含有脲桥结构的苯氧乙酰胺衍生物的合成与表征

为了开发新型高效低毒杀菌剂,设计合成了5个未见文献报道的含有脲桥结构的苯氧乙酰胺类化合物,其结构经元素分析,1H NMR和IR确证.     

The drawing behavior of Y-Ba-Cu-O sol from non-aqueous solution by a complexing process

A complexing process is developed to prepare Y-Ba-Cu-O superconducting fibers. The process is not identical to typical sol-gel processes; here the resulting gel network is built up by hydrogen bonding linkage among complexing species in non-aqueous solution. Cu acetate, [Cu(OAC)₂], Ba methoxyethoxide [Ba(ORE)₂] and Y acetate [Y(OAC)₃] are used as precursors for preparing homogeneous gels while -methacrylic acid (HOAA) and diethylenetriamine (DETA) as complexing agents, and methoxyethanol (REOH) as solvent. Fibers drawn from a sol obtained through reduced pressure present no or little deformation at 80°MoC via adjusting the amount of DETA and HOAA. Cu(OAC)₂, Ba(ORE)₂ and Y(OAC)₃ in the complexing process have been demonstrated to form gels without hydrolysis and condensation at ambient atmosphere. The relationships between the drawing behavior of sols and gel structure with different amounts of DETA and HOAA are suggested. The concentration region of drawing the gel fibers with no or little deformation heated at 80°MoC is also found.     

Synthesis and Characterization of Novel Organosoluble Methyl Substituted Poly(aryl Ether Ketone)s Containing Sulfone Linkage

Several new methyl substituted poly(aryl ether ketone)s containing sulfone linkage with inherent viscosities of 0.62–0.84 dL/g have been prepared from 4,4′‐bis(2‐methylphenoxy)diphenylsulfone and 4,4′‐bis(3‐methylphenoxy)diphenylsulfone with terephthaloyl chloride and isophthaloyl chloride by electrophilic Friedel‐Crafts acylation in the presence of DMF with anhydrous AlCl₃ as a catalyst in 1,2‐dichloroethane, respectively. These polymers having weight‐average molecular weight in the range of 71,000–49,000 are all amorphous and show high glass transition temperatures ranging from 167 °C to 191 °C, excellent thermal stability at temperatures over 400 °C in air or nitrogen, high char yields of 51–58% in nitrogen and good solubility in CHCl₃ and polar solvents such as DMF, DMSO and NMP at room temperature.     

Synthesis and properties of new soluble aromatic polyamides and polyimides on the basis of N,N′‐bis(3‐aminobenzoyl)‐N,N′‐diphenyl‐1,4‐phenylenediamine

A new N‐phenylated amide (N‐phenylamide) unit containing aromatic diamine, N,N′‐bis(3‐aminobenzoyl)‐N,N′‐diphenyl‐1,4‐phenylenediamine, was prepared by the condensation of N,N′‐diphenyl‐1,4‐phenylenediamine with 3‐nitrobenzoyl chloride, followed by catalytic reduction. Two series of organosoluble aromatic poly(N‐phenylamide‐imide)s and poly(N‐phenylamide‐amide)s with inherent viscosities of 0.58–0.82 and 0.56–1.21 dL/g were prepared by a conventional two‐stage method and the direct phosphorylation polycondensation, respectively, from the diamine with various aromatic dianhydrides and aromatic dicarboxylic acids. All polyimides and polyamides are amorphous and readily soluble in many organic solvents such as N,N‐dimethylacetamide and N‐methyl‐2‐pyrrolidone. These polymers could be solution cast into transparent, tough, and flexible films with high tensile strengths. These polyimides and polyamides had glass‐transition temperatures in the ranges of 230–258 and 196–229 °C, respectively. Decomposition temperatures of the polyimides for 10% weight loss all occurred above 500 °C in both nitrogen and air atmospheres. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2564–2574, 2002     

Mass spectrometric determination of selenenylsulfide linkages in rat selenoprotein P

The reversible formation of a selenenylsulfide linkage in mammalian thioredoxin reductase was identified as having a key role in its activity. Identification of selenenylsulfide and/or diselenide linkages is therefore critical to the determination of the structure and function of selenoproteins. A selenopeptide, (298)SGSAITUQCAENLPSLCSUQGLFAEEK(324) (U=selenocysteine), was isolated from a tryptic digest of rat selenoprotein P. Its two cysteine residues and two selenocysteine (Sec) residues were determined to be present in oxidized form by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The selenopeptide was subjected to partial reduction by dithiothreitol with immediate alkylation by iodoacetamide. This process was monitored by MALDI-TOFMS to determine the number of alkylations that had taken place. The partially reduced and alkylated peptides were then analyzed by nano-electrospray ionization tandem mass spectrometry and the results indicated that selenenylsulfide linkages Sec304-Cys314 and Cys306-Sec316 were present. It is concluded that selenoprotein P contains these two selenenylsulfide bonds.     

Hierarchical fractal‐structured allophanate‐derived network formation in bulk polyurethane synthesis

Polyurethanes are among the most applied and researched polymers worldwide. Nevertheless, polyurethane synthesis is accompanied by a side‐reaction occurring between isocyanate groups and the secondary nitrogen of already formed urethane groups, leading to the formation of crosslinking allophanates. This inevitably requires the development of highly diagnostic direct analytical methods that can be performed in the solid state of the polymer. The present research focused on the direct investigation and diagnostic determination of the chemical structure formation in bulk polyurethane synthesis, using a combination of Fourier transform infrared and solid‐state ¹³C nuclear magnetic resonance analysis. Polyurethane syntheses were performed in bulk and designed as to obtain significantly strong diagnostic analytical measurements signals for the accurate identification of each of the investigated chemical structures. The present research results led to the conclusive analytical identification of allophanate formation during polyurethane synthesis. In addition, the occurrence of a new reaction mechanism was discovered in the present research. It was demonstrated in the present research that this newly described reaction occurs via the further reaction of the allophanate secondary nitrogen with an isocyanate group, the reaction creating a tertiary nitrogen and an additional reactive secondary nitrogen, and so on, in a consecutive step progression, leading to the formation of a 3‐dimensional hierarchical fractal‐like crosslinked polymeric structure. Solid‐state ¹³C nuclear magnetic resonance analysis results were highly consistent with the Fourier transform infrared results. The discovery of this newly described reaction can facilitate the optimization of industrial processes and potentially opens a new door to the development of a vast variety of biomedical and nanotechnology applications.     

Reactivity of urethanes at high temperature: Transurethanization and side reactions

The reactivity of urethanes based on 1,6‐hexamethylene diisocyanate (HDI) and 4,4′‐methylene diphenyl diisocyanate (MDI) was investigated at temperatures between 190 °C and 235 °C. Diurethane model compounds end‐capped with either 1‐dodecanol (D‐core‐D) or 1‐hexadecanol (H‐core‐H) were mixed and annealed at high temperature. The core was either MDI or HDI. The transurethanization reaction was followed based on the formation of the compounds (H‐core‐D). The amount of H‐core‐D and of side products, which had formed after variable annealing times, were identified with ¹H NMR, FTIR, SEC, and MALDI‐TOF. Transurethanization was considerably faster for MDI‐based urethanes than for HDI‐based urethanes. Only traces of side products were formed during annealing of MDI‐based urethanes, whereas a significant amount of allophanates was formed from HDI‐based urethanes under the same conditions. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 621–629     

On cohomological dimension and depth under linkage

Some relations between cohomological dimensions and depths of linked ideals are investigated and discussed by various examples.     

A Review of Surface Functionalized Amine Terminated Dendrimers for Application in Biological and Molecular Sensing

Dendrimers are three dimensional nanosized synthetic molecules that have internal cavities and numerous surface groups. In recent times they have received increased attention in sensing applications. For dendrimers to be used as sensors, they most commonly require functionalization at their surface. This is because the surface is generally the first point of contact between the dendrimer and the outside world, hence surface functionalization serves to selectively home in on the target analyte. Further, sensor signals may be transmitted through surface functionalities e.g. fluorochromic molecules. It is therefore important to document surface functionalization approaches. Dendrimers with amine surface groups have the advantage of being able to be conjugated to other molecules via an amide linkage, which is one of the most fundamental and widespread chemical bonds in nature. In this paper we demonstrate the properties of dendrimers that make them so applicable to sensing. We review several methods for functionalizing dendrimers via an amide linkage, as well as present a review of surface functionalized polyamidoamine, polyamine, and polypeptide dendrimers that have been employed for biological, chemical and molecular sensing.     

两个由铜离子与Waugh-型阴离子构筑的化合物的合成、晶体结构及表征

通过水热合成得到了一个新颖的包含四核铜配合物的无机-有机杂化化合物[CuCl(H₂O)₄)][CuCl(H₂O)(Phen)][{(CuPhen)₂Cl₂}₂(bdc)]₂[P₂W₁₈O₆₂]·5H₂O(1)(Phen=1,10-phenanthroline和bdc=1,4-benzenedicarboxylate),对其进行了元素分析、红外光谱、热重、电化学等表征,并用X-射线单晶衍射测定了它的晶体结构。化合物1含有由Cl和bdc桥连的四核铜配合物阳离子[{(CuPhen)₂Cl₂}₂(bdc)]²⁺。此外,化合物1的电化学研究表明其对亚硝酸的还原具有很好的电催化活性。