重复使用性。限制因素,如pH和竞争离子或有机剂进行了深入的研究。此外,还测量了加标的河水样本以证明其适用性。所提出的传感器放置在任何传统的荧光光谱仪中,为所有需要快速,易于使用,便携式和可再生分析仪的化学家提供了一种创新的无扰动分析Zn2+的方法,而不需要分析物专用仪器。
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引用次数: 1
A highly selective and sensitive ratiometric fluorescent probe for quantitative detection of Al(III) in different natural matrices 一种高选择性、高灵敏度的比率荧光探针用于不同天然基质中Al(III)的定量检测
IF 3.2 3区 化学 Q3 CHEMISTRY, ANALYTICAL Pub Date : 2022-05-11 DOI: 10.1088/2050-6120/ac6eca
R. Shanmugapriya, P. S. Kumar, C. Nandhini, K. Satheeshkumar, K. Vennila, K. Elango
A highly selective and sensitive assay of Al(III) using ratiometric fluorescence enhancement is reported in an aqueous solution. The probe (named RS5) exhibits a red-shift of 54 nm upon binding with Al(III) ion. The significant enhancement response of RS5 at 481 nm is attributed to the formation of a 1:1 complex between the probe and Al(III), wherein RS5 acts as a tridentate NNN-donor ligand. The complexation process is ascertained by 1H, 13C, and 27Al NMR and HR-MS spectral techniques. The binding constant of the complex is determined to be 1.3 × 105 M−1. The ratiometric change in fluorescence upon complexation with Al(III) is ascribed to an increase in intramolecular charge transfer (ICT) transition along with chelation enhanced fluorescence (CHEF) processes. The probe can be applied for monitoring Al(III) in a pH range of 6–8. The limit of detection (LOD) of RS5 for the examination of Al(III) is found to be 0.3 μM. With an aim to understand the sensing behavior of RS5, the optical properties of the probe and its Al(III) complex are investigated using density functional theory (DFT) and time-dependent density functional theory (TD-DFT) methods. The probe is successfully employed for the determination of Al(III), with very high recovery percentages, in natural matrices like deep well water, tap water, drinking water, pond water, river water, bovine serum albumin (BSA) solution and blood serum.
报道了在水溶液中使用比率荧光增强对Al(III)进行高选择性和灵敏的测定。探针(命名为RS5)在与Al(III)离子结合时表现出54nm的红移。RS5在481nm处的显著增强反应归因于探针和Al(III)之间形成1:1的络合物,其中RS5充当三齿NNN供体配体。通过1H、13C和27Al NMR和HR-MS光谱技术确定了络合过程。该配合物的结合常数为1.3×105M−1。与Al(III)络合后荧光的比率变化归因于分子内电荷转移(ICT)跃迁以及螯合增强荧光(CHEF)过程的增加。该探针可用于监测pH范围为6-8的Al(III)。RS5检测Al(III)的检出限为0.3μM。为了了解RS5的传感行为,使用密度泛函理论(DFT)和时间相关密度泛函理论方法(TD-DFT)研究了探针及其Al(III)配合物的光学性质。该探针成功地用于测定天然基质如深井水、自来水、饮用水、池塘水、河水、牛血清白蛋白(BSA)溶液和血清中的Al(III),具有很高的回收率。
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引用次数: 4
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Methods and Applications in Fluorescence
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