Simultaneous Determination of Gallic Acid and Folic Acid in Fruit Juice Samples Using Square Wave Voltammetry at Electrochemically Pretreated Carbon Paste Electrode

An efficient sensor was developed for the simultaneous determination of gallic and folic acid in juice samples using an electrochemically pretreated carbon paste electrode. The electrode was characterized by CV and EIS. The electrochemical behavior of GA and FA was evaluated by CV and SWV. The electrode exhibited high electrocatalytic activity towards GA and FA due to high surface area. Under the optimized condition, linear plots in the ranges of 0.08–13 μM and 0.1 to 15 μM were obtained for GA and FA, respectively. The proposed method was successful for the simultaneous determination of GA and FA in juice samples with satisfactory recovery.     

Combined Intrinsic and Extrinsic Proton Conduction in Robust Covalent Organic Frameworks for Hydrogen Fuel Cell Applications

Developing new materials for the fabrication of proton exchange membranes (PEMs) for fuel cells is of great significance. Herein, a series of highly crystalline, porous, and stable new covalent organic frameworks (COFs) have been developed by a stepwise synthesis strategy. The synthesized COFs exhibit high hydrophilicity and excellent stability in strong acid or base (e.g., 12 m NaOH or HCl) and boiling water. These features make them ideal platforms for proton conduction applications. Upon loading with H₃PO₄, the COFs (H₃PO₄@COFs) realize an ultrahigh proton conductivity of 1.13×10^?1 S cm^?1, the highest among all COF materials, and maintain high proton conductivity across a wide relative humidity (40–100 %) and temperature range (20–80 °C). Furthermore, membrane electrode assemblies were fabricated using H₃PO₄@COFs as the solid electrolyte membrane for proton exchange resulting in a maximum power density of 81 mW cm^?2 and a maximum current density of 456 mA cm^?2, which exceeds all previously reported COF materials.     

依托度酸哌嗪盐的制备及其性能表征

制备了依托度酸和哌嗪的有机盐,并得到了其晶体结构。 结构解析结果表明,依托度酸羧基上的氢转移到哌嗪的氮原子上,N—H••••O氢键是维持结构稳定的主要分子间相互作用。 与原药相比,新合成的盐的本征溶出速率和平衡溶解度分别提高了2.1倍和4.8倍。 此外,新合成的盐具有良好的水合稳定性,在25 ℃,相对湿度95%的条件下暴露28 d未发生相变。作为依托度酸的第一个有机盐,该盐是依托度酸有前景的固体存在形式。     

光自旋霍尔效应中横移的影响因素研究

研究了光束在空气与电介质分界面传输产生的自旋霍尔效应,揭示了光束重心横移分别与偏振态、折射率差以及入射角三者之间的定性关系.研究发现各光场横移都随偏振参量增大而增大,左、右旋椭圆偏振光的横移等值反向,圆偏振态下的横移比椭圆偏振态下的横移大.改变折射率差的大小,反射光横移随折射率差的增大而减小,但当折射率差接近零时,反射...     

金属钯纳米颗粒/氮化钛复合材料对水中2,4-二氯苯酚的电催化氢化脱氯（英文）

随着社会经济的快速发展,含氯有机物,特别是含氯苯系物,在农业、化工和医药等领域的使用量逐年增多,而使用过程中不合理的排放和控制致使含氯苯系物对生态环境,特别是水体环境的污染日趋严重.含氯苯系物具有高致毒致癌性,易生物富集,且很难被完全降解矿化,已被国家环保局认定为优先控制污染物.常规的废水处理工艺,如吸附、氧化及生物降解等,效率不高,且具有二次污染风险.电催化氢化脱氯技术是一种新型特别针对废水中含氯有机污染物的处理工艺,是通过在阴极电解还原水,原位生成原子态氢,以进攻苯环上C.Cl键,通过C.Cl键断裂H原子取代,使含氯苯系物完全转化为苯系物,达到去毒去害化的目的,近年来越来越受到研究者的关注.在整个电催化氢化脱氯技术中,高效稳定的电催化剂合成是关键,决定着脱氯效率、脱氯动力学、产物选择性及能量的利用率.本文报道了一种简易、无需添加任何表面活性剂的湿式还原法制备金属钯/氮化钛(Pd/TiN)和金属钯/碳(Pd/C)复合材料.在该复合材料中,金属钯颗粒具有均一的纳米尺寸(约5.0 nm)和球状形貌,且均匀分布在TiN和C载体上.作为针对水体中代表性含氯苯系物2,4-二氯苯酚的电催化氢化脱氯反应催化剂,Pd/TiN所展现的活性和稳定性均优于TiN和Pd/C,这源于TiN载体的促进作用.当TiN与Pd复合时,相应形成的Pd-TiN界面可改变Pd表面的电子结构,进一步优化Pd产活性氢及其吸附活化2,4-二氯苯酚的性能,因而其催化氢化脱氯活性增加.阴极工作电压是该催化反应中一个重要操作参数,决定了电催化氢化脱氯的效率和最终产物的构成.实验表明,.0.80 V vs Ag/AgCl是最佳操作电压,此时2,4-二氯苯酚的电催化氢化脱氯效率最高,可达到93.27%,且可实现最大程度的2,4-二氯苯酚向苯酚转化.脱氯反应路径研究发现,在Pd/TiN催化剂上2,4-二氯苯酚脱氯反应路径为2,4-二氯苯酚→对位一氯苯酚,邻位一氯苯酚→苯酚,但Pd/TiN对邻位和对位的C.Cl键断裂基本没有选择性.本文提供了一种新的有效调控Pd材料电催化氢化脱氯性能的方法,可望用于其他氢化反应体系的高效催化剂的设计合成,同时可推动电催化氢化脱氯技术在环境污染修复中的应用.     

Hierarchical chlorine-doped rutile TiO2 spherical clusters of nanorods: Large-scale synthesis and high photocatalytic activity

In this study, we report the synthesis of hierarchical chlorine-doped rutile TiO₂ spherical clusters of nanorods photocatalyst on a large scale via a soft interface approach. This catalyst showed much higher photocatalytic activity than the famous commercial titania (Degussa P25) under visible light (λ>420 nm). The resulting sample was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), nitrogen adsorption, X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectroscopy, ¹H solid magic-angle spinning nuclear magnetic resonance (MAS-NMR) and photoluminescence spectroscopy. On the basis of characterization results, we found that the doping of chlorine resulted in red shift of absorption and higher surface acidity as well as crystal defects in the photocatalyst, which were the reasons for high photocatalytic activity of chlorine-doped TiO₂ under visible light (λ>420 nm). These hierarchical chlorine-doped rutile TiO₂ spherical clusters of nanorods are very attractive in the fields of environmental pollutants removal and solar cell because of their easy separation and high activity.     

Observation of Spontaneous C=C Bond Breaking in the Reaction between Atomic Boron and Ethylene in Solid Neon

A ground‐state boron atom inserts into the C=C bond of ethylene to spontaneously form the allene‐like compound H₂CBCH₂ on annealing in solid neon. This compound can further isomerize to the propyne‐like HCBCH₃ isomer under UV light excitation. The observation of this unique spontaneous C=C bond insertion reaction is consistent with theoretical predictions that the reaction is thermodynamically exothermic and kinetically facile. This work demonstrates that the stronger C=C bond, rather than the less inert C?H bond, can be broken to form organoboron species from the reaction of a boron atom with ethylene even at cryogenic temperatures.     

各向异性超常介质中的反常线性现象

从麦克斯韦方程组出发,结合超常介质的特殊性质,分析了电磁波在一种具有线性色散关系的各向异性超常介质中的传播特性。在线性色散关系的情况下,得到了超常介质的介电张量和磁导率张量各元素之间的条件表达式。根据能量守恒定律和电磁场的边界连续性条件,在横电波(TE)和横磁波(TM)入射时,分析了折射波矢和能流与入射波矢和能流方向之间的关系。发现无论是TE波还是TM波,在这种介质中传输时,都产生了光准直的现象,且TE波和TM波的传输方式是相反的。     

31P chemical shift of adsorbed trialkylphosphine oxides for acidity characterization of solid acids catalysts

A comprehensive study has been made to predict the adsorption structures and (31)P NMR chemical shifts of various trialkylphosphine oxides (R3PO) probe molecules, viz., trimethylphosphine oxide (TMPO), triethylphosphine oxide (TEPO), tributylphosphine oxide (TBPO), and trioctylphosphine oxide (TOPO), by density functional theory (DFT) calculations based on 8T zeolite cluster models with varied Si-H bond lengths. A linear correlation between the (31)P chemical shifts and proton affinity (PA) was observed for each of the homologous R3PO probe molecules examined. It is found that the differences in (31)P chemical shifts of the R3POH(+) adsorption complexes, when referring to the corresponding chemical shifts in their crystalline phase, may be used not only in identifying Br?nsted acid sites with varied acid strengths but also in correlating the (31)P NMR data obtained from various R3PO probes. Such a chemical shift difference therefore can serve as a quantitative measure during acidity characterization of solid acid catalysts when utilizing (31)P NMR of various adsorbed R3PO, as proposed in our earlier report (Zhao; et al. J. Phys. Chem. B 2002, 106, 4462) and also illustrated herein by using a mesoporous H-MCM-41 aluminosilicate (Si/Al = 25) test adsorbent. It is indicative that, with the exception of (TMPO), variations in the alkyl chain length of the R3PO (R = C(n)H(2n+1); n > or = 2) probe molecules have only negligible effect on the (31)P chemical shifts (within experimental error of ca. 1-2 ppm) either in their crystalline bulk or in their corresponding R3POH(+) adsorption complexes. Consequently, an average offset of 8 +/- 2 ppm was observed for (31)P chemical shifts of adsorbed R3PO with n > or = 2 relative to TMPO (n = 1). Moreover, by taking the value of 86 ppm predicted for TMPO adsorbed on 8T cluster models as a threshold for superacidity (Zheng; et al. J. Phys. Chem. B 2008, 112, 4496), a similar threshold (31)P chemical shift of ca. 92-94 ppm was deduced for TEPO, TBPO, and TOPO.     

Building addressable libraries: the use of electrochemistry for spatially isolating a heck reaction on a chip

Pd(0) was generated at preselected sites on an electrochemically addressable chip and then utilized to effect a Heck reaction. The Pd(0) was confined to the preselected electrodes with the use of allylmethyl carbonate. Unlike most mediated electrochemical reactions, the electrolysis in this case was not used to convert a stoichiometric process into a catalytic one by recycling the metal. Instead, the unique environment of the chip was used to interfere with a catalytic process to make it stoichiometric. This was done to gain spatial control over the reaction. The development of a strategy for conducting Pd(0)-catalyzed reactions on the chips should greatly expand the synthetic chemistry available for building chip-based libraries.