环丙沙星的光谱性质、质子化作用与荧光量子产率

研究了环丙沙星(ciprofloxacin, CIP)在不同pH条件下的荧光光谱、紫外吸收光谱和质子化作用,测量了CIP在中性条件下的荧光量子产率。在H+浓度大于1 mol·L-1的HCl介质中,CIP分子(简写为HL)可以结合3个质子而以H₄L3+形式存在,有微弱的荧光,最大荧光发射波长(λ_ｍａｘ)为456 nm。在pH 0～2的酸性条件下,CIP主要以H₃L2+形式存在,λ_ｍａｘ为450 nm,荧光较弱,荧光强度随pH的升高而上升。在pH 2～4时,CIP主要以H₂L+形式存在,具有强荧光,λ_ｍａｘ仍为450 nm。当pH＞4时,λ_ｍａｘ逐步蓝移到414 nm,荧光强度随pH的升高而稍有降低,同时紫外吸收光谱也有明显变化,表明H₂L+随pH升高而失去质子,以双极离子HL形式存在。当pH＞8时,荧光强度随pH升高而减弱至消失,表明HL逐步失去质子,转化为无荧光的阴离子L-。在分子形态变化过程中,最大荧光激发波长始终在275 nm附近,但最大荧光发射波长有较大变化。在pH 7.0的缓冲溶液中,以硫酸奎宁为参比,测得CIP在最大荧光激发波长275 nm处的荧光量子产率为0.12。     

A multi‐addressable molecular switch based on a novel diarylethene with an imidazo [4,5‐f] [1,10] phenanthroline unit

A novel unsymmetrical diarylethene with an imidazo [4,5‐f] [1,10] phenanthroline unit has been synthesized, and its properties including photochromism and fluorescence have been investigated. It showed favorable photochromism and functioned as notable fluorescence switches by photoirradiation in both solution and a poly (methylmethacrylate) film. Moreover, the interaction between the phenanthroline unit of its closed‐ring isomer with trifluoroacetic acid caused a notable change in its absorption, accompanied by an evident color change from magenta to slateblue. Its fluorescence could be modulated by trifluoroacetic acid and triethylamine. By adding enough amount of trifluoroacetic acid in chloroform, its emission peak hypochromatic shifted from 501 nm to 456 nm, and the intensity increased significantly with a concomitant change of color from bright cyan to bright blue. However, its emission intensity decreased notably by 95% with a fluorescence color change from bright cyan to dark gray by the addition of triethylamine. Copyright © 2013 John Wiley & Sons, Ltd.     

CaAl_2Si_2O_8∶Eu,Ce,Tb单基三元掺杂荧光材料的制备及其光谱学特征研究

采用高温固相法制备了CaAl_2Si_2O_8∶Eu,Ce,Tb单基三元掺杂的荧光材料。使用X射线衍射仪(XRD)、拉曼光谱仪(Raman)和荧光分光光度计(PL)等测试手段对该荧光材料进行表征。采用XRD表征了样品的物相组成,测试结果表明稀土离子Eu~(2+)置换Ca~(2+)并没有引起CaAl_2Si_2O_8基质晶格结构的变化。拉曼光谱分析证实了样品中硅氧四面体和铝氧四面体的存在,表明了Eu~(2+)替代Ca~(2+)的数量与晶体形态畸变程度有关,Eu~(2+)进入基质晶格的数量影响着硅(铝)氧四面体的数量。PL测试结果表明样品在325nm光激发下,其发射峰主要表现为426nm(蓝光区)的强宽带发射峰和541nm(绿光区)的弱发射峰,其中426nm处的宽带发射峰可通过高斯拟合成三个位于393,419和474nm的拟合峰;对比分析荧光性能以及同等合成条件下样品荧光强度的不同,确定了该荧光材料在三掺Eu∶Ce∶Tb的摩尔比为1∶1∶1.5时所发射荧光最强。CIE色度图坐标显示三种掺杂比例下制备的荧光材料均发射蓝色荧光,光显色性好,色温低,是一种适合作为紫外-近紫外激发的LED用蓝色荧光材料。     

Achieving Multicolor Upconversion Emissions without Changing Compositions

It is widely recognized that a proper way of adjusting fluorescence color is meaningful for pushing forward upconversion materials to be utilized in anti-counterfeiting, display and solid-state lightning applications. Traditional routes that apply different host materials and/or doping categories to adjust fluorescence color have shown large color region tunability yet have to rely on complex synthesis process accompanied with time and raw material consumption. In this work, in order to get a wide luminous color gamut without depending on reciprocating synthesis, we desinged and provided a high-sensitizer-concentration upconversion crystals, hexagonal NaLuF₄:Yb³⁺/Er³⁺ (50/2 mol%), whose red-to-green emission intensity ratio can be conveniently tuned from 2.69 to 4.96 by simply modulating excitation power densities. The promoted three-photon-population progress of red emission achieved by using an intensive excitation laser is considered to be responsible for the facile upconversion modulation. The results may provide new ideas for emission color control that based on external parameters in identical host and the greatly amplified excitation power-sensitivity of NaLuF₄:Yb³⁺/Er³⁺ (50/2 mol%) is highly potential for fluorescence anti-fake and colorful display applications.

     

Determination of Hypochlorite via Fluorescence Change from Blue to Green Based on 4-(1 H-imidazo [4,5-f] [1,10]-phenanthrolin-2-yl) Benzaldehyde Oxime

The new design strategy will provide the possibility for preparing a dynamic sensor by employing the inhibition of C?=?N isomerization. In this work, the functional probe 4-(1 H-imidazo [4,5-f] [1,10]-phenanthrolin-2-yl) benzaldehyde oxime (compound 4) has been synthesized and such molecule gives rise to blue emission. Due to the incorporation of hypochlorite, the oxime group can be oxidized to the structure of aldehyde. As a result, the molecular motif exhibits sharp emission change from blue to green due to the addition of hypochlorite with enough sensitivity and selectivity (detection limit?=?53 nM, linear range 0.5-8.0 µM). It has also been used for monitoring ClO^? by employing solution color change and the absorption signal difference could effectively rule out the effects of interference species. To our knowledge, it will be the first case of a highly selective hypochlorite sensor derived from oxime isomerization reaction based on phenanthroline backbone.

     

A Hybrid Coumarin-Semifluorescein-Based Fluorescent Probe for the Detection of Cysteine

A new type of turn-on fluorescent probe CF-AC for the detection of Cys was firstly reported. The probe exhibited an excellent response to Cys with high selectively and sensitivity. In the presence of Cys, two fluorescence emission peaks at 525 nm and 650 nm appeared accompanied by the fluorescence color change from blue to red. Morever, the probe had good biocompatibility and could be successfully used for fluorescence imaging of Cys in MCF-7 cells.     

检测Fe~(3+)/F~-的双功能喹哪啶衍生物荧光探针

对一种简单结构的喹哪啶衍生物作为离子荧光探针的性能进行了研究。探针由8-羟基喹哪啶的2-位引入水杨醛构成,通过双键连接喹啉环与苯环以及推-拉电子基团构成大共轭结构,使其发光量子产率提高;探针分子中的氮、氧原子提供了良好的配位作用点,能选择性与离子配合而使荧光性质发生变化。在乙腈/水溶液中,Fe~(3+)与探针形成1∶1的配合物而使其荧光猝灭,配合为自发的熵驱动放热过程。红外光谱和1 H NMR滴定推测探针分子中的两个羰基氧和氮的孤对电子参与Fe~(3+)络合,光诱导引发电子转移过程导致荧光猝灭。在乙腈溶液中,F~-使探针在415nm处的荧光峰降低,在560nm处出现新荧光峰,形成比率荧光,荧光由蓝色变为黄色至橙红色。同时,F~-使探针在280和340nm处的紫外吸收峰降低,在455nm处出现新的吸收峰,形成比率吸收,颜色由无色变为黄色至橙色。1 H NMR滴定推测探针分子与F~-是通过氢键作用。为一种同时检测阴、阳离子的双功能探针,荧光法对Fe~(3+)和F~-的检出限分别低至13.6nmol·L~(-1)和1.6μmol·L~(-1),紫外法对F~-的检出限低至16.5μmol·L~(-1)。利用探针对F~-识别时明显的颜色变化,建立了可视性,快速度,易操作的目视检测微量F~-的方法。     

Synthesis and Investigation of Derivatives of 1,8-Naphthalimide with a Red Emission via an Aromatic Nucleophilic Substitution Reaction

1,8-Napthalimides (NIs) have been widely used as fluorescent molecules in biological, chemical, and medical fields because NIs shows high stability and various fluorescence properties under different conditions. However, NIs typically display a fluorescence emission wavelength in the range of 350 – 550 nm which can be notably interfered with by autofluorescence in living cells, significantly limiting their bio-applications. Moreover, low solubility in aqueous media is another major limitation for NIs. In this project, four derivatives of NIs (1–4) have been synthesized via an aromatic nucleophilic substitution reaction and their photophysical properties have been investigated in various media (water, MeOH, MeCN, DMSO, EtOAc, and THF). All of these derivatives (1–4) show a long emission wavelength around 600 nm and high solubility in polar solvents. Particularly molecules (1–4) show the longest emission (624–629 nm) in water and the fluorescence intensity is not significantly varied in the range of pH 4–11. These unique features, long emission wavelength, high solubility, and high stability in difference pH media, will allow these derivative (1–4) to be used as excellent labeling reagents in the biological system.

     

激光激励下镝离子掺杂氟硼酸盐玻璃荧光体的辐照参数

采用高温熔融法制备了镝离子掺杂氟硼酸盐玻璃荧光体,利用积分球绝对光谱测试系统,在453 nm蓝色激光二极管激发下,对玻璃荧光体的荧光光谱进行表征,解析出玻璃荧光体的相关绝对荧光参量。测试与计算结果表明,1.0 Wt% Dy₂O₃掺杂玻璃荧光体在功率15.81 mW的蓝色激光激发下,净发射光谱功率是286.91 μW,发射光子数为17.17×1014 cps,其荧光量子产率达到25.86%。为提高玻璃荧光体对泵浦激光的利用率,减少残余激光成分,进而改善组合光品质,制备了大体积的1.5 Wt% Dy₂O₃掺杂玻璃荧光体,在高功率的蓝色激光激发下获得白色照明效果,该玻璃荧光体在激发功率分别为56.0和252.7 mW的激光激发下,组合荧光对应的色坐标分别是(0.316, 0.287)和(0.303,0.268)。激光激励下的高效白色发光表明Dy3+掺杂氟硼酸盐玻璃荧光体在激光照明领域具有良好的应用前景。     

中药常山水浸液的荧光光谱研究

报道了中药常山沸水浸取液的荧光光谱。在三维荧光等高线光谱图中出现3个喹唑啉类生物碱(常山的主要活性成分)的荧光峰,其激发波长分别为235,270和320 nm,发射波长均为430 nm。三维荧光等高线光谱是一种形象的指纹图谱,可以作为中药定性分析的依据。在pH 3～6范围内,常山水浸液二维荧光激发光谱的形状随pH的变化而改变,推测是由于喹唑啉类生物碱分子中喹唑酮环上N-1的质子化所致。在近中性条件下,常山水浸液的荧光强度与溶液浓度之间有良好的线性关系,可以作为喹唑啉类生物碱定量分析的基础。     

Blue Cooperative Luminescence In Yb3+-Doped Barium Gallogermanate Glass Excited At 976 nm

The Yb³⁺-doped barium gallogermanate glass has been prepared via the conventional melt method. The absorption spectra, the near infrared emission spectra, the upconversion emission spectra and the differential scanning calorimetry have been measured. Bright blue upconversion emission centered at 476 nm has been observed under the 976 nm laser diode excitation at room temperature. The blue upconversion emission mechanism has been discussed on the blue emission intensity and the measured lifetime. The slope of the log-log plot of the blue emission intensity versus the pump power is equal to 1.98, and the blue luminescence decay time is half of the near infrared fluorescence decay time, confirming that the blue emission comes from Yb³⁺-Yb³⁺ pairs cooperative upconversion mechanism. The result of differential scanning calorimetry suggests that this type of glass is suitable as a potential candidate for fiber drawing.     

Gold‐Cluster‐Based Dual‐Emission Nanocomposite Film as Ratiometric Fluorescent Sensing Paper for Specific Metal Ion

A dual‐emission ratiometric fluorescent sensing film for metal ion detection is designed. This dual‐emission film is successfully prepared from chitosan, graphitic carbon nitride (g‐C₃N₄), and gold nanoclusters (Au NCs). Here, it is shown that the g‐C₃N₄ not only serves as the fluorescence emission source, but also enhances the mechanical and thermal stability of the film. Meanwhile, the Au NCs are adsorbed on the surface of chitosan film by the electrostatic interaction. The as‐prepared dual‐emission film can selectively detect Cu²⁺, leading to the quench of red fluorescence of Au NCs, whereas the blue fluorescence from g‐C₃N₄ persists. The ratio of the two fluorescence intensities depends on the Cu²⁺ concentration and the fluorescence color changes from orange red to yellow, cyan, and finally to blue with increasing Cu²⁺ concentration. Thus, the as‐prepared dual‐emission film can be worked as ratiometric sensing paper for Cu²⁺ detection. Furthermore, the film shows high sensitivity and selectivity, with low limit of detection (LOD) (10 ppb). It is observed that this novel gold‐cluster‐based dual‐emission ratiometric fluorescent sensing paper is an easy and convenient way for detecting metal ions. It is believed that this research work have created another avenue for the detection of metal ions in the environment.     

Optical parameters and upconversion fluorescence in Tm3+/Yb3+ codoped tellurite glass

Tm³⁺/Yb³⁺ codoped tellurite glass has been prepared. Density, refractive index, optical absorption, Judd-Ofelt parameters and spontaneous transition probabilities of Tm³⁺ have been measured and calculated, respectively. Intense blue three-photon upconversion fluorescence and S-band (1470 nm) fluorescence were investigated under the excitation of a 980 nm diode laser at room temperature. Judd-Ofelt parameters, strong blue three-photon upcoversion emission of Tm³⁺ in glass indicate that Tm³+/Yb³⁺ codoped tellurite glass is a promising blue color upconversion optical and laser material. In addition, experiment results showed the 980 nm laser was more efficient than 808 nm laser when pumping Tm³⁺/Yb³⁺ codoped tellurite glass, Tm³⁺/Yb³⁺ codoped tellurite glass also could be a promising material for S-band amplification.     

基于CIE色度图的博尔塔拉河与精河水体荧光峰发光性初探

以艾比湖主要入湖河流博尔塔拉河及精河水体为研究对象,使用寻峰法找出水体荧光峰,采用色坐标分析法对博尔塔拉河与精河水体荧光发射光谱特性及荧光峰的发光性进行分析。首先,博尔塔拉河与精河水体的荧光发射光谱均含有3个荧光峰,各荧光峰的出现位置与峰强度大小均不同。博尔塔拉河第二荧光峰远大于第一荧光峰或第一荧光峰与第二荧光峰基本持平;精河前5个样点的3个荧光峰强度随波长增大呈依次递减分布,6号采样点第一荧光峰与第二荧光峰基本持平。其次,博尔塔拉河与精河3个荧光峰在色坐标中分布位置大致相同,且各点的荧光峰分布较为聚集,均在蓝光区域,属蓝光发射。最后,各荧光峰在CIE坐标中聚集分布,第一荧光峰在色坐标最底端;第二荧光峰分布在第一荧光峰上端,x坐标与第一荧光峰接近;第三荧光峰整体聚集分布在蓝光区域的右上角。     

A New Dual-peak Fluorescent Probe for Water Content Detection Made From Taxus

In this paper, the leaves of Taxus were used as the sole carbon source, and two kinds of carbon dots blue and red, with different properties, were synthesized by the hydrothermal method under different conditions. The red carbon dots were quenched in the water, and the blue carbon dots had stable fluorescence properties in water environment. The bimodal fluorescence probe formed by mixing could accurately and stably measure the water content in ethanol, which was in the range of 82.5%-100%, is highly correlated with the fluorescence intensity ratio (I₄₈₁/I₆₇₈) of mixed carbon dots under 390 nm excitation light, with R²?=?0.995 and the detection limit as low as 0.31%. The experimental materials are environmentally friendly, low in cost, and simple to operate, as well as the water content measured by proportional fluorescence has high accuracy, which provides a new method for measuring moisture in ethanol.

     

甲醛功能化聚乙烯亚胺/曙红Y比率荧光法测定六偏磷酸钠

在微波辅助条件下,合成了甲醛功能化的聚乙烯亚胺(FPEI),在激发波长为340 nm时,FPEI的荧光发射波长470 nm,紫外灯下发蓝色荧光。在此激发条件下,曙红Y(Y eosin Y, EY)的荧光发射波长为540 nm,发绿色荧光。在酸性介质中,FPEI和 EY 通过静电作用形成FPEI/EY复合物,导致EY 在540 nm 的荧光显著猝灭,而FPEI本身的荧光只有微弱的降低。当加入六偏磷酸钠(SHMP)时,SHMP、EY与FPEI发生竞争结合,由于SHMP与FPEI表面质子化氨基的静电作用强于EY,EY从FPEI/EY复合物中释放导致540 nm荧光强度逐渐恢复。当SHMP与FPEI/EY 混合时,EY 540 nm荧光强度与FPEI 470 nm 荧光强度的比值(F₅₄₀/F₄₇₀)与SHMP浓度呈较好的线性关系,在紫外灯照射下体系的荧光由蓝色逐渐变为绿色,由此建立了FPEI/EY比率荧光快速测定SHMP的新方法。在最优条件下,线性范围为0.1~4.2 μmol·L-1,检出限(3σ)为38 nmol·L-1。该方法选择性好、简单、快速, 已成功应用于茶饮料中SHMP的分析检测。     

Effects of flash boiling injection on in-cylinder spray,mixing and combustion of a spark-ignition direct-injection engine

Higher engine efficiency and ever stringent pollutant emission regulations are considered as the most important challenges for today's automotive industry. Fast evaporation and combustion technique has caused unprecedented attention due to its potential to solve both of the above challenges. Flash boiling, which features a two-phase flow that constantly generates vapor bubbles inside the liquid spray is ideal to achieve fast evaporation and combustion inside direct-injection (DI) gasoline engines. In this study, three spray conditions, including liquid, transitional flash boiling and flare flash boiling spray were studied for comparison under cold start condition in a spark-ignition direct-injection (SIDI) optical gasoline engine. Optical access into the combustion chamber includes a quartz linear and a quartz insert on the piston. In separate experiments, we recorded the crank angle resolved spray morphology using laser scattering technique, and distribution of fuel before ignition employing laser induced fluorescence technology, as well as time-resolved color images of flame with high-speed camera. The spray morphology during the intake stroke shows stronger plume-plume and plume-air interaction under flash boiling condition, as well as smaller penetration. Then around the end of compression (before ignition), the fuel distribution is also shown to be more homogeneous with less cyclic variation under flash boiling. Finally, from the color images of the flame, it was found that with the increase of superheat degree, the diffusion rate of blue flame (generated by excited molecules) is higher, which is considered to be related with the larger fractal dimension of the flame front. Also, the combustion is more complete with less yellow flame under flash boiling.     

Upconversion fluorescence spectroscopy of Er~(3+)-doped lead oxyfluorosilicate glass

Upconversion fluorescence emission of Er3+-doped oxyfluorosilicate glass excited at 975 nm is experimentally investigated. The results reveal that the intense green and red emission, and weak blue emission centered at 525, 543, 655, and 410 nm, respectively. A two-photon upconversion process is assigned to the green and red emission while a three-photon process is responsible for blue upconversion. The possible upconversion mechanisms are discussed based on excited state absorption and energy transfer between excited Er3+ ions. The intense upconversion fluorescence of Er3+-doped lead oxyfluorosilicate glass may be a potentially useful material for developing upconversion optical devices.     

天然及有机充填处理绿松石的荧光光谱研究

绿松石常见蓝色、绿色和杂色等颜色,其中蓝色和绿色者因颜色鲜艳,价值最高,因此绿松石优化处理品也多为蓝色和绿色。利用有机树脂对质松色浅的绿松石进行充填处理（简称“有机充填”）是目前最主要的绿松石优化处理方式,常见浸胶和注胶两种处理类型。采用基础宝石学测试、红外吸收光谱仪、三维荧光光谱仪和X射线荧光光谱仪等测试技术分别对天然绿松石、浸胶和注胶充填处理绿松石的宝石学特征及谱学特征进行了系统的对比分析和研究。研究结果显示,天然绿松石紫外灯长波下具中等至弱荧光,荧光强度与色调和致密程度相关,浸胶绿松石长波荧光强于相同颜色天然绿松石,注胶绿松石长、短波下均具有中等至弱荧光。浸胶绿松石的红外吸收光谱显示,除绿松石本身特征峰外,还可见1 739 cm-1附近ν(C═O)吸收峰和2 926和2 851 cm-1亚甲基的吸收峰,注胶绿松石除羰基及亚甲基吸收峰更强外,还可见1 508 cm-1处苯环骨架特征吸收峰。三维荧光光谱测试显示,天然蓝色绿松石具有一个Ex为370 nm的中等强度特征荧光峰、半峰宽约为100 nm,绿色、杂色系和低致密度绿松石荧光极弱;蓝色浸胶绿松石具有Ex为380～400 nm内的强对称荧光特征峰,绿色浸胶绿松石可见一较强的荧光特征峰,半峰宽约为80 nm;蓝色注胶绿松石具有两个Ex分别为278和390 nm附近的较弱强度荧光特征峰,绿色注胶绿松石具有中等强度的荧光峰、半峰宽约为150 nm,荧光峰区域范围增大可能因为含有较多有机物。结合X射线荧光光谱仪分析Fe对绿松石的荧光会产生一定抑制作用。绿松石荧光特征和三维荧光光谱测试作为无损检测技术,具有测试简便、快捷、有效的特点,对准确鉴定绿松石和有机充填处理品具有重要的现实意义。     

溶剂热法合成橙-绿双波段荧光碳点

荧光碳点具有激发波长依赖的独特性质,有望基于此制备检测溶液pH值的荧光探针。以柠檬酸和尿素为原料、N,N-二甲基甲酰胺为溶剂,采用一步溶剂热法在200℃下保温12 h制备了一种新型的具有橙-绿双波段荧光发射性能的水溶性碳点。采用透射电子显微镜、X射线衍射、拉曼光谱、傅里叶变换红外光谱和X射线光电子能谱等方法对荧光碳点的组成和形貌进行了表征,还通过荧光发射光谱和紫外-可见吸收光谱对其光学性能进行了研究。结果表明,制备的碳点粒径为2.7~4.3 nm,表面带有大量含氧官能团,具有良好的水分散性。在440 nm和540 nm波长光激发下分别呈现绿色(500 nm)和橙色(590 nm)双波段荧光发射。合成的荧光碳点发光性能对pH值具有敏感性:在强碱性溶液中,590 nm的荧光强度比水溶液中提高了6.71倍,同时吸收峰的蓝移使得自然光下其溶液颜色发生了明显改变,具有强碱性指示剂的作用;在pH值为2~6的酸性溶液中,500 nm与590 nm发光峰强度比与pH值之间呈现良好的线性关系,展现了作为pH值比率荧光探针的应用潜力。