Molecular Weight Characteristics Research Articles

A Theoretical Investigation of the Polyaddition of an AB2+A2+B4 Monomer Mixture.

Hyperbranched polymers (HBPs) are widely applied nowadays as functional materials for biomedicine needs, nonlinear optics, organic semiconductors, etc. One of the effective and promising ways to synthesize HBPs is a polyaddition of AB2+A2+B4 monomers that is generated in the A2+CB2, AA'+B3, A2+B'B2, and A2+C2+B3 systems or using other approaches. It is clear that all the foundational features of HBPs that are manufactured by a polyaddition reaction are defined by the component composition of the monomer mixture. For this reason, we have designed a structural kinetic model of AB2+A2+B4 monomer mixture polyaddition which makes it possible to predict the impact of the monomer mixture's composition on the molecular weight characteristics of hyperbranched polymers (number average (DPn) and weight average (DPw) degree of polymerization), as well as the degree of branching (DB) and gel point (pg). The suggested model also considers the possibility of a positive or negative substitution effect during polyaddition. The change in the macromolecule parameters of HBPs formed by polyaddition of AB2+A2+B4 monomers is described as an infinite system of kinetic equations. The solution for the equation system was found using the method of generating functions. The impact of both the component's composition and the substitution effect during the polyaddition of AB2+A2+B4 monomers on structural and molecular weight HBP characteristics was investigated. The suggested model is fairly versatile; it makes it possible to describe every possible case of polyaddition with various monomer combinations, such as A2+AB2, AB2+B4, AB2, or A2+B4. The influence of each monomer type on the main characteristics of hyperbranched polymers that are obtained by the polyaddition of AB2+A2+B4 monomers has been investigated. Based on the results obtained, an empirical formula was proposed to estimate the pg = pA during the polyaddition of an AB2+A2+B4 monomer mixture: pg = pA = (-0.53([B]0/[A]0)1/2 + 0.78)υAB2 + (1/3)1/2([B]0/[A]0)1/2, where (1/3)1/2([B]0/[A]0)1/2 is the Flory equation for the A2+B4 polyaddition, [A]0 and [B]0 are the A and B group concentration from A2 and B4, respectively, and υAB2 is the mole fraction of the AB2 monomer in the mixture. The equation obtained allows us to accurately predict the pg value, with an AB2 monomer content of up to 80%.

Comparative Analysis of Catalase Activity in Plants: Spectrophotometry and Native PAGE Approaches.

Catalase, a pivotal enzyme in plant antioxidative defense mechanisms, plays a crucial role in detoxifying hydrogen peroxide, a reactive oxygen species (ROS). In this chapter, a comparative analysis of catalase activity was conducted using two distinct methodologies: spectrophotometry and non-denaturing polyacrylamide gel electrophoresis (PAGE). The spectrophotometric approach allowed the quantification of catalase activity by measuring the breakdown rate of hydrogen peroxide, while native PAGE enabled the separation and visualization of catalase isozymes, based on their native molecular weight and charge characteristics, and specific staining assay. Both methods provide valuable insights into catalase activity, offering complementary information on the enzyme's functional diversity and distribution within different plant tissues. This study integrates different techniques, previously described, to comprehensively elucidate the role of catalase in plant metabolism. Furthermore, it provides the possibility of obtaining a holistic understanding of antioxidant defense mechanisms by considering both total activity and isoenzyme distribution of catalase enzyme.

Specifics of Pharmacokinetics and Biodistribution of 5-Fluorouracil Polymeric Complex.

Monomeric methacrylic acid was used to synthesize polymers; 2-phenylpropane-2-ilbenzodithioate was used for the synthesis of poly(methacrylic acid). To study the molecular-weight characteristics of poly(methacrylic acid) by gel permeation chromatography, an experimental neoplasm model was obtained by grafting PC-1 cancer cells. Blood samples were drawn from the tail vein at different points in time. The rats were sacrificed via decapitation after drawing the last pharmacokinetic blood sample. To study the biodistribution, internal organs were isolated and analyzed. The measurements were carried out by high-performance liquid chromatography. Our results demonstrate that incorporation in a polymeric complex changes the pharmacokinetics and biodistribution profile of 5-FU. The polymeric complex was shown to accumulate to a higher level in the lung and spleen. The results obtained are the basis for further studies to verify the efficacy of the 5-Fluorouracil polymeric complex.

Single‐Component Catalysts for the Vinyl‐Addition Polymerization of Norbornene and its Derivatives

AbstractVinyl‐addition polynorbornenes are versatile templates for the targeted design of high‐performance materials for various applications such as membrane gas separation, micro‐ and optoelectronics, fuel cells, sensors, and catalyst supports. The cornerstone of the synthesis of these compounds is the choice of catalyst used for polymerization. Previous review articles focused on two‐ and three‐component catalytic systems with cocatalysts used for vinyl‐addition polymerization (VAP). Hence, this Review discusses the advances in the design and development of single‐component neutral and cationic catalysts for the VAP of norbornenes. The catalyst structure, catalytic activity, and molecular weight characteristics of the polymers produced using these catalysts are elucidated.

Non-aldehyde resins based on resorcinol and natural alkylresorcinols modified with styrene

The use of natural alkylresorcinols produced in Estonia (5-methylresorcinol, HONEYOL80 fraction) instead of the expensive resorcinol reduces the cost of the synthesized resins while maintaining their high technological characteristics. Resins based on resorcinol (R), 5-methylresorcinol (5-MR), HONEYOL80, dicyclopentadiene (DCPD), and styrene (S) were synthesized in the presence of an acid catalyst. Their physical and chemical characteristics have also been studied. It was shown that depending on the mole ratio of the components of the formulation, resins with different softening temperatures (66 to 97 °C), ash content of 0.04 to 0.39 wt%, and a low content of volatile components at 105 °C, including moisture, were obtained. The best conditions for the synthesis of resins with a softening point of 94 °C–97 °C are molar ratio of R (5-MR): DCPD: S = 1: 0.5: 0.3 at temperature 135 °C–170 °C, synthesis time 5 h 30 min. The synthesized resins did not require additional processing under a vacuum. The presence of unreacted resorcinol and 5-methylresorcinol (quantitatively and qualitatively) in the final product, the homogeneity, and molecular weight characteristics of the resin composition (qualitatively) were determined by TLC and GPC.

Polyisobutylenes with Controlled Molecular Weight and Chain-End Structure: Synthesis and Actual Applications.

The polymerization of isobutylene allows us to obtain a wide spectrum of polyisobutylenes (PIBs) which differ in their molecular weight characteristics and the chemical structure of chain-end groups. The bulk of the PIBs manufactured worldwide are highly reactive polyisobutylenes (HRPIBs) with -C(Me)=CH2 end-groups and low-molecular weights (Mn < 5 kDa). HRPIBs are feedstocks that are in high demand in the manufacturing of additives for fuels and oils, adhesives, detergents, and other fine chemicals. In addition, HRPIBs and CMe2Cl-terminated PIBs are intensively studied with the aim of finding biomedical applications and for the purpose of developing new materials. Both chain control (molecular weight and dispersity) and chemoselectivity (formation of exo-olefinic or -CMe2Cl groups) should be achieved during polymerization. This review highlights the fundamental issues in the mechanisms of isobutylene polymerization and PIB analysis, examines actual catalytic approaches to PIBs, and describes recent studies on the functionalization and applications of HRPIBs and halogen-terminated PIBs.

Modeling of Poly(Ethylene Terephthalate) Homogeneous Glycolysis Kinetics.

Polymer composites with various recycled poly(ethylene terephthalate)-based (PET-based) polyester matrices (poly(ethylene terephthalate), copolyesters, and unsaturated polyester resins), similar in properties to the primary ones, can be obtained based on PET glycolysis products after purification. PET glycolysis allows one to obtain bis(2-hydroxyethyl) terephthalate and oligo(ethylene terephthalates) with various molecular weights. A kinetic model of poly(ethylene terephthalate) homogeneous glycolysis under the combined or separate action of oligo(ethylene terephthalates), bis(2-hydroxyethyl) terephthalate, and ethylene glycol is proposed. The model takes into account the interaction of bound, terminal, and free ethylene glycol molecules in the PET feedstock and the glycolysis agent. Experimental data were obtained on the molecular weight distribution of poly(ethylene terephthalate) glycolysis products and the content of bis(2-hydroxyethyl) terephthalate monomer in them to verify the model. Homogeneous glycolysis of PET was carried out at atmospheric pressure in dimethyl sulfoxide (DMSO) and N-methyl-2-pyrrolidone (NMP) solvents with catalyst based on antimony trioxide (Sb2O3) under the action of different agents: ethylene glycol at temperatures of 165 and 180 °C; bis(2-hydroxyethyl) terephthalate at 250 °C; and oligoethylene terephthalate with polycondensation degree 3 at 250 °C. Homogeneous step-by-step glycolysis under the successive action of the oligo(ethylene terephthalate) trimer, bis(2-hydroxyethyl) terephthalate, and ethylene glycol at temperatures of 250, 220, and 190 °C, respectively, was also studied. The composition of products was confirmed using FTIR spectroscopy. Molecular weight characteristics were determined using gel permeation chromatography (GPC), the content of bis(2-hydroxyethyl) terephthalate was determined via extraction with water at 60 °C. The developed kinetic model was found to be in agreement with the experimental data and it could be used further to predict the optimal conditions for homogeneous PET glycolysis and to obtain polymer-based composite materials with desired properties.

Application of chromatography in purification and structural analysis of natural polysaccharides: A review.

Polysaccharides are widely distributed in natural sources from monocytic microorganisms to higher animals, and are found in a variety of biological activities in recent decades. Natural polysaccharides have the characteristics of large molecular weight, diverse composition, and complex structure, so their purification and structural analysis are difficult issues in research. Chromatography as a powerful separation technique, plays an irreplaceable role in the separation and structural analysis of natural polysaccharides, especially in the purification of polysaccharides, the separation of hydrolysates, and the analysis of monosaccharide composition. The separation mechanisms and application of different chromatographic methods in the studies of polysaccharides were summarized in this review. Moreover, the advantages and drawbacks of various chromatography methods were discussed as well.

Neutral Red and Safranin Т in the Photopolymerization of Methyl Methacrylate and Other (Meth)Acrylate Monomers

Features of the polymerization of methyl methacrylate and a number of other (meth)acrylate monomers in the presence of catalytic systems based on phenazine dyes (Neutral Red and Safranin Т) under visible light irradiation are investigated. It is shown that amines of various structure as well as air oxygen affect the kinetic features of polymerization and the molecular weight characteristics of polymers. It is found that polymerization may proceed in the controlled mode up to high conversions at room temperature and a low photocatalyst concentration, among them without preliminary degassing of the reaction medium.

Polymer-polymer HDPE blends

The article presents the results of a study of the addition of high-viscosity unimodal HDPE on the complex of physicochemical, rheological and strength properties of PE100. The analysis of thermal properties according to TGA/DTA data as well as the results of studying the composition of volatile products, and the molecular weight characteristics of individual components and blends are presented. The conducted studies have shown that the introduction of high-viscosity unimodal HDPE into bimodal PE100 makes it possible to control the rheological characteristics of the material, shifting the “melt breakdown” to the area of high shear rates, i.e. to increase the processability of the original PE 100, and expand the processing range, which may be useful in the production of extruded sheets and profile products. At the same time, the strength characteristics of the finished product will remain at the level of PE100.

Functionalized phenoxy-imine catalyst for synthesizing highly crystalline nascent UHMWPEs: 2: The non-isothermal crystallization kinetics towards the nascent less entangled UHMWPEs

The morphologies and molecular weight characteristics of nascent UHMWPEs were reported in our previous work. In order to understand the effect of entanglement state on non-isothermal crystallization behaviors and kinetics of the nascent UHMWPEs, a comprehensive thermal analysis was implemented. The nascent UHMWPEs were confirmed as nascent less entangled UHMWPEs from annealing-crystallization-melting cycles. Jeziorny and Mo methods were applied to describe the non-isothermal crystallization kinetics of the UHMWPEs. The effects of entanglement density (molecular weight) and cooling rate on the crystallization temperature and rate were investigated. The crystallization temperature was seldom affected by molecular weight, but decreased with increasing cooling rate. The crystallization enthalpy showed an increasing trend with decreasing molecular weight or cooling rate. The crystallization rate increased with increasing cooling rate or decreasing molecular weight.

Effect of Solvent and Monomer Ratio on the Properties of Polyphenylene Sulphone.

For the first time, the effect of the solvent and monomer ratio on molecular weight, chemical structure, and mechanical, thermal, and rheological characteristics of polyphenylene sulfone has been studied. When dimethylsulfoxide (DMSO) is used as a solvent, cross-linking occurs during the processing of the polymer, which is accompanied by an increase in melt viscosity. This fact sets a pressing need for the complete removal of DMSO from the polymer. The best solvent used for the production of PPSU is N,N-dimethylacetamide. This study of the molecular weight characteristics of polymers by gel permeation chromatography showed the stability of the polymers practically does not change with a decrease in molecular weight. The synthesized polymers correspond in tensile modulus to the commercial analog Ultrason-P, while exceeding it in terms of tensile strength and relative elongation at break. Thus, the developed polymers are promising for spinning hollow fiber membranes with a thin selective layer.

Properties of Polysulphones Synthetized for Forming of Porous Hollow-Fiber Membranes

For the first time, for the problem of hollow fiber membranes spinning, polysulfones in a wide range of molecular weights (42 000–184 000 g/mol) were synthesized in such aprotic dipolar solvents as dimethylacetamide, N-methyl-2-pyrollidone, and dimethyl sulfoxide. The dependence of the thermal and mechanical properties of polysulfones on molecular weight characteristics has been studied. A comparison of the mechanical properties of the synthesized PSF, commercial PSF Ultrason S 6010 (BASF, Germany) and PSF-150 (JSC Institute of Plastics, Russia) showed that the synthesized polymers are not inferior to commercial analogues. Some synthesized polymers surpass commercial PSF in terms of elasticity and strength modulus. Based on the study of the spinning solutions dynamic viscosity, promising PSF samples were selected for the formation of porous hollow fiber supports. It was found that hollow-fiber porous support from a PSF sample with a molecular weight of 110 000 g/mol have a high nitrogen permeability of 47.5 m3/m2 · h · bar. Such supports are promising for casting highly permeable composite membranes with a thin selective layer.

Lignin Valorization for Added-Value Chemicals: Kraft Lignin versus Lignin Fractions

Lignin is a raw material that can potentially be converted into valuable compounds through depolymerization reactions in addition to its use as a polymer or material. However, the chemical recalcitrance and the heterogeneous composition and structure of lignin make it challenging to establish processes that add value to this complex aromatic biopolymer. In this work, solvent fractionation was applied to obtain lignin fractions with a narrowed molecular weight and specific structural characteristics, improving its homogeneity and purity. A kraft lignin was submitted to fractionation using different ratios of acetone, ranging from 60 to 15% v/v, in aqueous mixtures. The composition, structure, and molecular weight of each fraction were studied and their potential applications were evaluated. The most water-soluble fraction has more phenolic OH, less aliphatic OH groups, and shows the lowest content of aryl-ether linkages, which is in accordance with its highest degree of condensation. On the other hand, the insoluble fraction from the mixture with 60% of acetone has the lowest molecular weight and the highest content of inorganic material. Radar plots were applied for lignin fractions evaluation and the fraction with the highest potential (IF 30:70) was submitted to alkaline oxidation with O2. The results were compared with the products yielded from kraft lignin. An increase of about 13 and 19% was found for vanillin and syringaldehyde, respectively, when the fraction IF 30:70 was submitted to oxidation. In conclusion, the proposed fractionation process showed to be an effective method to obtain lignin fractions with specific composition and structural characteristics that could improve its potential as a source of high added-value monomeric phenolic compounds.

Features of Methyl Methacrylate Polymerization Mediated by Methylene Blue and Ethyl 2-Bromoisobutyrate under Photoirradiation Conditions

Using methyl methacrylate polymerization as an example, the features of polymer synthesis in the presence of the catalytic system [methylene blue + ethyl 2-bromoisobutyrate] at room temperature under visible light irradiation are investigated. The effect of polymerization conditions, including the light irradiation wavelength and various structure activators, on the monomer conversion and molecular weight characteristics of polymers is estimated. It is shown that polymerization can proceed in the controlled mode under mild temperature conditions according to the atom transfer mechanism (Metal Free Atom Transfer Radical Polymerization) to high conversions at low photocatalyst concentrations.

Betulin‐containing bioactive amphiphilic copolymers: Synthesis, characterization and self‐assembly

AbstractBetulin, a natural triterpene possessing a wide range of biological activities, has been modified via Steglich esterification to produce a methacrylate derivative capable of participating in radical polymerization. The modification is intended to increase the solubility of betulin, which is almost insoluble in water, by incorporating into the composition of an amphiphilic copolymer. The resulting solubility of betulin in water increased from 8·10−5 mg/mL to more than 10 mg/mL per betulin. For this, well‐defined biocompatible thermoresponsive copolymers with high betulin content have been synthesized through the conventional and RAFT copolymerizations of betulin methacrylate (BeMA) with methoxy oligo(ethylene glycol) methacrylate (MOEGMA). BeMA was more reactive in the BeMA‐MOEGMA pair; the resulting copolymers were slightly enriched with BeMA units (r1 = 1.70, r2 = 0.93). The copolymers exhibited LCST‐type behavior. LCST was tuned by balancing the hydrophobic betulin and hydrophilic OEG fragments. The molecular weight characteristics of polymers and their behavior in aqueous and organic solutions have been studied. Copolymers obtained by conventional polymerization had lower cloud points than RAFT copolymers of the same composition. The copolymers are characterized by low critical micelle concentrations that decrease as the BeMA fraction in the copolymers increases. RAFT copolymers were shown to form unimolecular micelles resistant to dissociation, which is promising for their use in targeted drug delivery.

Effect of chemically modified lignin addition on the physicochemical properties of PCL nanofibers

In this study, a chemically modified lignin additive was successfully prepared to improve the physicochemical properties of biodegradable polycaprolactone (PCL)-based nanofibers. The molecular weight and surface functional group characteristics of lignin were effectively controlled through a solvent fractionation process using ethanol. Then, PCL-g-lignin was successfully synthesized by using ethanol-fractionated lignin as a platform for the PCL grafting process. Finally, PCL/PCL-g-lignin composite nanofibers were simply prepared by adding PCL-g-lignin to the PCL doping solution and performing a solution blow spinning process. The addition of PCL-g-lignin could dramatically improve the physical and chemical properties of PCL nanofibers, and in particular, the tensile strength (0.28 MPa) increased by approximately 280 % compared to the conventional PCL. In addition, the lignin moiety present in PCL-g-lignin was able to impart UV blocking properties to PCL nanofibers, and as a result, it was possible to effectively suppress the photolysis phenomenon that occurred rapidly in existing PCL nanofibers. Therefore, PCL-g-lignin may be widely used not only as a reinforcing agent of existing biodegradable nanofibers but also as a functional additive for UV protection.

Garlic polysaccharide-Cr (III) complexes with enhanced in vitro and in vivo hypoglycemic activities

This study aimed to prepare a complex of Cr (III) and garlic polysaccharides (GPs) and evaluate the in vitro and in vivo hypoglycemic activities of GPs and GP-Cr (III) complexes. The chelation of GPs with Cr (III) increased molecular weight, modified crystallinity, and altered morphological characteristics, through targeting the OH of hydroxyl groups and involving the C–O/O–C–O structure. The GP-Cr (III) complex had a higher thermal stability over 170–260 °C and higher stability throughout the gastrointestinal digestion. In vitro, the GP-Cr (III) complex exhibited a significantly stronger inhibitory effect against α-glucosidase compared with the GP. In vivo, the GP-Cr (III) complex at a high dose (4.0 mg Cr/kg body weight) generally had a higher hypoglycemic activity than the GP in (pre)-diabetic mice induced by a high-fat and high-fructose diet, based on indices like body weight, blood glucose levels, glucose tolerance, insulin resistance, insulin sensitivity, blood lipid levels, and hepatic morphology and function. Therefore, GP-Cr (III) complexes could be a potential Cr (III) supplement with an enhanced hypoglycemic activity.

Fate of Naturally Dissolved Organic Matter and Synthetic Organic Compounds Subjected to Drinking Water Treatment Using Membrane, Activated Carbon, and UV/H2O2 Technologies.

Organic pollutants are toxic and are present in drinking water. The conventional processes of most water plants can basically meet the discharge standard. However, based on the improvement of the objective of organic pollutants control and the constant change of water characteristics, the results may not be ideal. This study evaluates the effectiveness of different treatments such as microfiltration, nanofiltration, reverse osmosis, activated carbon, and ultraviolet irradiation/H2O2 in terms of the removal of organic pollutants. Among the DOM results, nanofiltration, reverse osmosis, and activated carbon showed optimal performance due to the characteristics of processes and the compound properties. However, the risks of low-molecular-weight organic residue and byproduct formation are still present. Thirty-nine species of synthetic organic compounds (SOC) were qualitatively and semiquantitatively analyzed. Different technologies showed varying removal capabilities for SOC based on their properties and many substances coexisted leading to abnormal removal performances. These residual organics showed the characteristics of lower molecular weight, more hydrophilicity, further unknown impacts, and with risk of DBPs. Based on the above insights, possible methods can be rationally chosen for on-demand decontamination of organics in unconfined aquatic environment and long-time impact on water characteristics and human health also should be considered.

Spatiotemporal response of dissolved organic matter diversity to natural and anthropogenic forces along the whole mainstream of the Yangtze River

The Yangtze River, the largest river in Asia, plays a crucial role in linking continental and oceanic ecosystems. However, the impact of natural and anthropogenic disturbances on composition and transformation of dissolved organic matter (DOM) during long-distance transport and seasonal cycle is not fully understood. By using a combination of elemental, isotopic and optical techniques, as well as Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS), we investigated DOM abundance and composition along the whole mainstream at highly spatial resolution in the dry and early wet seasons. Our findings showed that the concentration and flux of dissolved organic carbon (DOC) in the Yangtze River was much lower compared with other worldwide larger rivers. The distribution of δ13CDOC and higher abundance of humic-like fluorescent component and highly unsaturated and phenolics (HUPs) compound reflected a prominent contribution of allochthonous DOM. Further optical and molecular analysis revealed humic-like fluorescent components were coupled with CHO molecules and HUPs compound with higher aromatic, unsaturated, molecular weight and stable characteristics between upstream and midstream reaches. With increasing agricultural and urban land downstream, there were more heteroatomic formulae and labile aliphatic and protein-like compounds which were derived from human activities and in situ primary production. Meanwhile, DOM gradually accumulates with slow water flow and additional autochthonous organics. Weaker solar radiation and water dilution during the dry/cold season favours highly aromatic, unsaturated and oxygenated DOM compositions. Conversely, higher discharge during the wet/warm season diluted the terrestrial DOM, but warm temperatures could promote phytoplankton growth that releases labile aliphatic and protein-like DOM. Besides, chemical sulfurization, hydrogenation and oxygenation were found during molecular cycling processes. Our research emphasizes the active response of riverine DOM to natural and anthropogenic controls, and provides a valuable preliminary background to better understand the biogeochemical cycling of DOM in a larger river.