离子选择电极—流动注射分析法动力学测定葡萄糖存在下的果糖

本文将离子电极与流动注射分析相结合，利用３０℃下，在强碱性介质中，果糖和葡萄糖与２，４－二硝基酚钠反应速度明显差异，动力学测定了葡萄糖存在下果糖的含量。自制了２，４－二硝基酚电极作为动力学电位测定用的工作电极。本法测定果糖的范围为０．０２～１．００ｍｏｌ／Ｌ，其ＲＳＤ为４．０％～４．９％，ＲＥ为１．０～５．０％；当Ｃ葡／Ｃ果≤３倍时，葡萄糖的干扰不超过５％；本法也曾成功地用于果葡萄浆测定，其ＲＳＤ     

Sodium dithionite initiated addition of 1-bromo-1-chloro-2,2,2-trifluoroethane to allylaromatics: Facile synthesis of conjugated dienes substituted with terminal CF3 group

Sodium dithionite effectively promotes the addition of 1-bromo-1-chloro-2,2,2-trifluoroethane to the terminal double bond of allylbenzenes 1. The reactions proceeded in MeCN/H₂O to give a 3:1 mole ratio of diastereoisomers of 1-(2-bromo-4-chloro-5,5,5-trifluoropentyl)benzenes 2 as the main products together with small amounts of its reductive debromination products 3. Total yields of 2 and 3 were dependent on the nature of the aromatic ring substituents in 1. Treatment of adducts 2 with DBU in refluxing hexanes resulted in double dehydrohalogenation affording, in good yields, conjugated dienes 4 (1,1,1-trifluoro-5-phenyl-2,4-pentadienes) terminated with the CF₃ group at the one end and the phenyl group at the opposite end. These dienes were found to be sufficiently reactive to undergo Diels-Alder condensation with active dienophiles to give trifluoromethylated carbocycles. The reactions of CF₃CHClBr with allylheterocycles were less successful and lead to low yields of mixtures of hardly separable compounds or to polymeric resins.     

Determination of enantiomeric composition of samples by multivariate regression modeling of spectral data obtained with cyclodextrin guest-host complexes-Effect of an achiral surfactant and use of mixed cyclodextrins

The determination of the enantiomeric composition of samples by chemometric modeling of spectral data was investigated for samples of N,N′-bis-(-methylbenzyl) sulfamide and tryptophan methyl ester hydrochloride. Multivariate regression models (PLS-1) were developed from spectral data obtained on solutions containing N,N′-bis-(-methylbenzyl)sulfamide or tryptophan methyl ester hydrochloride in the presence of sodium dodecyl sulfate and mixed cyclodextrin host molecules. The regression models were subsequently used to predict the enantiomeric composition of laboratory-prepared test samples of N,N′-bis(-methylbenzyl)sulfamide or tryptophan methyl ester hydrochloride. The capability of the models to accurately predict the enantiomeric composition was evaluated in terms of the root-mean-square percent relative error (RMS %R.E.) as calculated from the results obtained with independently prepared validation sets of samples. It was found that the presence of SDS in most cases either had little effect on the predictive ability of the model or it actually reduced the predictive ability of the model. Moreover, it was found that the use of mixed CDs, either in the presence or absence of SDS, reduced the predictive ability of the regression model when compared with results obtained with individual CDs.     

Monosaccharides as silicon chelators: pentacoordinate bis(diolato)(phenyl)silicates with the cis-furanose isomers of common pentoses and hexoses

Five-coordinate phenylsilicates are formed from the reaction of trimethoxy(phenyl)silane with monosaccharides in methanol in the presence of a stoichiometric amount of base. Five complexes have been isolated and characterized with two ketoses and three aldopentoses. The silicon central atom in [K([18]crown-6)][PhSi(beta-D-Fruf 2,3H-2)2].MeOH (1, Fru=fructose) is part of two chelate rings, with the ligands being beta-D-fructofuranose-O2,O3 dianions. The beta-furanose isomer is best suited for silicon ligation because it exhibits a torsion angle close to 0 degrees for the most acidic diol function, thus assuring a flat chelate ring. The same structural principles are also found in [K([18]crown-6)][PhSi(beta-D-Araf1,2H-2)2].2 MeOH (2, Ara=arabinose), [K([18]crown-6)][PhSi(alpha-D-Ribf1,2H-2)2] (3, Rib=ribose), [K([18]crown-6)][PhSi(alpha-D-Xylf1,2H-2)2]. acetone (4, Xyl=xylose), and [K([18]crown-6)][PhSi(alpha-D-Rulf2,3H-2)2] (5, Rul=ribulose).     

A simple method for fabrication of sole composition nickel hexacyanoferrate modified electrode and its application

Nickel hexacyanoferrate film modified gold electrode was prepared by a simple chemical deposition procedure from a fresh prepared solution containing ferricyanide, Ni²⁺, and sodium nitrate. The resultant films have solo composition and are significantly stable as compared to the electrochemically deposited NiHCF films. For different concentrations of Na⁺ in the solution, the formal potential values of NiHCF shift according to the Nernstian behavior with a slope of 48 mV in the range of 10⁻⁴ to 1.0 M. The NiHCF film was also used for the electrocatalytic oxidation of ascorbic acid. The anodic peak current observed in cyclic voltammetry increased with the ascorbic acid concentration. At a fixed potential under hydrodynamic conditions, the calibration plot was linear over the ascorbic acid concentration range 0.1-12 mM.     

High-pressure synthesis and structural behavior of sodium orthonitrate Na3NO4

Sodium orthonitrate (Na₃NO₄) is an unusual phase containing the first example of isolated tetrahedrally bonded NO₄³⁻ groups. This compound was obtained originally by heating together mixtures of Na₂O and NaNO₃ for periods extending up to >14 days in evacuated chambers. Considering the negative volume change between reactants and products, it was inferred that a high-pressure synthesis route might favor the formation of the Na₃NO₄ compound. We found that the recovered sample is likely to be a high-pressure polymorph, containing NO₄³⁻ groups as evidenced by Raman spectroscopy. The high-pressure behavior of Na₃NO₄ was studied using Raman spectroscopy and synchrotron X-ray diffraction in a diamond anvil cell above 60 GPa. We found no evidence for major structural transformations, even following laser heating experiments carried out at high pressure, although broadening of the Raman peaks could indicate the onset of disordering at higher pressure.     

Sodium dithionite initiated addition of CF2Br2 to β-pinene and reactions of the adduct: Synthesis and the reactivity of new 1,1-difluorodienes

Sodium dithionite effectively promotes the addition of dibromodifluoromethane to the exocyclic double bond of β-pinene. The reaction proceeded in a MeCN/H₂O system to give almost quantitatively an adduct, 1-(2-bromo-2,2-difluoroethyl)-4-(2-bromoisopropyl)-cyclohexene, as the sole product. On treatment of the adduct with 2,2,6,6-tetramethylpiperidine elimination of HBr only from the (CH₃)₂CHBr group occurred to give a mixture of regioisomeric dienes, while treatment with 50% KOH under phase transfer catalysis conditions or with K₂CO₃ in DMF resulted in total dehydrobromination to give trienes possessing an exocyclic CHCF₂ group. Surprisingly, the main course of the reactions of the adduct with DBU (1,8-diazabicyclo[5.4.0]undece-7-ene) and also with t-BuOK in THF was elimination of HBr only from the CH₂CF₂Br group to afford 1-(2,2-difluorovinyl)-4-(2-bromoisopropyl)cyclohexene as the main product. Catalytic hydrogenation of the adduct followed by treatment with DBU afforded a conjugated diene, 1-(2,2-difluorovinyl)-4-isopropylcyclohexene. Compounds bearing the CHCF₂ group are new 1,1-difluorodienes which readily reacted with 4-phenyl-3H-1,2,4-triazoline-3,5-dione to give cycloadducts, derivatives of triazolo[1,2-α]cinnoline.     

A simple and general route for the preparation of pure and high crystalline nanosized lanthanide silicates with the structure of apatite at low temperature

Rare earth silicates with the structure of apatite are attracting considerable interest since they show oxygen ion conductivities higher than that of yttria-stabilized zirconia (YSZ) at moderate temperature. Based on the hydrothermal synthesis we presented a simple one step process for the direct preparation of the pure and the high crystalline nanosized rare earth silicates with the structure of apatite under a mild condition (230 °C). Since the preparation of the high crystalline silicon based rare earth apatites is performed at high temperature previously and accompanied by subsequent process of grinding, results of this work provide a promising alternative of the existing methodology. Furthermore, due to the relatively low temperature of the preparation of these materials, high doping of monovalent cation can be done, which was not achieved before.     

钠离子电池用高性能锑基负极材料的调控策略研究进展

锑(Sb)具有高的理论比容量、较小的电极极化、合适的Na⁺脱嵌电位、价格低廉以及环境友好的优势,而成为一种具有较大应用前景的钠离子电池负极材料。但是,Sb基负极材料的一个重要挑战是在循环过程中高比容量伴随着大的体积变化,进而导致活性材料粉化,并从集流体上脱落,这大大限制了其在钠离子电池领域的大规模应用。因此,如何解决Sb基负极材料充放电过程中体积膨胀问题对于高性能的钠离子电池设计是至关重要的。本文详细综述和讨论了Sb基材料的结构-性能关系及其在钠离子电池中的应用,详细介绍了钠离子电池Sb基负极材料在氧化还原反应机理、形貌设计、结构-性能关系等方面的最新研究进展。本综述的主要目的是探讨影响Sb基负极材料性能的决定因素,从而提出有前途的改性策略,以提高其可逆容量和循环稳定性。最后,对Sb基钠离子电池负极材料的未来发展、面临的挑战和前景进行了展望。本文可为Sb负极材料的构建和优化提供具体的观点,阐明了Sb基负极材料未来的发展方向,从而促进钠离子电池的快速发展和实际应用。     

原位透射电镜研究正交相五氧化二铌纳米片的电化学储钠机制

由于正交相五氧化二铌(T-Nb₂O₅)为ReO₃型层状结构,锂、钠离子可以在其(001)平面快速脱嵌,而在[001]方向的传输一般较难。本研究通过原位透射电子显微镜(Transmission Electron Microscope,TEM)方法研究钠在T-Nb₂O₅纳米片(001)面内及[001]方向的钠离子电化学嵌入行为,发现由于纳米片晶体存在大量的位错和畴界,钠离子可通过这些缺陷穿越(001)面扩散,并进而在深层的(001)面内快速扩散。同时,本研究还发现刚合成的T-Nb₂O₅纳米片在[001]方向上存在调制结构,存在交替分布的压应变和张应变区域,而钠离子的嵌入可以调节这些应变分布。