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排序方式: 共有191条查询结果,搜索用时 62 毫秒
81.
We report the first synthesis of a disyndiotactic polymer through topochemical polymerization using di(4-methoxybenzyl)muconate as the 1,3-diene dicarboxylate monomer. It provides a tritactic polymer under photoirradiation in the crystalline state, as a result of the alternate molecular stacking in a column formed in the crystals with aid of weak hydrogen bonds such as CH/pi and CH...O intermolecular interactions. 相似文献
82.
This paper proposes a new method for simultaneous analysis of unsaturated disaccharides derived from glycosaminoglycans by enzymatic digestion with chondroitinase ABC, based on high-performance capillary electrophoresis (HPCE) of their 1-phenyl-3-methyl-5-pyrazolone derivatives. The O-sulphate group is stable in this derivatization, and this method allows reproducible microdetermination of glycosaminoglycans. This paper also demonstrates the applicability of this method to estimation of urinary chondroitin sulphates. Urinary creatinine as an inherent internal standard could also be estimated by HPCE, though in another mode of separation, i.e. ion-exchange electrokinetic chromatography. 相似文献
83.
Significant levels of enantioselectivity were obtained in 1,3-dipolar cycloadditions of 2-benzopyrylium-4-olate generated from the Rh(2)(OAc)(4)-catalyzed decomposition of o-methoxycarbonyl-alpha-diazoacetophenone. This reaction utilized chiral 2,6-bis(oxazolinyl)pyridine (Pybox)--rare earth metal triflate complexes as chiral Lewis acid catalysts. The reactions with several benzyloxyacetaldehyde derivatives catalyzed by a Sc(III)--Pybox-i-Pr complex (10 mol %) proceeded smoothly to yield endo-adducts selectively with high enantioselectivity (up to 93% ee). For the reaction with benzyl pyruvate, the Sc(III)-Pybox-i-Pr complex (10 mol %) catalyzed the reaction effectively in the presence of trifluoroacetic acid (10 mol %) to yield an exo-adduct with both high diastereo- and enantioselectivity (94% ee). This catalytic system was efficiently applied to the reactions with several other alpha-keto esters with high exo- and enantioselectivities (up to 95% ee). In contrast to the reaction with carbonyl compounds, Yb(III)--Pybox-Ph complex (10 mol %) was found to be effective to obtain high enantioselectivity (96% ee) of diastereoselectively produced exo-cycloadduct in the reaction with 3-acryloyl-2-oxazolidinone. 相似文献
84.
Evaluation of glycosylation for quality assurance of antibody pharmaceuticals by capillary electrophoresis 总被引:1,自引:0,他引:1
The development of monoclonal antibody (mAb) pharmaceuticals has rapidly generated in this decade, and there are currently 23 FDA-approved mAb pharmaceuticals. Carbohydrate chains in mAb pharmaceuticals play important roles for the expression of their biological activities such as antibody-dependent cellular cytotoxicity, whereas the oligosaccharide profile is easily changed depending on the manufacturing conditions. Therefore, the evaluation of carbohydrate chains in detail is quite important for quality control in the development of mAb from early phases, but oligosaccharides in mAb have high heterogeneity and full characterization of oligosaccharide moiety in mAb has been a challenging target. Capillary electrophoresis (CE) is a powerful tool for the evaluation of glycan occupancy and oligosaccharide profile. This review focuses mainly on the application of CE to the analytical studies on glycosylation in mAb pharmaceuticals developed in our laboratory. The related techniques including the full-image microchip isoelectric focusing and the newly developed mass spectrometry technologies are also shown. The combination of the techniques described in this review will be a good guide for the evaluation of glycosylation for quality assurance of antibody pharmaceuticals by CE from the early stage of the development to the marketing stage. 相似文献
85.
Yoshinori Nakano Eriko Sato Akikazu Matsumoto 《Journal of polymer science. Part A, Polymer chemistry》2014,52(20):2899-2910
We prepared the sequence‐controlled block copolymers including poly(1‐adamantyl acrylate) (PAdA) and poly(n‐butyl acrylate) sequences as the hard and soft segments, respectively, by the organotellurium‐mediated living radical polymerization. The thermal, optical, and mechanical properties of the adamantane‐containing block copolymers with polar 2‐hydroxyethyl acrylate (HEA) and acrylic acid (AA) repeating units were investigated. The microphase‐separated structures of the block copolymers were confirmed by the differential scanning calorimetry and atomic force microscopy observations as well as dynamic mechanical measurements. The α‐ and β‐dispersions due to the main‐chain and side group molecular motions, respectively, of the hard and soft segments were observed. Their transition temperatures and activation energies increased due to the formation of intermolecular hydrogen bonding by the introduction of the HEA and AA repeating units. The effects of the hydrogen bonding on their tensile elasticity, strength, and strain were also evaluated. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2899–2910 相似文献
86.
Reversible addition‐fragmentation chain transfer polymerization of diisopropyl fumarate using various dithiobenzoates as chain transfer agents 下载免费PDF全文
Kohei Takada Akikazu Matsumoto 《Journal of polymer science. Part A, Polymer chemistry》2017,55(19):3266-3275
Dialkyl fumarates as 1,2‐disubstituted ethylenes exhibit unique features of radical polymerization kinetics due to their significant steric hindrance in propagation and termination processes and provide polymers with a rigid chain structure different from conventional vinyl polymers. In this study, we carried out reversible addition‐fragmentation chain transfer polymerization of diisopropyl fumarate (DiPF) in bulk at 80 °C using various dithiobenzoates with different leaving R groups as chain transfer agents to reveal their performance for control of molecular weight, molecular weight distribution, and chain end functionality of the resulting poly(DiPF) (PDiPF). 2‐(Ethoxycarbonyl)‐2‐propyl dithiobenzoate ( DB1 ) and 2,4,4‐trimethyl‐2‐pentyl dithiobenzoate ( DB2 ) underwent fragmentation and reinitiation at a moderate rate and consequently led to the formation of PDiPF with well‐controlled chain structures. It was confirmed that molecular weight of PDiPF produced by controlled polymerization with DB1 and DB2 agreed with theoretical one and molecular weight distribution was narrow. Dithiobenzoate and R fragments were introduced into the polymer chain ends with high functionality as 95% by the use of DB1 . In contrast, polymerizations using 1‐(ethoxycarbonyl)benzyl dithiobenzoate ( DB3 ), 1‐phenylethyl dithiobenzoate ( DB4 ), and 2‐phenyl‐2‐propyl dithiobenzoate ( DB5 ) resulted in poor control of molecular weight, molecular weight distribution, and chain end structures of PDiPF. Fragmentation and reinitiation rates of the used benzoates as chain transfer agents significantly varied depending on the R structures in an opposite fashion; that is, introduction of bulky and conjugating substituents accelerated fragmentation, but it retarded initiation of DiPF polymerization. It was revealed that balance of fragmentation and reinitiation was important for controlled polymerization of DiPF. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3266–3275 相似文献
87.
A Kakehi S Ito H Suga S Sakurai T Kobayashi 《Chemical & pharmaceutical bulletin》2001,49(11):1401-1405
New compounds having two indolizine nuclei in a molecule were prepared in low to moderate yields from the reactions of potassium 2-indolizinethiolates with 1,omega-dihalides such as 1,2-diiodoethane, 1,3-dibromopropane, 1,4-dibromobutane, alpha,alpha'-dichloro-o-xylene, and alpha,alpha'-dichloro-p-xylene. Most of the products had the conformation in which the two indolizine rings in the molecule are as remote as possible, but only 1,2-bis[[(2-indolizinyl)thio]methyl]benzene derivatives, prepared from potassium 2-indolizinethiolates and alpha,alpha'-dichloro-o-xylene, showed a weak attractive interaction between the two indolizine nuclei in the X-ray analysis and the nuclear Overhauser and exchange spectroscopy (NOESY) spectrum. 相似文献
88.
Total N-linked oligosaccharide profiling method for recombinant monoclonal antibody (rmAb) using capillary electrophoresis with laser-induced fluorescence detection (CE-LIF) and an approach for detailed structural analysis of N-linked oligosaccharide were developed. A CE-LIF method using 2-aminobenzoic acid (2-AA) as a fluorogenic reagent allowed sensitive detection of several minor peaks besides typical asialo-biantennary complex type oligosaccharides in the analysis of N-linked oligosaccharide from a commercial rmAb pharmaceutical, rituximab. These minor peaks were successfully assigned as sialo-biantennary complex type and high-mannose type oligosaccharides by comparison with the migration times of 2-AA derivatized oligosaccharides which were separately fractionated and determined by high-performance liquid chromatography (HPLC) and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). In development of biopharmaceuticals, it is important to evaluate these minor oligosaccharides, because some of these minor glycans are likely to influence immunogenicity and clearance rate in vivo. The repetitive analysis using CE-LIF showed excellent precision in relative corrected peak areas. These results demonstrate that the present CE-LIF method is applicable for both structural characterization and quantitative profiling of N-linked oligosaccharides derived from rmAb pharmaceuticals. The present method will be a powerful tool for rapid, quantitative and exhaustive evaluation of N-linked oligosaccharides in various stages of rmAb pharmaceutical development such as clone selection, bioprocess control, and routine lot release testing to ensure product efficacy and consistency. 相似文献
89.