Highly insulating alkane rings with destructive σ-interference

Science China Chemistry - Destructive quantum interference (DQI) provides a unique approach to controlling the leakage current in the OFF state of molecular devices. However, the DQI in...     

From Polymer to Monomer: Cleavage and Rearrangement of Si‐O‐Si Bonds after Oxidation Yielded an Ordered Cyclic Crystallized Structure

Polymerization reactions are very common in the chemical industry, however, the reaction in which monomers are obtained from polymers is rarely invesitgated. This work reveals for the first time that oxone can break the Si‐O‐Si bond and induce further rearrangement to yield an ordered cyclic structure. The oxidation of P1 , which is obtained by reaction of 2,2′‐1,2‐ethanediylbis(oxy)bis(ethanethiol) (DBOET) with 1,3‐divinyl‐1,1,3,3‐tetramethyldisiloxane (MM^Vi), with oxone yielded cyclic crystallized sulfone–siloxane dimer ( P1‐ox ) after unexpected cleavage and rearrangement of the Si‐O‐Si bond.     

Analysis of Para Red and Sudan Dyes in Egg Yolk by UPLC–MS–MS

Matrix solid-phase dispersion (MSPD) with alumina N as adsorbent has been used for extraction of para red, Sudan 1, Sudan 2, Sudan 3, and Sudan 4 dyes from egg yolk. The extracts were analyzed by ultra-performance liquid chromatography–tandem mass spectrometry (UPLC–MS–MS). Mean recovery for the five dyes ranged from 63.2 to 98.6%, with CV 0.55–10.00%. One sample was confirmed to contain 0.3 mg kg^?1 Sudan 4.     

LC–MS–MS Quantitative Determination of Ursolic Acid in Human Plasma and Its Application to Pharmacokinetic Studies

A sensitive and specific liquid chromatography–electrospray ionization-tandem mass spectrometry method has been developed and validated for the identification and quantification of ursolic acid in human plasma using glycyrrhetic acid as an internal standard. The method involves extraction with methyl tert-butyl ether. The analyte was separated on a C₁₈ column and analyzed in multiple reaction monitoring mode with a negative electrospray ionization interface using the [M–H]? ions, m/z 455.4 for ursolic acid and m/z 469.5 → m/z 425.5 for glycyrrhetic acid. The method was validated over the concentration range of 0.86–110.0 μg L^?1. The intra- and inter-day precisions were less than 13.53% relative standard deviation (RSD) and the accuracy was within ?4.76% in terms of relative error (RE). The lower limit of quantification was 0.86 μg L^?1 with acceptable precision and accuracy. There were almost no matrix effects. Recovery of ursolic acid from spiked drug-free plasma was higher than 68%. The method was used to study the pharmacokinetic profile of ursolic acid in human plasma after oral administration of Jieyu capsules.     

Integration of paper-based microfluidic devices with commercial electrochemical readers

The combination of simple Electrochemical Micro-Paper-based Analytical Devices (EμPADs) with commercially available glucometers allows rapid, quantitative electrochemical analysis of a number of compounds relevant to human health (e.g., glucose, cholesterol, lactate, and alcohol) in blood or urine.     

A unique approach to the concise synthesis of highly optically active spirooxazolines and the discovery of a more potent oxindole-type phytoalexin analogue

Drug-lead synthesis through rapid construction of chiral molecular complexity around the biologically relevant framework using a highly efficient strategy is a key goal of organic synthesis. Molecules bearing a spirooxindole-type framework exhibit important bioactivities. Herein, we present a highly efficient and convenient strategy that allows rapid construction of unique optically active spiro[oxazoline-3,3'-oxindole]s through the organocatalyzed asymmetric synthesis of spirocyclic thiocarbamates via an aldol reaction. Preliminary biological evaluation of several of the spirooxazolines using a model of acute neuroinflammation revealed promising antipyretic activity and provided an opportunity to discover new antipyretic agents.     

Organocatalytic asymmetric synthesis of substituted 3-hydroxy-2-oxindoles via Morita-Baylis-Hillman reaction

We report a highly enantioselective Morita-Baylis-Hillman (MBH) reaction of isatins and acrolein to provide enantiomerically enriched 3-substituted 3-hydroxyoxindoles, which could serve as valuable synthetic building blocks. This is also the first time that a ketone has been used as the electrophile and acrolein as the nucleophile in a highly enantioselective catalytic asymmetric MBH reaction. Hatakeyama's catalyst, β-isocupreidine (1), turned out to be a powerful catalyst for this transformation.     

Crystallization mechanism and microstructure evolution of Li2O–Al2O3–SiO2 glass-ceramics with Ta2O5 as nucleating agent

Li₂O–Al₂O₃–SiO₂ glass-ceramics were prepared with Ta₂O₅ as nucleating agent, the crystallization mechanism and microstructure evolution were investigated by DTA, XRD, and SEM technologies. With increasing amount of Ta₂O₅ from 2 to 6 mol%, the crystallization activation energy decreased from 297.73 to 218.66 kJ mol^?1, while the crystallization index increased from 1.76 to 3.39. In addition, the cluster of dendritic crystals and lamellar structure obtained in T-2 glass-ceramics indicated a typical two-dimensional crystallization mechanism, and the formation of spherical β-quartz solid solution in T-4 specimens, with average size of 50–70 nm, was mainly due to bulk crystallization mechanism. It was considered that Ta₂O₅ promoted the nucleation and crystallization of LAS glass by precipitating the crystalline precursor phase of Ta₂O₅, which acted as nuclei for the subsequent crystal growth. Eventually, the diffusion and crystallization process, microstructure morphology, as well as the secondary grain growth were also investigated.     

Band structure studies on crystalline C60, Ca3C60, and Ca5C60

The three-dimensional EHMO crystal orbital calculations for crystalline C₆₀, Ca₃C₆₀, and Ca₅C₆₀ are reported. The ground states of both undoped solid C₆₀ and partially doped Ca₃C₆₀ are found to be insulating with an indirect energy gap of 1.2 and 0.5 eV, respectively. In contrast, Ca₅C₆₀ forms a metallic conducting phase with a set of three half-filled bands crossing the Fermi level, which is found to be located close to a peak of the density of state. The character of crystal orbitals near the Fermi level for both Ca₃C₆₀ and Ca₅C₆₀ is completely carbonlike. In both cases, the Ca atoms are almost fully ionized and C₆₀ molecules form a stable negative charge state with six to 10 additional electrons. © 1995 John Wiley & Sons, Inc.     

三波长分光光度法研究：Ⅲ.两测量波长法提高测定灵敏度

本实验利用两测量波长法提高三波长光光度法的灵敏度，选择合适的波长组合，消除两种共存组分的干扰，使△Ａ＝Ａλ１＋Ａλ２－ＫＡλ３只与待测组分的浓度有关，灵敏度一般均高于单波长法。以相对误差为选择波长组合的标准，编制了程序，用计算机选择合适的波长组合，验证结果令人满意。