Formation,structure, and elasticity of loosely crosslinked epoxy-amine networks. I. Statistics of formation

Using the theory of branching processes based on cascade substitution, relations are derived for structural parameters characterizing network formation from diepoxide, monoepoxide, and diamine for various initial compositions. The different reactivities of the hydrogen atoms of the primary and secondary amino groups (the latter being formed in the reaction) and possibly different reactivities of epoxy groups in diepoxide and monoepoxide are taken into account. Relations are derived for the critical conversion at the gel point and for changes as a function of conversion in the average molecular weight in the pregel stage, changes in the sol and gel contents, effective functionality of the crosslinks, and concentration of elastically active network chains. The derivation includes the trapping factor that appears in the theory of permanent interchain interactions (trapped entanglements) of the Langley type. An analysis of the approximation usually employed in the statistical theory based on network formation from dyads of structural units shows that this approach is quite satisfactory for small differences in the reactivities of epoxy groups in diepoxide and monoepoxide.     

Spray drying of sol-gel precursors for the manufacturing of PZT powders

The preparation of fine PZT-powders via spray drying is described. The precursor solution was composed of Zr- and Ti-n-propoxide and lead acetate trihydrate or basic lead acetate. The hydrolysis and condensation reactions were controlled by the addition of acetylacetone as chelating agent.Depending on water content and solvent in the initial sols, spray dried micronsized gel powders with different morphologies and hydrolytic reactivities were obtained.     

Monte Carlo simulation of diepoxides and monoepoxides cured with amines

The diepoxide–monoepoxide–diamine curing systems are investigated with a Monte Carlo simulation. The dependence of the molecular weight distribution (MWD), gel fraction, and cycle rank of the polymers on the differences in the epoxy reactivities and the contents of the monoepoxide as a reactive diluent are discussed. Before gelation, the MWD of the curing systems with a lower content of the monoepoxide is broader than the MWD of the curing systems with a higher content, and it leads to a lower critical conversion. The gel fraction and cycle rank of the polymers decrease with an increasing amount of the diluent. Even fully cured, the system with a 0.6 epoxy molar fraction of the monoepoxide still has a large fraction of sol, about 49%. Although the various reactivities of the monoepoxide result in different ways of forming gels during curing, the final gel fractions are always near 100% as long as the epoxy molar fraction of the diluent is no more than 0.2. The profiles of the molecular weights of the polymers calculated by the model are in agreement with the experimental data. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1857–1868, 2002     

Clinical applications of lectin affinity electrophoresis.

Principles and several modifications of lectin affinity electrophoresis are described. The results obtained using these newly developed techniques are reviewed for individual glycoproteins, the altered lectin reactivities of which have some clinical implications, showing different lectin reactivities, which occur not only on malignant transformation but also in association with inflammatory process and hormonal action.     

Mass spectrometric identification of proteins and characterization of their post-translational modifications in proteome analysis

High-throughput DNA sequencing has resulted in increasing input in protein sequence databases. Today more than 20 genomes have been sequenced and many more will be completed in the near future, including the largest of them all, the human genome. Presently, sequence databases contain entries for more than 425.000 protein sequences. However, the cellular functions are determined by the set of proteins expressed in the cell--the proteome. Two-dimensional gel electrophoresis, mass spectrometry and bioinformatics have become important tools in correlating the proteome with the genome. The current dominant strategies for identification of proteins from gels based on peptide mass spectrometric fingerprinting and partial sequencing by mass spectrometry are described. After identification of the proteins the next challenge in proteome analysis is characterization of their post-translational modifications. The general problems associated with characterization of these directly from gel separated proteins are described and the current state of art for the determination of phosphorylation, glycosylation and proteolytic processing is illustrated.     

The hydroamination of alkenes with sulfonamides catalyzed by the recyclable silica gel supported triflic acid

The vast applications of triflic acid (TfOH) in catalysis are severely limited by its corrosive and fuming properties. Immobilization of TfOH on silica gel well solves these problems and affords efficient recovery and reusability of TfOH. Two types of supported TfOH, the prepared silica gel supported TfOH and the in situ silica gel adsorbed TfOH, both exhibit good catalytic activity and reusability in the hydroamination of alkene with sulfonamide. The in situ silica gel adsorbed catalyst has been used for 5 runs with maintained reactivities and yields, which are superior to the performance of the prepared silica gel supported TfOH. For a series of alkenes and various sulfonamides, the heterogeneous hydroamination reactions catalyzed by both types of silica gel supported TfOH to afford similar moderate to excellent yields.     

Mass spectrometric identification of proteins and characterization of their post-translational modifications in proteome analysis

High-throughput DNA sequencing has resulted in increasing input in protein sequence databases. Today more than 20 genomes have been sequenced and many more will be completed in the near future, including the largest of them all, the human genome. Presently, sequence databases contain entries for more than 425.000 protein sequences. However, the cellular functions are determined by the set of proteins expressed in the cell – the proteome. Two-dimensional gel electrophoresis, mass spectrometry and bioinformatics have become important tools in correlating the proteome with the genome. The current dominant strategies for identification of proteins from gels based on peptide mass spectrometric fingerprinting and partial sequencing by mass spectrometry are described. After identification of the proteins the next challenge in proteome analysis is characterization of their post-translational modifications. The general problems associated with characterization of these directly from gel separated proteins are described and the current state of art for the determination of phosphorylation, glycosylation and proteolytic processing is illustrated. Received: 16 December 1999 / Accepted: 17 December 1999     

Unique structural topology and reactivities of the ABD tricycle in phomactin A

Stereoselective and transannular reactivities are described for the ABD tricyclic manifold of phomactin A that possesses a unique structural topology.     

Improved detection of amylase activity by sodium dodecyl sulfate-polyacrylamide gel electrophoresis with copolymerized starch

An improved method, based on sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) for detection of amylase activity is described. This method will allow better characterization of certain amylases than that obtained by the Davis technique. The main features of the technique are: (i) identification of amylase bands and molecular mass determination are possible in the same gel; (ii) the hydrolysis of copolymerized substrate during electrophoretic separation is prevented using very low temperatures instead of inactivating agents such as chelating agents; and (iii) the technique is applicable to reveal amylase activity in a wide range of biological samples. The method is not useful for enzymes sensitive to SDS and for high molecular mass amylases.     

Photocatalysis on titanium oxide catalysts: Approaches in achieving highly efficient reactions and realizing the use of visible light

The photocatalytic reactivities of various Ti-based photocatalysts have been investigated for various different types of reactions in order to achieve as highly efficient photocatalytic reactivities as possible. The reactivity of powdered TiO2 is dramatically enhanced by the addition of small amounts of Pt which initiates an effective charge separation of the photo-formed electrons and holes. The highly dispersed titanium oxide species prepared and encapsulated within the zeolite cavities as well as into the SiO 2 matrices exhibit high photocatalytic reactivities due to the high reactivities of their charge transfer excited states. With regard to the use of visible light, ion implantation of metal ions such as Cr or V into powdered TiO2 catalysts has been found to modify the electronic state of TiO 2 , resulting in the shift of the absorption band to longer wavelength regions, i.e., into the visible light region. The extent of the shift strongly depends on the type and concentration of the implanted metal. The present study focuses on the preparation of the photocatalysts, a detailed characterization of the active sites and their dynamics, the direct detection of the reaction intermediate species, as well as a clarification of the mechanisms behind the observed photocatalytic reactions at the molecular level. This work significantly contributes to advances in the design of photocatalysts which will be able to operate efficiently and effectively not only under UV irradiation but, most ideally, under visible light.     

Characterization of zinc dialkyl dithiophosphate lubricating oil additives by high-voltage zone electrophoresis

A method is described for the rapid qualitative characterization of zinc dialkyl dithiophosphate oil additives by high-voltage zone electrophoresis, on a silica gel substrate. Samples of lubricating oils and lubricating oil additive packages can be analysed directly, as solutions in light petroleum (b.p. 80–100°).     

活性导向的化学探针在氨基酸反应活性表征中的应用进展

原创药物的研制得益于蛋白质新靶标的发现,而新靶标的发现依赖于高可信度、高通量的药物-蛋白质相互作用分析方法。蛋白质作为生命功能的执行者,其表达量、空间定位与结构差异直接影响药效的发挥。目前,超过85%的蛋白质尚被认为是无法成药的,主要原因是缺少药物分子靶向的空腔以及相应的反应活性位点。因此,基于蛋白质组学层次实现对氨基酸反应活性位点的表征成为原创共价靶向药物设计的关键,也是克服难以成药靶标蛋白问题的关键。近年来,质谱技术的飞速发展极大地推动了基于蛋白质组学技术的药物-靶蛋白相互作用研究。其中基于活性的蛋白质组分析(ABPP)策略是利用活性位点导向的化学探针分子在复杂样品中实现功能状态酶和药物靶标等蛋白质的检测。基于化学探针的开发和质谱定量技术的发展,ABPP技术在氨基酸反应活性表征研究中展现出重要的应用潜力,将助力于药物新靶标的发现和药物先导化合物的开发。ABPP策略主要基于蛋白质的活性特征进行富集,活性探针作为ABPP策略的核心,近年来取得了飞速进展。该文回顾了ABPP策略的发展历程,重点介绍基于广谱活性探针的ABPP技术在多种氨基酸反应活性筛选领域的研究进展,并对其在药物靶点发现中...     

Theoretical investigations of the reactivities of saturated five-membered ring N-heterocyclic carbenes with heavier group 14 elements

The potential energy surfaces for the chemical reactions of group 14 carbenes have been studied using density functional theory (B3LYP/LANL2DZ). Five saturated five-membered-ring N-heterocyclic carbene Dipp[upper bond 1 start]N(CH(2))(2)N(Dipp)E[upper bond 1 end]: (five-ring-E:) species, where E = C, Si, Ge, Sn and Pb, have been chosen as model reactants in this work. Also, four kinds of chemical reactions; addition of water, methane insertion, alkene cycloaddition and dimerization, have been used to study the chemical reactivities of these group 14 carbenes. The present theoretical investigations suggest that the relative carbenic reactivity decreases in the order: C > Si > Ge > Sn > Pb. That is, the heavier the group 14 atom (E), the more stable is the carbene towards chemical reactions. This may be the reason that there have been many instances reported of the synthesis and characterization of stable group 14 five-membered-ring N-heterocyclic carbene species with various alkyl protecting substituents at room temperature. Furthermore, the singlet-triplet energy splitting of the five-ring-E:, as described in the configuration mixing model attributed to the work of Pross and Shaik, can be used as a diagnostic tool to predict their reactivities. The results obtained allow a number of predictions to be made.     

Kinetic analysis of curing of tetraepoxides and diamines in the presence of etherification side reactions

The theory of branching processes is used to describe the polymer network formation resulting from the reaction of tetraepoxides with diamines using various initial compositions. Differences in reactivities of primary and secondary amine groups and the reaction between the epoxide groups and reaction-generated hydroxyl groups are taken into account; however, intramolecular reactions in the pregel stage are neglected. Expressions are derived for the critical epoxide conversion at the gel point, molecular weight in the pregel stage, changes in sol and gel fraction in the post-gel stage, and the concentration of elastically active network chains as a function of reaction conditions. The analysis of the simulation results shows that etherification reactions significantly raise the concentration of elastically active network chains of the mixture under stoichiometric excess of epoxide groups.     

The Radiation-Induced Copolymerization of Methyl Methacrylate with Di- and Trimethacrylates

The rates and gel formation of the radiation-induced co-polymerization of a number of dimethacrylates and trimethylol propane trimethacrylate with methyl methacrylate has been studied in detail. The rates were found to be linked to the nature and amount of gel formed rather than to differences in the reactivities of the monomers.     

A chiral low-molecular-weight gelator based on binaphthalene with two urea moieties: modulation of the CD spectrum after gel formation

The synthesis and characterization of a new chiral LMWG 1 based on the axially chiral binaphthalene with two urea moieties were described. A transparent gel in cyclohexane with LMWG 1 was obtained and characterized by SEM, XRD and CD techniques. The results of 1H NMR measurement indicated that the intermolecular H-bonds and pi-pi interaction may be responsible for the gel formation. It was demonstrated that the gel phase could be destroyed by addition of F- due to the disruption of intermolecular H-bonds. After gel formation, modulation of the CD spectrum of 1 was observed.     

Structural analysis of protein complexes with sodium alkyl sulfates by small-angle scattering and polyacrylamide gel electrophoresis

Small-angle X-ray (SAXS) and neutron (SANS) scattering is used to probe the structure of protein-surfactant complexes in solution and to correlate this information with their performance in gel electrophoresis. Proteins with sizes between 6.5 to 116 kDa are denatured with sodium alkyl sulfates (SC(x)S) of variable tail lengths. Several combinations of proteins and surfactants are analyzed to measure micelle radii, the distance between micelles, the extension of the complex, the radius of gyration, and the electrophoretic mobility. The structural characterization shows that most protein-surfactant complexes can be accurately described as pearl-necklace structures with spherical micelles. However, protein complexes with short surfactants (SC(8)S) bind with micelles that deviate significantly from spherical shape. Sodium decyl (SC(10)S) and dodecyl (SC(12)S, more commonly abbreviated as SDS) sulfates result in the best protein separations in standard gel electrophoresis. Particularly, SC(10)S shows higher resolutions for complexes of low molecular weight. The systematic characterization of alkyl sulfate surfactants demonstrates that changes in the chain architecture can significantly affect electrophoretic migration so that protein-surfactant structures could be optimized for high resolution protein separations.     

Gel Permeation Chromatography of Unsaturated Polyester Resins. Possibilities and Limitations

Abstract

The use of gel permeation chromatography (GPC) for the characterization of unsaturated polyester resins is demonstrated on several examples. Number-average molecular weights determined by this method are compared to data obtained by means of vapor pressure osmometry (VPO) and by end group analysis (EG). The determination of the polyester resin composition as a function of molecular weight by stop-and-go UV scanning procedure is described. A comparison of theoretical and experimental molecular distribution is applied to the estimation of branching extent.     

Early cure behavior of a liquid dicyanate ester resin

The early cure behavior of 4,4‐dicyanato 1,1‐diphenolethane resin with and without incorporating Cr(acac)₃, Co(acac)₃, and Cu(acac)₂, respectively, as catalysts was investigated by gel permeation chromatography. The curing intermediates were separated by the column elution method and characterized by Fourier transform infrared, ¹H, and ³C NMR spectroscopies. The results indicated that the formed dimer in the early cure stage is a straight chain containing a primary amino group. The formed triazine ring in the trimer has a strong catalytic effect on the remaining cyanate groups so that the reactivity of the trimers was significantly increased. The reactivities of the curing intermediates decreased with molecular size until 7‐mer was reached. The initial monomer consumption is described by second‐order‐rate kinetics. In the presence of metal acetylacetonates, the curing reactions may be accelerated, but they did not change the reaction path and preceding sequence of reactivities. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3085–3092, 2001     

Examples of Using 3D-GPC-TREF for Polyolefin Characterization

Summary: Selected examples of using 3D-GPC-TREF to solve polyolefin characterization problems are described in this paper. The term 3D-GPC-TREF stands for a home-build hybrid system of gel permeation chromatograph (GPC) coupled with the capability of the temperature rising elution fractionation (TREF) that includes three online detectors, i.e. the infrared (IR), the differential-pressure viscometer (DP), and the light scattering (LS) detectors.