Kinetic and mechanistic studies on the oxidation of pyrrolidine by bis(hydrogenperiodato)argentate(III) complex anion

The kinetics of oxidation of pyrrolidine by bis(hydrogenperiodato)argentate(III) complex anion ([Ag(HIO₆)₂]^5?) was studied in alkaline medium, with reaction temperatures in the range of 15.0–30.0 °C. The experiments indicated that the oxidation follows an overall second-order reaction, being first-order in both Ag(III) and pyrrolidine. The observed second-order rate constants, k′, decreased with increasing [IO₄ ^?] but increased slightly with increasing [OH^?]. The influence of ionic strength on the reaction rate was also investigated. The oxidation resulted in oxidative deamination of pyrrolidine, giving 4-hydroxybutyrate as the product. A reaction mechanism is proposed which includes an equilibrium between [Ag(HIO₆)₂]^5? and [Ag(HIO₆)₂(OH)(H₂O)]^2?; these two Ag(III) species are reduced by pyrrolidine in parallel rate-determining steps. The rate equation derived from the proposed mechanism can explain the experimental observations. The rate constants of the rate-determining steps, together with the associated activation parameters, were calculated accordingly.     

Analysis of an aggregation‐based algebraic two‐grid method for a rotated anisotropic diffusion problem

A two‐grid convergence analysis based on the paper [Algebraic analysis of aggregation‐based multigrid, by A. Napov and Y. Notay, Numer. Lin. Alg. Appl. 18 (2011), pp. 539–564] is derived for various aggregation schemes applied to a finite element discretization of a rotated anisotropic diffusion equation. As expected, it is shown that the best aggregation scheme is one in which aggregates are aligned with the anisotropy. In practice, however, this is not what automatic aggregation procedures do. We suggest approaches for determining appropriate aggregates based on eigenvectors associated with small eigenvalues of a block splitting matrix or based on minimizing a quantity related to the spectral radius of the iteration matrix. Copyright © 2015 John Wiley & Sons, Ltd.     

Efficient approach to allylated quinolines via palladium-catalyzed cyclization–allylation of 1-azido-2-(2-propynyl) benzenes with allyl methyl carbonate

The palladium-catalyzed cyclization–allylation reaction of ortho-azido propynylbenzenes 1 and allyl methyl carbonate 2d gives the corresponding allylated quinolines in moderate to good yields. The reaction of 1-azido-2-(2-propynyl)benzene 1a proceeds smoothly with 10 mol % Pd(PPh₃)₄ and 5 equiv K₃PO₄ or NaOAc in DMF at 100 °C to afford 3,4-diallylquinoline 3a in 69% yield in the case of R² = H and 3-allylquinoline 4 in 67% yield in the case of R² ≠ H.     

Synthesis of cholate-based pyridinium receptor and its recognition toward l-tryptophan

Four cholate-based pyridinium compounds were synthesized and their binding abilities toward unmodified amino acids were investigated by UV spectroscopy and fluorescence emission spectroscopy. Studies revealed that the recognition process involved hydrogen bonding, electrostatic force, and π–π interaction. The receptor 4a was found to recognize l-tryptophan specifically, and the complex was studied by ¹H NMR spectroscopy. The receptors 4b and 4c showed very little recognition ability toward l-tryptophan, indicating the important role of the benzyl group at pyridinium ring.     

Self‐Assembly of Five 8‐Hydroxyquinolinate‐Based Complexes: Tunable Core,Supramolecular Structure,and Photoluminescence Properties

Five new Zn^II complexes, namely [Zn₃(L)₆] ( 1 ), [Zn₂(Cl)₂(L)₂(py)₂] ( 2 ), [Zn₂(Br)₂(L)₂(py)₂] ( 3 ), [Zn(L)₂(py)] ( 4 ), and [Zn₂(OAc)₂(L)₂(py)₂] ( 5 ), were prepared by the solvothermal reaction of ZnX₂ (X^?=Cl^?, Br^?, F^?, and OAc^?) salts with a 8‐hydroxyquinolinate ligand (HL) that contained a trifluorophenyl group. All of the complexes were characterized by elemental analysis, IR spectroscopy, and powder and single‐crystal X‐ray crystallography. The building blocks exhibited unprecedented structural diversification and their self‐assembly afforded one mononuclear, three binuclear, and one trinuclear Zn^II structures in response to different anions and solvent systems. Complexes 1 – 5 featured four types of supramolecular network controlled by non‐covalent interactions, such as π???π‐stacking, C? H???π, hydrogen‐bonding, and halogen‐related interactions. Investigation of their photoluminescence properties exhibited disparate emission wavelengths, lifetimes, and quantum yields in the solid state.     

Synthesis and Chromatographic Evaluation of Perfluorooctyl Stationary Phase for Separation of Basic Compounds

Fluorinated stationary phases provide unique separation effect on basic compounds, due to the fluorine atoms, and pentafluorophenyl stationary phases (PFPs) are the most widely used. Considering that some fluoroalkyls have higher fluorine contents than PFPs do, it is speculated that fluoroalkyl stationary phases should have potential new applications. Herein, we synthesized a silica-based stationary phase bonding perfluoroctyl (FC8) proved by characterization through elemental analysis and solid-state ¹³C cross-polarization/magic-anglespinning nuclear magnetic resonance. The chromatographic behavior of the stationary phase was evaluated with test compounds. In addition, to further study the applicability of FC8 materials, Corydalis decumbens (Thunb.) Pers. fraction, considered as a challenging medicine on reversed-phase chromatography columns, was chosen as a test sample. Results demonstrated that the FC8 stationary phase had better and more satisfactory separation performance than the PFP stationary phase on basic compounds.

     

Synthesis of Fluorescent Carbon Dots and Their Application in Ascorbic Acid Detection

Water-soluble fluorescent carbon dots (CDs) were synthesized by a hydrothermal method using citric acid as the carbon source and ethylenediamine as the nitrogen source. The repeated and scale-up synthetic experiments were carried out to explore the feasibility of macroscopic preparation of CDs. The CDs/Fe³⁺ composite was prepared by the interaction of the CDs solution and Fe³⁺ solution. The optical properties, pH dependence and stability behavior of CDs or the CDs/Fe³⁺ composite were studied by ultraviolet spectroscopy and fluorescence spectroscopy. Following the principles of fluorescence quenching after the addition of Fe³⁺ and then the fluorescence recovery after the addition of asorbic acid, the fluorescence intensity of the carbon dots was measured at λex = 360 nm, λem = 460 nm. The content of ascorbic acid was calculated by quantitative analysis of the changing fluorescence intensity. The CDs/Fe³⁺ composite was applied to the determination of different active molecules, and it was found that the composite had specific recognition of ascorbic acid and showed an excellent linear relationship in 5.0–350.0 μmol·L⁻¹. Moreover, the detection limit was 3.11 μmol·L⁻¹. Satisfactory results were achieved when the method was applied to the ascorbic acid determination in jujube fruit. The fluorescent carbon dots composites prepared in this study may have broad application prospects in a rapid, sensitive and trace determination of ascorbic acid content during food processing.     

Determination of PEGylation homogeneity of polyethylene glycol-modified canine uricase

Polyethylene glycol-modified canine uricase (PEG-UHC) was prepared by modifying the ε-amino group of lysine residues on the canine uricase (UHC) protein to near-saturation with 5 kDa monomethoxyl-polyethylene glycol succinimide (mPEG-SPA-5k). In order to accurately determine the PEGylation uniformity of PEG-UHC, CZE, 3–8% gradient gel SDS-PAGE, and imaging CIEF (iCIEF) analyses were compared. CZE could not effectively separate PEG-UHC proteins with different degrees of modification, 3–8% gradient gel SDS-PAGE could separate PEG-UHC into seven gel bands; however, most of the gel bands were smeared or blurred, and the separation of PEG-UHC samples by iCIEF was significantly better than that by 3–8% gradient gel SDS-PAGE. Under denatured conditions, iCIEF separated 12 pI peaks, and could also accurately quantify the relative monomer PEG-UHC content. More than 85% of the total monomeric PEG-UHC was conjugated with 7–12 PEG molecules; of this 85%, approximately 40% was conjugated with 9–10 PEG molecules. These results demonstrated that iCIEF exhibits good potential for determining the PEGylation homogeneity of PEGylated protein drugs.     

飞行试验大数据技术及展望

现代航空武器装备综合化和信息化程度越来越高,飞行试验测试数据的种类增多,测试数据量剧增,飞行试验进入了大数据时代。试飞大数据的来临,对试验数据的获取、记录、传输和处理等传统技术及模式产生了强大的冲击,也提出了严峻的挑战。本文在简要介绍大数据概念及国外研究应用现状的基础上,通过总结分析飞行试验数据的新特征、新需求,提出了“试飞大数据”的概念,得出飞行试验数据是典型大数据的结论;按照试飞测试流程和大数据技术范畴,重点分析了试飞大数据技术中的数据获取、交换、记录、传输、监控、处理、存储等关键技术,最后,对试飞大数据技术的应用前景进行了展望。     

Characterization of Cr‐doped Sb2Te3 films and their application to phase‐change memory

Phase‐change memory (PCM) is regarded as one of the most promising candidates for the next‐generation nonvolatile memory. Its storage medium, phase‐change material, has attracted continuous exploration. Along the traditional GeTe–Sb₂Te₃ tie line, the binary compound Sb₂Te₃ is a high‐speed phase‐change material matrix. However, the low crystallization temperature prevents its practical application in PCM. Here, Cr is doped into Sb₂Te₃, called Cr–Sb₂Te₃ (CST), to improve the thermal stability. We find that, with increase of the Cr concentration, grains are obviously refined. However, all the CST films exhibit a single hexagonal phase as Sb₂Te₃ without phase separation. Also, the Cr helps to inhibit oxidation of Sb atoms. For the selected film CST_10.5, the resistance ratio between amorphous and crystalline states is more than two orders of magnitude; the temperature for 10‐year data retention is 120.8 °C, which indicates better thermal stability than GST and pure Sb₂Te₃. PCM cells based on CST_10.5 present small threshold current/voltage (4 μA/0.67 V). In addition, the cell can be operated by a low SET/RESET voltage pulse (1.1 V/2.4 V) with 50 ns width. Thus, Cr–Sb₂Te₃ with suitable composition is a promising novel phase‐change material used for PCM with high speed and good thermal stability performances. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)