超分子化合物的荧光增敏效应及浊点萃取-荧光光谱法测定氟比洛芬

比较氟比洛芬在乙醇介质,及对其浊点萃取后在非离子型表面活性剂Tergitol15-S-7胶束-乙醇介质中的荧光光谱,发现氟比洛芬的荧光发射峰有明显红移的现象,且荧光信号显著增强。研究证实Tergitol 15-S-7与氟比洛芬激发态分子之间的超分子作用力是荧光增强的主要原因。据此,提出了一种浊点萃取-荧光光谱法测定氟比洛芬的新方法。在优化的实验条件下,氟比洛芬测定的线性范围为1.0×10-8~1.0×10-6 mol·L-1,检出限为1.1×10-9 mol·L-1。     

Surface‐Enhanced Raman Scattering Based on Controllable‐Layer Graphene Shells Directly Synthesized on Cu Nanoparticles for Molecular Detection

Graphene shells with a controllable number of layers were directly synthesized on Cu nanoparticles (CuNPs) by chemical vapor deposition (CVD) to fabricate a graphene‐encapsulated CuNPs (G/CuNPs) hybrid system for surface‐enhanced Raman scattering (SERS). The enhanced Raman spectra of adenosine and rhodamine 6G (R6G) showed that the G/CuNPs hybrid system can strongly suppress background fluorescence and increase signal‐to‐noise ratio. In four different types of SERS systems, the G/CuNPs hybrid system exhibits more efficient SERS than a transferred graphene/CuNPs hybrid system and pure CuNPs and graphene substrates. The minimum detectable concentrations of adenosine and R6G by the G/CuNPs hybrid system can be as low as 10^?8 and 10^?10 M , respectively. The excellent linear relationship between Raman intensity and analyte concentration can be used for molecular detection. The graphene shell can also effectively prevent surface oxidation of Cu nanoparticles after exposure to ambient air and thus endow the hybrid system with a long lifetime. This work provides a basis for the fabrication of novel SERS substrates.     

A new myrsinol-type diterpene polyester from Euphorbia dracunculoides Lam

A new myrsinol-type diterpene polyester, 14-deoxo-3β-O-propinoyl-2α,5α,7β,15β-tetra-O-acetyl-14α-O-benzoyl-myrsinol (1), and its known analogue, 14-deoxo-3β-O-prorionyl-5α,15β-di-O-acetyl-7β-O-nicotinoyl-myrsinol-14β-acetate (2), together with a monoterpenoid, pubinernoid A (3), two indole alkaloids, neoechinulin A (4) and dihydroxyisoechinulin A (5), two benzene derivatives, siringin (6) and (3-methoxyphenyl) acetic acid (7), were isolated from the 70% acetone extract of the aerial parts of Euphorbia dracunculoides Lam. Their structures were elucidated on the basis of spectroscopic evidence and comparison with literature reports. The absolute configuration of 1 was deduced by comparing experimental and calculated ECD spectra. Among them, compounds 4 and 5 were first obtained from the plant source. In addition, the ¹³C NMR data of compound 2 was reported for the first time.     

High-internal-phase-emulsion polymeric monolith coupled with liquid chromatography–electrospray tandem mass spectrometry for enrichment and sensitive detection of trace cytokinins in plant samples

High-internal-phase-emulsion polymers (polyHIPEs) show great promise as solid-phase-extraction (SPE) materials because of the tremendous porosity and highly interconnected framework afforded by the high-internal-phase-emulsion (HIPE) technique. In this work, polyHIPE monolithic columns as novel SPE materials were prepared and applied to trace enrichment of cytokinins (CKs) from complex plant samples. The polyHIPE monoliths were synthesized via the in-situ polymerization of the continuous phase of a HIPE containing styrene (STY) and divinylbenzene (DVB) in a stainless column, and revealed highly efficient and selective enrichment ability for aromatic compounds. Under the optimized experimental conditions, a method using a monolithic polyHIPE column combined with liquid chromatography–electrospray tandem mass spectrometry (LC–MS–MS) was developed for the simultaneous extraction and sensitive determination of trans-zeatin (tZ), meta-topolin (mT), kinetin (K), and kinetin riboside (KR). The proposed method had good linearity, with correlation coefficients (R ²) from 0.9957 to 0.9984, and low detection limits (LODs, S/N?=?3) in the range 2.4–47 pg mL^?1 for the four CKs. The method was successfully applied to the determination of CKs in real plant samples, and obtained good recoveries ranging from 68.8 % to 103.0 % and relative standard deviations (RSDs) lower than 16 %.     

Determination of hexavalent chromium in traditional Chinese medicines by high‐performance liquid chromatography with inductively coupled plasma mass spectrometry

An analytical method that combined high‐performance liquid chromatography with inductively coupled plasma mass spectrometry has been developed for the determination of hexavalent chromium in traditional Chinese medicines. Hexavalent chromium was extracted using the alkaline solution. The parameters such as the concentration of alkaline and the extraction temperature have been optimized to minimize the interconversion between trivalent chromium and hexavalent chromium. The extracted hexavalent chromium was separated on a weak anion exchange column in isocratic mode, followed by inductively coupled plasma mass spectrometry determination. To obtain a better chromatographic resolution and sensitivity, 75 mM NH₄NO₃ at pH 7 was selected as the mobile phase. The linearity of the proposed method was investigated in the range of 0.2–5.0 μg L^?1 (r² = 0.9999) for hexavalent chromium. The limits of detection and quantitation are 0.1 and 0.3 μg L^?1, respectively. The developed method was successfully applied to the determination of hexavalent chromium in Chloriti lapis and Lumbricus with satisfactory recoveries of 95.8–112.8%.     

基于罗丹明B的激活型α-酮戊二酸荧光探针

α-酮戊二酸(α-KA)是人体三羧酸循环的一个重要代谢中间体,异柠檬酸脱氢酶-1(IDH1)及异柠檬酸脱氢酶-2(IDH2)的突变将导致α-KA转化为2-羟基戊二酸(2HG),该过程与急性骨髓性白血病(AML)密切相关,因此检测人体内α-KA的含量变化具有重要意义。本文以罗丹明B作为荧光基团,通过将罗丹明B与水合肼反应得到能够检测α-KA的荧光增强型探针RBN,并优化了检测温度、pH及响应时间等条件。研究表明,RBN对α-KA表现出很好的选择性,不受人体内常见氨基酸、化学结构类似的羰基化合物及活性氧化物(ROS)的影响,具有潜在的应用价值。     

A pH-activatable and aniline-substituted photosensitizer for near-infrared cancer theranostics

This work reports a newly designed pH-activatable and aniline-substituted aza-boron-dipyrromethene as a trifunctional photosensitizer to achieve highly selective tumor imaging, efficient photodynamic therapy (PDT) and therapeutic self-monitoring through encapsulation in a cRGD-functionalized nanomicelle. The diethylaminophenyl is introduced in to the structure for pH-activatable near-infrared fluorescence and singlet oxygen (¹O₂) generation, and bromophenyl is imported to increase the ¹O₂ generation efficiency upon pH activation by virtue of its heavy atom effect. After encapsulation, the nanoprobe can target α_vβ₃ integrin-rich tumor cells via cRGD and is activated by physiologically acidic pH for cancer discrimination and PDT. The fascinating advantage of the nanoprobe is near-infrared implementation beyond 800 nm, which significantly improves the imaging sensitivity and increases the penetration depth of the PDT. By monitoring the fluorescence decrease in the tumor region after PDT, the therapeutic efficacy is demonstrated in situ and in real time, which provides a valuable and convenient self-feedback function for PDT efficacy tracking. Therefore, this rationally designed and carefully engineered nanoprobe offers a new paradigm for precise tumor theranostics and may provide novel opportunities for future clinical cancer treatment.     

Ferric Phosphate Hydroxide Microstructures Affect Their Magnetic Properties

Uniformly sized and shape-controlled nanoparticles are important due to their applications in catalysis, electrochemistry, ion exchange, molecular adsorption, and electronics. Several ferric phosphate hydroxide (Fe₄(OH)₃(PO₄)₃) microstructures were successfully prepared under hydrothermal conditions. Using controlled variations in the reaction conditions, such as reaction time, temperature, and amount of hexadecyltrimethylammonium bromide (CTAB), the crystals can be grown as almost perfect hyperbranched microcrystals at 180 °C (without CTAB) or relatively monodisperse particles at 220 °C (with CTAB). The large hyperbranched structure of Fe₄(OH)₃(PO₄)₃ with a size of ∼19 μm forms with the “fractal growth rule” and shows many branches. More importantly, the magnetic properties of these materials are directly correlated to their size and micro/nanostructure morphology. Interestingly, the blocking temperature (T_B) shows a dependence on size and shape, and a smaller size resulted in a lower T_B. These crystals are good examples that prove that physical and chemical properties of nano/microstructured materials are related to their structures, and the precise control of the morphology of such functional materials could allow for the control of their performance.