Determination of Polymer Molecular Weight by GPC in the Low Molecular Weight Region

Abstract

In order to determine the molecular weight of a polymer by GPC in the low MW region, a secondary calibration method can be established when polymer standards of the analysed polymer are not available (1). The efficiency of this method has been checked for the system poly(methyl methacrylate) (PMMA-methyl ethyl ketone (MEK) using polystyrene (PS) standards. When the solvent is poor for one of the polymers, limitations arise due to the secondary separation effects. Furthermore, a GPC method is proposed for the determination of the Dondos-Benoīt constants (A₁ A₂) which must be known for the above-mentioned calibration. This method uses either two or at least one polydisperse polymer sample.     

Gemini Surfactants as New,Low Molecular Weight Gelators of Organic Solvents and Water

As many as 1200 solvent molecules can be entrapped by one molecule of the cationic dimeric surfactants 1 to form a gel in CHCl₃. These new gelators contain chiral counterions and form gels with both organic solvents and water upon their assembly into helical aggregates, which have similar structures in both media.     

Dimensional Separation Of Low Molecular Weight Compounds

Abstract

The current status of separation of low molecular weight compounds by size exclusion chromatography and the hybrid modes, size partition and size adsorption chromatography is reviewed.     

改性低分子量聚异戊二烯橡胶的合成与应用

采用阴离子溶液聚合法合成了低分子量3,4-聚异戊二烯(LPI), 并对其进行改性, 制备了硅氧烷改性的低分子量3,4-聚异戊二烯(MLPI), 将其应用于白炭黑补强的溶聚丁苯橡胶(SSBR)复合材料, 探究了端基改性物LPI-丙基甲基二甲氧基硅烷(LPI-CMDS)、 LPI-丙基三甲氧基硅烷(LPI-CTMS)、 LPI-丙基三乙氧基硅烷(LPI-CTES)和接枝改性物3-巯丙基三乙氧基硅烷接枝改性LPI(LPI-g-MTS)对SSBR复合材料中白炭黑的分散以及硫化胶性能的影响. 混炼胶的应变扫描和结合胶含量分析结果表明, MLPI增强了填料与聚合物之间的相互作用, 改善了白炭黑在复合材料中的分散, 其中LPI-g-MTS因活性位点多, 效果最佳; 与填充LPI的复合材料相比, 硫化胶的物理机械性能, 尤其是填充LPI-g-MTS后硫化胶的300%定伸应力和拉伸强度分别提升了89.66%和27.15%, 这为改善白炭黑在非极性橡胶中的分散提供了一条新途径.     

Progress in Molecular Dynamics and Hansen Solubility Parameters of Low Molecular Weight Gels北大核心CSCD

Recently,the use of computational methods such as Molecular Dynamics（MD）simulations and Hansen Solubility Parameters （HSPs）to study the behavior of small molecule gelators has attracted much attention. MD simulation is a computational method based on classical mechanics and is one of the preferred techniques for understanding the process of small molecule gelators. The MD simulation can more accurately analyze the gelation trend or assembly behavior of small molecule gelators,dynamically and graphically display the self-assembly process,effectively reveal the relationship between the structure of small molecule gelators and related gelation behavior,and quantitatively analyze non-covalent bond interactions such as hydrogen bonds,π-π stacking,van der Waals interactions,ionic bonding and solvophobic interactions. By performing molecular dynamics simulations on known gelators/non-gelators,parameters related to gelation behavior in the simulated data are extracted,and the linear correlation is measured by fitting the Pearson correlation coefficient to finally predict the gelation behavior of a certain class of small molecules. On the other hand,the empirical model developed according to the HSPs is the most representative,which consists of the energy of dispersion interaction（δd）,the energy of polar interaction（δp）and H-bonding energy（δh ）between molecules. These three parts determine the coordinate point of the three-dimensional space（Hansen space）. According to the range of the point,it can be determined whether the organic small molecule can form a gel in a specific solvent. In this paper,representative works published recently in the field of organic small molecule gels by using MD simulations and empirical models are reviewed. Some comments on the assembly behavior of gelators,the regulation and prediction of non-covalent bond interactions on gelation ability are made. © 2022, Science Press (China). All rights reserved.     

Analysis of Low Molecular Weight Homologues of Fiber-Forming Polycondensates

Oligomers belong to the gray area between low molecular weight chemistry and macromolecular chemistry. Although they represent an undesirable “natural impurity” in fiber-forming polycondensates, they serve as useful model compounds for the corresponding polymers in fundamental research. Whereas for many years new classes of oligomers were being made preparatively accessible and the isolation of higher oligomers in pure form was being pursued, at the present time the emphasis is on analysis. By a combination of classical chemical and instrumental methods of analysis from polymer and organic chemistry, the identification of oligomers of unknown structure, the analytical control of their synthesis and the determination of their content in technical polymers has meanwhile become a routine task.     

Gelation Kinetics-Structure Analysis of pH-triggered Low Molecular Weight Hydrogelators

Properties such as shear modulus, gelation time, structure of supramolecular hydrogels are strongly dependent on self-assembly, gelation triggering mechanism and processes used to form the gel. In our work we extend reported rheology analysis methodologies to pH-triggered supramolecular gels to understand structural insight using a model system based on N−N’ Dibenzoyl-L-Cystine pH-triggered hydrogelator and Glucono-δ-Lactone as the trigger. We observed that Avrami growth model when applied to time-sweep rheological data of gels formed at lower trigger concentrations provide estimates of fractal dimension which agree well compared with visualization of the microstructure as seen via Confocal Laser Scanning Microscopy, for a range of gelator concentrations.     

低分子量壳聚糖制备与应用研究进展

低分子量壳聚糖因具有特殊的生物活性而日益受到人们的关注。本文概要介绍了近5年来国内外低分子量壳聚糖的研究进展,包括低分子量壳聚糖的制备方法,如酶降解法、酸水解法、氧化降解法、物理法等,以及低分子量壳聚糖在农业、医药、抗菌、化妆品、食品等方面的应用。     

血清中低分子量蛋白质的提取和鉴定

采用改进的圆盘凝胶电泳提取人血清中低分子量蛋白质, 去除了血清中分子量大于3×104的蛋白质, 将提取的低分子量蛋白质热变性后直接在溶液中酶解成肽, 经液相色谱-质谱分析, 并进行Mascot数据库检索, 确认出人血清中97种蛋白质.     

Disordered Low Molecular Weight Spiropyran Exhibiting Photoregulated Adhesion Ability

The functions of the materials composed of small molecules are highly dependent on their ordered molecular arrangements in both natural and artificial systems. Without ordered structure, small molecules hardly gain complicated functions, due to the absence of intermolecular covalent bond connection or strong network. Here, a low molecular weight spiropyran that could exhibit attractive photochromism and powerful adhesion property in disordered solid state is demonstrated. With maximum up to ∼8 MPa, the adhesion strength could be photoregulated in multiple levels, which also shows one-to-one correspondence to the specific color state. The working mechanism analysis on the photoregulated adhesion reveals that the isomer ratio of merocyanine form and the molecular packing density of spiropyran are the determining factors for the adhesion ability. The discovery of photoregulated adhesion from pure spiropyran provides a new strategy for developing functional materials by employing low molecular weight compounds.     

低分子量溴代聚苯乙烯的制备及应用

用溶液法合成了一系列低分子量的聚苯乙烯，其溴化产物（Ｂｒ－ＰＳ）的溴含量和热稳定性与美国同类产品Ｐｙｒｏ－Ｃｈｅｋ ＬＭ相当，分别用作聚苯乙烯树脂的阻燃剂，极限氧指数测定结果表明，其阻燃性也达到了Ｐｙｒｏ－Ｃｈｅｋ ＬＭ的水平。     

Displacement Chromatography of Proteins using Low Molecular Weight Anionic Displacers

A major impediment to the implementation of displacement chromatography has been the lack of suitable displacer compounds. Recently, it has been shown that low molecular weight dendritic polymers, protected amino acids and antibiotics can be successfully employed for displacement purification in cation-exchange systems. In this paper, a variety of low molecular weight anionic displacers are identified for the resolution of a bovine -lactoglobulin mixture into two closely related forms (A and B). A Dynamic Affinity plot is employed to evaluate the affinity of these low molecular weight compounds under various displacement conditions. In contrast to large polyelectrolyte displacers, the efficacy of these low molecular weight displacers are shown to be dependent on displacer concentration. In fact, the Dynamic Affinity Plot qualitatively predicts the transition from a displacement to a desorption regime with these low molecular weight displacers. In addition to the fundamental interest generated by low molecular weight displacers, it is likely that these displacers will have significant operational advantages as compared to large polyelectrolyte displacers. Furthermore, the ability to carry out selective displacement chromatography with these low molecular weight displacers offers significant potential for developing robust large scale displacement processes.     

Analysis of Low Molecular Weight Polymers with Gel Permeation Chromatography

Intrinsic viscosities and gel permeation chromatography (GPC) elution times were determined in toluene on commercially available standards of polystyrene (PSTY) and polymethyl methacrylate (PMMA) having M_n in the range of 10³ to 10⁵ and 10⁴ to 10⁶, respectively. In addition, elution times were determined on the discrete GPC peaks of dimer, trimer, tetramer, etc. as seen in lower molecular weight PSTY and PMMA. Intrinsic viscosities of oligomers were estimated by extrapolation of the Mark-Houwind-Sakurada equations determined from our data, and the results were used to establish a universal calibration curve over a wide range of molecular weights. A similar approach was taken by using literature data for the intrinsic viscosities of PSTY and PMMA in tetra-hydrofuran. It was verified by proton NMR that the universal calibration curve so constructed is useful at M_n, values as low as 300. No correction was necessary for chain length dependence of the detector response.     

A GPC Method for Analysis of Low Molecular Weight Drugs

Abstract

Gel permeation chromatography has been shown as a versatile method for the analysis of low molecular weight drugs. Aspirin and its hydrolysis product, salicylic acid, which differ in a molecular weight of 42 units have been efficiently separated by a retention time difference of 3.25 minutes. Qualitative idea of other impurities is also obtained.     

超积累植物体内的小分子螯合物质及其生理作用

螯合效应是超积累植物忍耐重金属的重要机理之一,不同的超积累植物对不同的重金属胁迫其体内产生的螯合物质不同。目前在超积累植物中发现的螯合物质以其分子量大小可分为两大类,即：草酸、组氨酸、苹果硫、柠檬酸及谷胱甘肽等小分子物质和金属硫蛋白、植物络合素、金属结合体及金属结合蛋白等大分子物质。本文就超积累植物体内的小分子螯合物质及其生理作用作一概述。     

Low Molecular Weight Norbornadiene Derivatives for Molecular Solar‐Thermal Energy Storage

Molecular solar‐thermal energy storage systems are based on molecular switches that reversibly convert solar energy into chemical energy. Herein, we report the synthesis, characterization, and computational evaluation of a series of low molecular weight (193–260 g mol^?1) norbornadiene–quadricyclane systems. The molecules feature cyano acceptor and ethynyl‐substituted aromatic donor groups, leading to a good match with solar irradiation, quantitative photo‐thermal conversion between the norbornadiene and quadricyclane, as well as high energy storage densities (396–629 kJ kg^?1). The spectroscopic properties and energy storage capability have been further evaluated through density functional theory calculations, which indicate that the ethynyl moiety plays a critical role in obtaining the high oscillator strengths seen for these molecules.     

Amphiphiles Based on d-Glucose: Efficient Low Molecular Weight Gelators

A series of novel amphiphiles were synthesized based entirely on renewable resources. Besides their efficacy as supramolecular gelators in a wide variety of organic solvents and also water, their surface properties as surfactants and emulsifiers have been determined. A methodical study revealed that the length of the hydrocarbon chains has a dramatic and decisive influence on the thermal stabilities of the obtained hydrogels.     

Elution Behavior of Low Molecular Weight Compounds in Gel Permeation Chromatography

Abstract

Elution behavior of organic compounds in gel permeation chromatography was investigated using chloroform as eluent. In aliphatic hydrocarbons, the elution counts decreased linearly with increasing the molecular volumes. In aromatic hydrocarbons, the relation between molecular volume and elution count slightly shifted toward lower counts. The elution counts in esters, ketones, amides, alcohols and carboxylic acids always fell in lower elution counts than expected by aliphatic hydrocarbons. This fact suggests that all these compounds are solvated by eluent molecules. Amines and chlorides exhibit an adsorption effect on cross-linked polystyrene gel. These compounds are eluted behind the corresponding hydrocarbons for given molecular volumes, which were obtained by dividing molecular weight by density.