Potential energy surface of thionylimide

The potential energy surface (PES) of thionylimide has been searched using ab initio MO and density functional calculations. The electronic structures of the isomers of HNSO have been studied using the HF/6‐31+G*, MP2(full)/6‐31+G*, and B3LYP/6‐31+G* levels. Final energies of these molecules have been calculated at the high‐accuracy G2 and CBS‐Q levels. The probable pathways of isomerization of thionylimide to its isomers (e.g., thiocyanic acid, HONS, nitrosothiols) have been explored by studying the three‐ or four‐membered transition states. This study identified total eight possible isomers ( 1–8 ) of HNSO, of which four ( 1–4 ) have already been realized experimentally. Of the remaining four ( 5–8 ), at least two ( 5, 7 ) can be generated experimentally. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006     

Theoretical Definition of a Functional Group and the Molecular Orbital Paradigm

It is the purpose of this review to demonstrate that the empirical classification of the observations of chemistry in terms of the properties assigned to functional groups is a consequence of and is predicted by physics. This is accomplished by showing that the atoms and functional groups of chemistry can be identified with bounded space-filling objects whose properties are defined by quantum mechanics. The quantum mechanical definition of a group is combined with a new pictorial representation of its form to obtain a unified picture which should make it eminently recognizable to chemists. This picture, when combined with the demonstrated ability of these groups to recover the measured properties of atoms in molecules, is offered as one which meets the expectations a chemist associates with the concept of a functional group. The manner in which this physical definition of a group differs fundamentally from models of functional groups based upon molecular orbital theory is discussed.     

Zur Struktur und Reaktivität des Diammoniumhexafluoromanganats(IV)

About the Structure and Reactivity of Diammonium Hexafluoromanganate(IV) Electrolytic oxidation of an aqueous suspension of MnF₂ containing NH₄F, and subsequent crystallization in 40% HF yields yellow crystals of (NH₄)₂MnF₆. It crystallizes in the hexagonal K₂MnF₆ type structure with the space group P6₃mc and a = 5.903; c = 9.565 Å; Z = 2. With in situ powder diffraction studies it is shown, that (NH₄)₂MnF₆ is gradually reduced in a NH₃ atmosphere between 30 and 230 °C to afford (NH₄)₃MnF₆, (NH₄)₂MnF₅, and finally NH₄MnF₃. (NH₄)₃MnF₆, thereby, forms a hitherto unknown cubic (a = 9.082 Å) high temperature modification with the cryolite type structure. Under N₂ the thermal decomposition of (NH₄)₂MnF₆ proceeds via NH₄MnF₄ to yield MnF₂.     

Electrochemical Response of Cobalt(II) in the Presence of Ammonia

The electrochemical oxidation of cobalt(II) at gold, boron‐doped diamond, basal and edge plane pyrolytic graphite, and highly oriented pyrolytic graphite electrodes in aqueous solutions containing NH₃ has been studied using cyclic voltammetry, with subsequent chemical and electrochemical processes explained in detail. Furthermore, the electro‐reduction of [Co(NH₃)₆]³⁺ in the presence of different electrolytes has also been studied to obtain a better understanding of the oxidation pathway of the Co(II)‐ammine complexes. In aqueous solution the mechanism can be described by the following scheme:     

Formation of SnO2 Nanoparticles on External Surface of NaY Zeolite

Tin dioxide nanoparticles of 5 nm in size were prepared on NaY zeolite external surface by impregnation of SnCl2 solution and subsequent calcination at 623 K. A SnO2-NaY based chemical sensor for detecting H2 was demonstrated.     

Microgel-based engineered nanostructures and their applicability with template-directed layer-by-layer polyelectrolyte assembly in protein encapsulation

A novel strategy for the fabrication of microcapsules is elaborated by employing biomacromolecules and a dissolvable template. Calcium carbonate (CaCO(3)) microparticles were used as sacrificial templates for the two-step deposition of polyelectrolyte coatings by surface controlled precipitation (SCP) followed by the layer-by-layer (LbL) adsorption technique to form capsule shells. When sodium alginate was used for inner shell assembly, template decomposition with an acid resulted in simultaneous formation of microgel-like structures due to calcium ion-induced gelation. An extraction of the calcium after further LbL treatment resulted in microcapsules filled with the biopolymer. The hollow as well as the polymer-filled polyelectrolyte capsules were characterized using confocal laser scanning microscopy (CLSM), scanning electron microscopy (SEM), and scanning force microscopy (SFM). The results demonstrated multiple functionalities of the CaCO(3) core - as supporting template, porous core for increased polymer accommodation/immobilization, and as a source of shell-hardening material. The LbL treatment of the core-inner shell assembly resulted in further surface stabilization of the capsule wall and supplementation of a nanostructured diffusion barrier for encapsulated material. The polymer forming the inner shell governs the chemistry of the capsule interior and could be engineered to obtain a matrix for protein/drug encapsulation or immobilization. The outer shell could be used to precisely tune the properties of the capsule wall and exterior. [Diagram: see text] Confocal laser scanning microscopy (CLSM) image of microcapsules (insert is after treating with rhodamine 6G to stain the capsule wall).     

Chemically Sensitive Field‐Effect Transistors and Chemiresistors: New Materials and Device Structures

Electronic sensor technology remains of widespread and intense interest. There are compelling needs to detect chemical species ranging from small molecules dispersed in the gas phase to complex biopolymers in aqueous solution. This review describes some recent advances in three main areas: chemically sensitive resistors (chemiresistors, CRs) including inorganic and organic based devices, field effect transistors (FETs) with semiconducting layers and/or gates with chemical sensitivity, and sensors based on the differential conductivity of nanotubes and nanowires. Results reported in the last two to three years are emphasized, highlighting some current trends in the development of sensors for applications such as diagnostics, process monitoring, and security.     

An Efficient and High‐Yield One‐Pot Synthesis of Bis(oxazoline)s

An efficient and mild one‐pot synthesis of bis(oxazoline) (BOX) ligands is developed from reactions of dicarboxy dichlorides with β‐amino alcohols in the presence of 11.0 equiv. NEt₃ followed by the addition of 3.6 equiv. methanesulfonyl chloride (MsCl). Nine different BOX ligands were prepared in excellent yields of ≥ 80%. Advantages of this improved synthesis are mild reaction conditions, short total reaction time of 9 h, and high isolated yields.     

全自动QuEChERS样品制备系统结合高效液相色谱-串联质谱法检测植物源性食品中34种农药残留

建立了全自动QuEChERS样品制备系统结合高效液相色谱-串联质谱（HPLC-MS/MS）同时检测植物源性食品中34种农药残留的分析方法。方法利用全自动QuEChERS样品制备系统涡旋振动和离心功能，将手动QuEChERS方法中样品提取和分散固相萃取相结合；优化了操作参数及前处理步骤，在多反应监测（MRM）模式下检测，基质匹配外标法定量。从方法学验证角度对全自动QuEChERS法与手动QuEChERS法进行了比较。结果表明：该方法中大多数农药在一定范围内呈现良好的线性关系，相关系数（R²）均大于0.99，检出限为0.76~3.60 μg/kg，定量限为2.28~10.80 μg/kg，加标回收率为53.0%~125.2%，相对标准偏差（RSD）<15.9%（n=5）。该方法与手动QuEChERS法的方法验证比对结果显示差异不明显，用于植物源性食品中多农药残留检测可有效降低劳动强度和出错概率。     

Molecular Basis of the Dynamic Strength of the Sialyl Lewis X—Selectin Interaction

The selectins are Ca²⁺‐dependent cell adhesion molecules that facilitate the initial attachment of leukocytes to the vascular endothelium by binding to a carbohydrate moiety as exemplified by the tetrasaccharide, sialyl Lewis X (sLeX). An important property of the selectin‐sLeX interaction is its ability to withstand the hydrodynamic force of the blood flow. Herein, we used single‐molecule dynamic force spectroscopy (DFS) to identify the molecular determinants within sLeX that give rise to the dynamic properties of the selectin/sLeX interaction. Our atomic force microscopy (AFM) measurements revealed that the unbinding of the selectin/sLeX complexes involves overcoming at least two activation barriers. The inner barrier, which determines the dynamic response of the complex at high forces, is governed by the interaction between the Fuc residue of sLeX and a Ca²⁺ ion chelated to the lectin domain of the selectin molecule, whereas the outer activation barrier can be attributed to interactions involving the sialic acid residue of sLeX. Due to their steep inner activation barriers, the selectin‐sLeX complexes are less sensitive to high pulling forces. Hence, besides its contribution to the bond energy, the Ca²⁺ ion also grants the selectin–sLeX complexes a tensile strength that is crucial for the selectin‐mediated rolling of leukocytes.