Cucurbit[7]uril promoting PdCl2-catalyzed cross-coupling reaction of benzyl halides and arylboronic acids in aqueous media

The research provides a novel approach for producing diarylmethane derivatives using CB[7]–NaCl–PdCl₂ catalyzed Suzuki cross-coupling reaction of benzyl chloride derivatives and arylboronic acids in ethanol aqueous solution.     

Influence of surface properties on the interfacial adhesion in carbon fiber/epoxy composites

A polyacrylonitrile‐based carbon fiber was electrochemically oxidized in an aqueous ammonium bicarbonate solution with current density of up to 2.76 A/m² at room temperature. X‐ray photoelectron spectroscopy revealed that the oxygen content increased with increasing current density before approaching saturation. The increase can be divided into two regions, the rapid increase region (0–1.78 A/m²) and a plateau region (1.78–2.76 A/m²). The surface chemistry analysis showed that the interlaminar shear strength (ILSS) value of the carbon fiber/epoxy composite could be improved by 24.7%. The carbon structure was examined using Raman spectroscopy in terms of order/disorder in the graphite structure and the results indicated that the relative percentage of graphite carbon in the form of sp² hybridization increased above a current density of 1.39 A/m². The increasing non‐polar graphite carbon on the carbon fiber surface decreased the surface energy. As a result, both the surface free energy () and its polar component () decreased when current density increased above 1.78 A/m². The ILSS value had no direct relationship with the nature and surface density of the oxygen‐containing functional groups nor with the carbon structure. It is the surface free energy (), especially the polar component (), which played a critical role in affecting the interfacial adhesion of carbon fiber/epoxy composites. The ILSS value changed with increasing current density and could be divided into three distinct regions, as chemical interaction region (I), anchor force region (II) and matrix damage region (III). Copyright © 2013 John Wiley & Sons, Ltd.     

Rapid analysis of phthalic acid esters in environmental water using fast elution gas chromatography with mass spectrometry and adaptive library spectra

A method for the fast determination of the components in a complex sample by using gas chromatography with mass spectrometry was developed and used for the quantitative analysis of phthalic acid esters in environmental water. In the method, the adaptively corrected mass spectra were used to compensate for the differences between the library spectra and the measured ones in the experiment. The correction was obtained by the iterative transformation of the library spectra using iterative target transformation factor analysis, and the resolution was performed by non‐negative immune algorithm using the corrected spectra. Rapid analysis of 16 phthalic acid esters in water samples was achieved using fast elution gas chromatography with mass spectrometry measurements. The results show that the mass spectra and chromatographic profiles of the phthalic acid esters can be obtained from the overlapping signal of 13 min elution, and accurate quantitative analysis can be obtained. The recoveries of the phthalic acid esters obtained by standard addition are between 90.3 and 107.4%, and the relative standard deviations obtained in repeated measurements are less than 9%.     

Rapid assessment of drug response in cancer cells using microwell array and molecular imaging

Selection of personalized chemotherapy regimen for individual patients has significant potential to improve chemotherapy efficacy and to reduce the deleterious effects of ineffective chemotherapy drugs. In this study, a rapid and high-throughput in vitro drug response assay was developed using a combination of microwell array and molecular imaging. The microwell array provided high-throughput analysis of drug response, which was quantified based on the reduction in intracellular uptake (2-[N-(7-nitrobenz-2-oxa-1,3-diazol-4-yl)amino]-2-deoxy-d-glucose) (2-NBDG). Using this synergistic approach, the drug response measurement was completed within 4 h, and only a couple thousand cells were needed for quantification. The broader application of this microwell molecular imaging approach was demonstrated by evaluating the drug response of two cancer cell lines, cervical (HeLa) and bladder (5637) cancer cells, to two distinct classes of chemotherapy drugs (cisplatin and paclitaxel). This approach did not require an extended cell culturing period, and the quantification of cellular drug response was 4–16 times faster compared with other cell-microarray drug response studies. Moreover, this molecular imaging approach had comparable sensitivity to traditional cell viability assays, i.e., the MTT assay and propidium iodide labeling of cellular nuclei;and similar throughput results as flow cytometry using only 1,000–2,000 cells. Given the simplicity and robustness of this microwell molecular imaging approach, it is anticipated that the assay can be adapted to quantify drug responses in a wide range of cancer cells and drugs and translated to clinical settings for a rapid in vitro drug response using clinically isolated samples.      

溶剂热合成可调控氧空位的Bi2MoO6纳米晶及其光催化氧化制喹啉和抗生素降解

近年来,半导体光催化在环境净化和有机合成领域的研究引起了广泛的重视.其中,在有机合成领域中,光催化技术已经应用在醇类、环己烷以及芳香族化合物的选择性氧化研究.而另一类具有特殊结构的有机物——N-杂环芳烃,在药物化学和材料科学中具有重要意义.而传统用于合成N-杂化芳烃的脱氢催化氧化反应通常需要高温高压的苛刻环境,传统方法通常还需要使用贵金属催化剂,这也增加了N-杂化芳烃的合成成本;另外,如果合成是均相催化过程,则催化剂难以实现回收利用.因此,开发室温常压条件下的非贵金属多相光催化技术具有巨大的应用前景.本文以能够被可见光驱动的钼酸铋半导体为催化剂,利用氧缺陷策略来提升钼酸铋的光催化氧化性能.不同于传统氧缺陷制备方法(氢气还原热处理、离子掺杂等),本文采用一种低成本的乙二醛辅助溶剂热的方法合成具有可调控的含氧空位Bi₂MoO₆催化剂(OVBMO).通过X射线粉末衍射(XRD)、扫描电镜、透射电镜、紫外可见漫反射吸收光谱、氮气物理吸附脱附、X射线光电子能谱(XPS)、电子自旋共振光谱、光致发光光谱及电化学测试等技术对制备的OVBMO材料进行了物理化学性质及能带研究.XPS,XRD,Raman和FT-IR结果表明,氧空位存在于[Bi₂O₂]²⁺和MoO₆八面体的层间.紫外可见漫反射结果表明,随着氧空位的引入,Bi₂MoO₆的光吸收范围扩大,带隙变窄.结合莫特肖特基和VBXPS分析获得OVBMO的能带位置,发现氧空位的存在不仅会导致禁带中出现缺陷带能级,还会导致价带顶位置上移,促进光生空穴的迁移.PL和电化学结果表明,氧空位的存在使得载流子浓度、载流子的分离能力与界面电荷迁移能力都有较大提升,这是因为氧空位引入的缺陷能级可以浅势捕获电子,抑制光催化剂中的电子与空穴的复合,改变化学反应的速率.同时,氧空位有助于捕获分子氧,分子氧与捕获的光生电子发生反应,产生更多的超氧自由基(·O₂)和空穴(h⁺),从而极大地提升光催化剂的氧化性能.因此,OVBMO在1,2,3,4-四氢喹啉脱氢氧化产生喹啉及系列抗生素(环丙沙星、四环素、盐酸土霉素)的降解反应中,表现出较好的光催化氧化性能.结合多种表征分析,本文还进一步阐明了OVBMO催化剂将1,2,3,4-四氢喹啉脱氢氧化为喹啉的自由基参与的多相催化反应机理.     

Development of a method to screen and isolate xanthine oxidase inhibitors from black bean in a single step: Hyphenation of semipreparative liquid chromatography and stepwise flow rate countercurrent chromatography

Black bean, in which isoflavones are the main active constituent, also contains saponins and monoterpenes. Soybean isoflavone is a secondary metabolite that is formed during the growth of soybean; it exhibits antioxidant and cardiovascular activities and traces estrogen-like effects. In this study, black bean isoflavones were extracted with n-butanol, and ultrafiltration–liquid chromatography–mass spectrometry was used to screen their activity. Subsequently, the inhibitors were isolated and purified using semipreparative liquid chromatography and stepwise flow rate countercurrent chromatography. Thereafter, five active compounds were identified using mass spectrometry and nuclear magnetic resonance experiments. Finally, the inhibition types of the xanthine oxidase inhibitors were determined using enzymatic kinetic studies. The IC₅₀ values of daidzin, glycitein-7-O-glucoside, genistin, daidzein, and genistein were determined to be 35.08, 56.22, 30.76, 68.79, and 95.37 μg/mL, respectively. Daidzin, genistin, and daidzein exhibited reversible inhibition, whereas glycitein-7-O-glucoside and genistein presented irreversible inhibition. This novel approach, which was based on ultrafiltration–liquid chromatography–mass spectrometry and stepwise flow rate countercurrent chromatography, is a powerful method for screening and isolating xanthine oxidase inhibitors from complex matrices. The study of enzyme inhibition types is helpful for understanding the underlying inhibition mechanism. Therefore, a beneficial platform was developed for the large-scale production of bioactive and nutraceutical ingredients.     

Highly Efficient Oxygen Reduction Reaction Fe-N-C Cathode in Long-durable Direct Glycol Fuel Cells

The oxygen reduction reaction in direct glycol fuel cells heavily relies on noble metal-based electrocatalysts. In this work, novel Pt group metal-free catalysts based on porous Fe-N-C materials are successfully synthesized as catalysts with high activity and durability for the cathode oxygen reduction reaction (ORR). Through the encapsulation of NH₄SCN salt, the surface elements and pore structure of the catalyst are effectively changed, and the active sites of Fe effectively are increased. The half-wave potential of the best Fe-N-C catalyst was –0.02 V vs. Hg/HgO in an alkaline environment. The porous Fe-N-C catalyst possesses a large specific surface area(1158 m²/g) and shows good activity and tolerance to glycol. The direct glycol fuel cell with the Fe-N-C cathode achieved a maximum power density of 62.2 mW/cm² with 4 mol/L KOH and 4 mol/L glycol solution at 25 °C and maintained discharge for more than 250 h at a 50 A/cm² current density.     

Accelerated kinetics of alkaline hydrogen evolution/oxidation reactions on dispersed ruthenium sites through N and S dual coordination

Efficient,robust and cost-effective electrocatalysts that catalyze hydrogen evolution/oxidation reaction(HER/HOR)in alkaline media are highly demanded.Recently,single-atom catalysts(SACs)have emerged as new promising candidates;however,the rational design of supports and the optimization of coordination environment between supports and metal atoms are challenging.In this work,we successfully fabricate atomically dispersed ruthenium(Ru)species,which are strongly coordinated by N and S dual heteroatoms on holey graphene(RuSA/NSG),as an excellent bifunctional catalyst for HER/HOR.In alkaline media,the developed catalyst exhibits high catalytic performance with a low overpotential of 57.3 mV to drive a current density of 10 mA cm^-1 for HER,and its mass activity is about 5.8 times higher than that of commercial Pt/C and Ru/C catalysts at an overpotential of 100 mV.Similarly,considerable HOR performance of Ru SA/NSG is verified to be superior to Pt/C and Ru/C.Furthermore,X-ray-based spectroscopy measurements and density-functional theory calculations have confirmed that,compared with Ru–N₄,the tailored Ru–N₄–S₂ with nearby S dopants can act as more active centers to greatly accelerate the sluggish HER/HOR kinetics in alkaline media.The present work provides a new atomic-level engineering strategy to modulate catalytic activities of SACs via the coordination design using dual heteroatoms on the carbon support.     

Responsive hyperbranched poly(formyl-1,2,3-triazole)s toward quadruple-modal information security protection

Science China Chemistry - Secrecy has received tremendous attention in modern information society. Innovative polymer-based fluorescent materials with multiple mode emission are quite desirable to...