Quantification of multiple compounds containing heterogeneous elements in the mixture by one‐dimensional nuclear magnetic resonance spectroscopy of different nuclei using a single universal concentration reference

One‐dimensional (1D) quantitative NMR (qNMR) is a useful tool for concentration determination due to its experimental simplicity and the direct proportionality of the integrated signal area to the number of nuclei spin. For complex mixtures, however, signal overlapping often in one‐dimensional quantitative ¹H NMR (1D ¹H qNMR) spectrum limits the accurate quantification of individual compound. Here, we introduced employing joint 1D qNMR methods of different nuclei, such as ¹H and ³¹P (or/and ¹⁹F), to quantify multiple compounds in a complex mixture using a single universal concentration reference. When the concentration ratio of several compounds containing different elements in a complex mixture is of interest, the result calculated from measured intensities from 1D qNMR of different nuclei is independent of the gravimetric error from the reference. In this case, the common reference also serves as a ‘quantitative bridge’ among these 1D qNMR of different nuclei. Quantitative analysis of choline, phosphocholine, and glycerophosphocholine mixture is given as an example using trimethylphosphine oxide ((CH₃)₃P(O)) as concentration reference. Compounds containing multiple elements, such as tetramethylammonium hexafluorophosphate (N⁺(CH₃)₄PF₆^?), are proposed as the common concentration reference for ¹H, ¹³C, ¹⁵N, ³¹P, and ¹⁹F qNMR for the quantitative analysis of complex mixture containing these different elements. We anticipate that the proposed joint 1D qNMR approach using a universal concentration reference will be a valuable alternative for simultaneous quantification of multiple compounds in a complex mixture due to its accuracy and single and simple sample preparation. Copyright © 2014 John Wiley & Sons, Ltd.     

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.     

Spin-state selective carbon-detected HNCO with TROSY optimization in all dimensions and double echo-antiecho sensitivity enhancement in both indirect dimensions

A carbon-detected TROSY-optimized experiment correlating 1HN, 15N, and 13C' resonances, referred to as c-TROSY-HNCO is presented, in which the 1HN and 15N TROSY effects are maintained in both indirect dimensions, while the directly detected 13C' is doubly TROSY-optimized with respect to 1HN and 15N. A new strategy for sensitivity enhancement, the so-called double echo-antiecho (dEA), is described and implemented in the c-TROSY-HNCO experiment. dEA offers sensitivity enhancement of square root of 2 in both indirect dimensions and is generally applicable to many multidimensional experiments. A carbon-detected HNCO experiment, c-HNCO, without TROSY optimization and sensitivity enhancement is also designed for comparison purposes. Relaxation simulations show that for a protein with a rotational correlation time of 10 ns or larger, the c-TROSY-HNCO experiment displays comparable or higher signal-to-noise (S/N) ratios than the c-HNCO experiment, although the former selects only 1/4 of the initial magnetization relative to the later. The high resolution afforded in the directly detected carbon dimension allows direct measurement of the doublet splitting to extract 1JCalphaC' scalar and 1DCalphaC' residual dipolar couplings. Simulations indicate that the c-TROSY-HNCO experiment offers higher precision (lower uncertainty) compared to the c-HNCO experiment for larger proteins. The experiments are applied to 15N/13C/2H/[Leu,Val]-methyl-protonated IIBMannose, a protein of molecular mass 18.6 kDa with a correlation time of approximately 10 ns at 30 degrees C. The experimental pairwise root-mean-square deviation for the measured 1JCalphaC' couplings obtained from duplicate experiments is 0.77 Hz. By directly measuring the doublet splitting, the experiments described here are expected to be much more tolerant to nonuniform values of 1JCalphaC' (or 1JCalphaC' + 1DCalphaC' for aligned samples) and pulse imperfections due to the smaller number of applied pulses in the "out-and-stay" coherence transfer in the c-HNCO-TROSY experiment relative to conventional 1H-detected "out-and-back" quantitative J correlation experiments. A carbon-detected TROSY-optimized experiment correlating 1HN, 15N, and 13C' resonances, referred to as c-TROSY-HNCO is presented, in which the 1HN and 15N TROSY effects are maintained in both indirect dimensions, while the directly detected 13C' is doubly TROSY-optimized with respect to 1HN and 15N. A new strategy for sensitivity enhancement, the so-called double echo-antiecho (dEA), is described and implemented in the c-TROSY-HNCO experiment. dEA offers sensitivity enhancement of in both indirect dimensions and is generally applicable to many multidimensional experiments.     

Ginsenoside Rb1 Mitigates Escherichia coli Lipopolysaccharide-Induced Endometritis through TLR4-Mediated NF-κB Pathway

Endometritis is the inflammatory response of the endometrial lining of the uterus and is associated with low conception rates, early embryonic mortality, and prolonged inter-calving intervals, and thus poses huge economic losses to the dairy industry worldwide. Ginsenoside Rb1 (GnRb1) is a natural compound obtained from the roots of Panax ginseng, having several pharmacological and biological properties. However, the anti-inflammatory properties of GnRb1 in lipopolysaccharide (LPS)-challenged endometritis through the TLR4-mediated NF-κB signaling pathway has not yet been researched. This study was planned to evaluate the mechanisms of how GnRb1 rescues LPS-induced endometritis. In the present research, histopathological findings revealed that GnRb1 ameliorated LPS-triggered uterine injury. The ELISA and RT-qPCR assay findings indicated that GnRb1 suppressed the expression level of pro-inflammatory molecules (TNF-α, IL-1β and IL-6) and boosted the level of anti-inflammatory (IL-10) cytokine. Furthermore, the molecular study suggested that GnRb1 attenuated TLR4-mediated NF-κB signaling. The results demonstrated the therapeutic efficacy of GnRb1 in the mouse model of LPS-triggered endometritis via the inhibition of the TLR4-associated NF-κB pathway. Taken together, this study provides a baseline for the protective effect of GnRb1 to treat endometritis in both humans and animals.     

石墨二炔及其电子转移增强特性

石墨二炔是由sp和sp²杂化的碳原子构成的新的碳同素异形体。由于石墨二炔具有独特的拓扑结构和电子结构、较高的电荷迁移率及优异的电子传输性能,使其与其他材料相互作用,可表现出独特的电子转移增强特性。本文基于石墨二炔的电子转移增强特性,概述了石墨二炔及其电子转移增强特性的最新研究进展,包括金属氧化物/石墨二炔、金属纳米颗粒/石墨二炔、聚合物/石墨二炔以及染料分子/石墨二炔等多种石墨二炔基材料。本文从理论和实验研究两个方面详细阐述了石墨二炔的电子转移增强特性、石墨二炔与不同材料的相互作用以及相关的应用。希望该综述能对石墨炔化学的发展起到一定的积极作用。     

Easily Separated and Recyclable Amino-functionalized PorousSiO2 Beads with 3D Continuous Meso/Macropore Channels

Amino-functionalized porous SiO₂ beads with a diameter of 200—800 μm(PSB-NH₂) have been successfully synthesized by grafting 3-aminopropyl-triethoxysilane onto meso/macroporous silica beads(PSB), in which the PSB was prepared by hydrothermal synthetic method with a porous hard template anion-exchange resin. The as-prepared materials were characterized by means of nitrogen sorption and transmission electron micrographs(TEM), showing the presence of 3D interconnected and continuous large mesopores and macropores inside. The beads were used to catalyze Knoevenagel condensation and proved to be highly active and selective due to the high accessibility of the reactants to the amino groups via the continuous 3D meso/macopores. Notably, such material in bead format facilitates the extremely straightforward separation from reaction solution without any centrifugation or filtration. Moreover, PSB-NH₂ proved to be a stable catalyst via leaching experiment test, and can be easily recovered and reused without significant loss of activity in successive catalytic cycles.     

基于苯基修饰策略的新型可溶液加工红光铱配合物的设计、合成及电致发光性能研究

利用向环金属配体的C-Ir键的对位进行苯基取代这一结构修饰策略,成功合成了两种新型铱（III）配合物（3PhNbt）₂Ir（acac）和（3OMePhNbt）₂Ir（acac）.相较其橙光发射的母体化合物（Nbt）₂Ir（acac）,两个目标化合物的抗结晶性、非晶态热稳定性及溶解性均有显著提高,其磷光发射带也发生了5~10 nm的红移.以（3PhNbt）₂Ir（acac）和（3OMePhNbt）₂Ir（acac）为发光客体材料所制备的单层溶液加工电致红光器件,其最大发光亮度分别为1830 cd·m^-2和6630 cd·m^-2,最大电流效率分别为2.4 cd·A^-1和8.7 cd·A^-1,CIE1931色坐标分别为（0.61,0.39）和（0.62,0.38）.相比之下,以母体化合物（Nbt）₂Ir（acac）为发光客体材料所制备的参比器件,其最大发光亮度则为1620 cd·m^-2,最大电流效率仅为1.5 cd·A^-1,CIE1931色坐标为（0.59,0.41）.上述研究结果表明：向C-Ir键对位进行苯基修饰可以在提高铱（III）配合物的可溶液加工性能的同时,获得更为红移的电致发光波长,是一种简单而有效的红光铱（III）配合物的分子设计策略.     

Ultrafast charge separation and long-lived charge separated state in photocatalytic CdS-Pt nanorod heterostructures

Colloidal semiconductor-metal nanoheterostructures that combine the light-harvesting ability of semiconductor nanocrystals with the catalytic activity of small metal nanoparticles show promising applications for photocatalysis, including light-driven H(2) production. The exciton in the semiconductor domain can be quenched by electron-, hole-, and energy transfer to the metal particle, and the competition between these processes determines the photocatalytic efficiency of these materials. Using ultrafast transient absorption spectroscopy, we show that, in CdS-Pt heterostructures consisting of a CdS nanorod with a Pt nanoparticle at one end, the excitons in the CdS domain dissociate by ultrafast electron transfer (with a half-life of ～3.4 ps) to the Pt. The charge separated state is surprisingly long-lived (with a half-life of ～1.2 ± 0.6 μs) due to the trapping of holes in CdS. The asymmetry in the charge separation and recombination times is believed to be the key feature that enables the accumulation of the transferred electrons in the Pt tip and photocatalysis in the presence of sacrificial hole acceptors.     

非线性光学中薛定谔型方程的整体吸引子

研究了一类非线性薛定谔型方程,描述了光波在光折射晶体中的传播.首先构造了该模型整体弱的吸引子,然后通过能量方程的精确分析,证明整体弱吸引子实际为系统整体强吸引子.最后给出了整体吸引子的分形维数和Hausdorff维数的上界估计.     

N型TOPCon晶硅太阳能电池光注入退火增效的研究

N型隧穿氧化层钝化接触(Tunnel Oxide Passivating Contacts,TOPCon)太阳能电池完成印刷烧结后,再经过光注入,效率有明显提升,主要表现在Voc(开路电压)及FF(填充因子)的提升.其机理在于通过温度和光照强度调节费米能级变化,控制H总量及价态来提高钝化性能.钝化膜层的质量、硅基体掺杂...