High Molecular Weight Polymers Research Articles

Extraction of ingredients from tea leaves using oxidative enzymatic reaction and optimization of extraction conditions

Peroxidase (POD) and polyphenol oxidase (PPO) are used as biocatalyst in many processes such as oxidization reactions, wastewater treatment, phenol synthesis and so on. The purpose of current study is enzymes extraction from biomass (tea leaves) as well as evaluation of their activation. Different parameters including temperature, buffer concentration, buffer type, buffer/tea leaves ratio, addition of high molecular weight polymers and emulsifiers, and pH were optimized in order to obtain the highest enzymes activity. Response Surface Methodology (RSM) procedure is employed for statistical analysis of enzymes extraction. It is understood from the result that PPO and POD possess the highest activity at temperatures of 25 °C and 50 °C, pH 7 and 5, buffer molarity of 0.1, and 0.05, buffer/tea leaves ratio = 5 for both, contact time = 20 min and 10 min, and presence of 6% and 3% PVP, 5% and 0% Tween 80 for PPO and POD, respectively. Amounts of highest activity for PPO and POD biocatalysts were calculated 0.42 U/mL and 0.025493 U/mL, respectively. Moreover, the entire inactivation of PPO took place after 30 min at 40 °C and 60 °C and 20 min at 80 °C. However, POD lost 35% of its activity after 30 min at 40 °C and 60 °C. The amount of 6% POD activity was kept after 45 min at 80 °C. Generally, it was indicated that POD was more resistant to thermal treatment than PPO.

Achieving highly efficient gene transfer to the bladder by increasing the molecular weight of polymer-based nanoparticles

Short dwell-time and poor penetration of the bladder permeability barrier (BPB) are the main obstacles to intravesical treatments for bladder diseases, and is evidenced by the lack of such therapeutic options on the market. Herein, we demonstrate that by finely tuning the molecular weight of our cationic polymer mucoadhesive nanoparticles, we enhanced our gene transfer, leading to improved adherence and penetrance through the BPB in a safe and efficient manner. Specifically, increasing the polymer molecular weight from 45 kDa to 83 kDa enhanced luciferase plasmid transfer to the healthy murine bladder, leading to 1.35 ng/g luciferase protein expression in the urothelium and lamina propria regions. The relatively higher molecular weight polymer (83 kDa) did not induce morphologic changes or inflammatory responses in the bladder. This approach of altering polymer molecular weight for prolonging gene transfer residence time and deeper penetration through the BPB could be the basis for the design of future gene therapies for bladder diseases.

Manufacturing technology of low-molecular-weight chitosan based on enzymatic hydrolysis

Chitosan is natural high molecular weight polymer of D-glucosamine and N-acetyl - D - glucosamine connected by 1,4 - b - glycoside bond with a molecular mass of 1000 kDa (and above), practical use is difficult because of high viscosity of its aqueous solutions even at low concentrations, and lack of solubility at neutral pH and, consequently, low biological activity. To reduce viscosity, improve the solubility and enhance biological activity of high molecular weight chitosan subjected to depolymerization. Chitosan, like other polysaccharides, is characterized by a hydrolysis reaction, which is due to the presence of glycoside bonds in the molecule that are lable to hydrolyzing agents, for example, aqueous solutions of acids, alkalis, as well as to the effect of some hydrolases. During hydrolysis, glycoside bonds are broken and, as a result, the molecular weight of chitosan decreases. However, these processes are accompanied by the formation of significant amounts of toxic products and require very costly disposal of waste before it is discharged into the environment. Chitin and chitosan are natural biopolymers and their synthesis, modification and degradation are associated with enzymatic transformations. It is the biodegradability to the usual substances for the body that is one of the main advantages of chitosan. It is obvious that the most appropriate method is the enzymatic hydrolysis of chitosan. As enzyme preparations for the degradation of chitin and chitosan, enzyme complexes of various origins are used. These can be enzymes from crab or krill hepatopancreas complexes, as well as pancreatin from the pancreas of cattle. But more often for this purpose, enzymes complexes with chitinolytic activity of microbiological origin are used. In this study, low-molecular-weight chitosan was obtained by enzymatic hydrolysis using the extracellular chitinolytic complex of Streptomyces kurssanovii. The resulting chitosan had a medium-viscosity molecular weight of 25-40 kDa. Carrying out two stages of fractionation (stepwise acidification and separation on membranes) made it possible to obtain chitosan fractions with a narrow distribution by molecular weight.

The inhibitory effect of in situ extracellular polymeric substances on trimethoprim adsorption by activated sludge

The extracellular polymeric substances (EPS) of activated sludge are a mixture of high molecular weight polymers secreted by microorganisms, which are mainly composed of proteins, polysaccharides and humic substances. It is widely accepted that EPS have a good adsorption ability for pollutants with different functional groups. However, recent studies showed the EPS had an inhibitory effect on pollutant sorption, which is contradictory to previous viewpoint. Therefore, in this study, three types of activated sludge with different EPS contents and compositions were used to investigate the role of EPS in an antibiotic-trimethoprim (TMP) sorption process at environmentally relevant concentration. The in situ experiments results showed the adsorption capacity of activated sludge for TMP were increased from 2.98, 5.37 and 28.33 μg/g VSS to 7.87, 12.93 and 150.24 μg/g VSS in nitrifying activated sludge, wastewater treatment plant activated sludge and anaerobic ammonia-oxidized activated sludge, respectively after EPS extracted. The adsorption process can be well described by the pseudo-second-order kinetic model. Results of zeta potential, contact angles and infrared spectrum showed TMP replacing proteins embedded into the cell membrane enhancing the TMP adsorption capacity of activated sludge after EPS extraction. Our results demonstrated that less proteins in EPS of activated sludge is more beneficial for TMP adsorption removal.

Quantification of branching within high molecular weight polymers with polyester backbones formed by transfer-dominated branching radical telomerisation (TBRT).

New branched polymerisations offer previously inaccessible macromolecules and architectural understanding is important as it provides insight into the branching mechanism and enables the determination of structure–property relationships. Here we present a detailed inverse gated 13C NMR characterisation of materials derived from the very recently reported Transfer-dominated Branching Radical Telomerisation (TBRT) approach to quantify branching and provide an insight into cyclisation.

Off-line analysis in the manganese catalysed epoxidation of ethylene-propylene-diene rubber (EPDM) with hydrogen peroxide.

The epoxidation of ethylene-propylene-diene rubber (EPDM) with 5-ethylidene-2-norbornene (ENB) as the diene to epoxidized EPDM (eEPDM) creates additional routes to cross-linking and reactive blending, as well as increasing the polarity and thereby the adhesion to polar materials, e.g., mineral fillers such as silica. The low solubility of apolar, high molecular weight polymers in the polar solvents constrains the catalytic method for epoxidation that can be applied. Here we have applied an in situ prepared catalyst comprising a manganese(ii) salt, sodium picolinate and a ketone to the epoxidation of EPDM rubber with hydrogen peroxide (H2O2) as the oxidant in a solvent mixture, that balances the need for polymer and catalyst/oxidant miscibility and solubility. Specifically, a mixture of cyclohexane and cyclohexanone is used, where cyclohexanone functions as a co-solvent as well as the ketone reagent. Reaction progress was monitored off-line through a combination of Raman and ATR-FTIR spectroscopies, which revealed that the reaction profile and the dependence on the composition of the catalyst are similar to those observed with low molar mass alkene substrates, under similar reaction conditions. The combination of spectroscopies offers a reliable method for off-line reaction monitoring of both the extent of the conversion of unsaturation (Raman) and the extent of epoxidation (FTIR) as well as determining side reactions, such as epoxide ring opening and further, aerobic oxidation. The epoxidation of EPDM described, in contrast to currently available methods, uses a non-scarce manganese catalyst and H2O2, and avoids side reactions, such as those that can occur with peracids.

A UHPLC-Q-TOF/MS method for the determination of poloxamer 124 and its application in a tissue distribution study in rats.

Poloxamers are commonly used pharmaceutical excipients. They are high molecular weight polymers formed from polypropylene oxide (PPO) and polyethylene oxide (PEO). However, PL124, a low molecular weight example in the poloxamer family, has rarely been reported, and there is no research into its tissue distribution in the body after administration. In this study, rat tissue samples were quantitatively studied via UHPLC-Q-TOF/MS after the intravenous administration of 10 mg kg-1 PL124. The quantitative method showed good sensitivity and selectivity. The linear range of PL124 was 0.1-5 μg mL-1 and the LLOQ was 0.1 μg mL-1. The relative error in terms of the accuracy was no higher than 13.9%, and the relative standard deviation in terms of the precision was no higher than 9.6%. The extraction recovery, matrix effect, and stability results of the established method were also satisfactory. The research showed that PL124 can be quickly distributed to large amounts of tissue, and tissue with higher levels of blood flow has higher concentrations. PL124 could be rapidly eliminated in 4 h from most organs, except the heart and liver. This study can be helpful for the further analysis of PL124.

Rheological behavior and fiber spinning of polyacrylonitrile (PAN)/Carbon nanotube (CNT) dispersions at high CNT loading

Rheological studies play an important role in polymer processing including fiber spinning. In the current work, rheological behavior has been studied for polyacrylonitrile (PAN)/carbon nanotube (CNT) dispersions in dimethyl formamide (DMF), where CNT loading is as high as 15 wt% of the total solids (polymer + CNT). The presence of CNTs increased the elastic-like and shear thinning behavior of the dispersions. The terminal slope of the log G′ versus log G″ curve, which was used to characterize the homogeneity of solution or dispersion, is dependent on the CNT concentration but independent of temperature between 0 and 60 °C. PAN/CNT-10 (90 wt% PAN +10 wt% CNT) and PAN/CNT-15 were gel spun at different conditions, with small diameter capillary at high shear rate and large diameter capillary at relatively low shear rate. For PAN/CNT-10, fiber spinning with lower molecular weight polymer showed increased continuous jetting time when compared to spinning with higher molecular weight polymer. In addition, the rheological behavior of PAN/cellulose nanocrystal (CNC) dispersion with 20–60 wt% CNC was also compared to that of the PAN/CNT dispersions. PAN/CNC and PAN/CNT share similarities in both rheological behavior and fiber spinning at high filler loading.

Partially bio‐based furyl‐functionalized organosoluble poly(ether ether ketone)s

AbstractA new series of partially bio‐based (co)poly(ether ether ketone)s bearing pendent furyl groups was synthesized by nucleophilic aromatic substitution polycondensation of varying molar proportions of 4,4′‐(furan‐2‐ylmethylene)bis(2‐methoxyphenol) and bisphenol‐A with 4,4′‐difluorobenzophenone. The chemical structures, compositions and random nature of (co)poly(ether ether ketone)s were confirmed by NMR spectroscopy. Inherent viscosities and number‐average molecular weights of the (co)poly(ether ether ketone)s were in the range 0.74–2.90 dL g−1 and 33 500–46 300 g mol−1, respectively, indicating the formation of reasonably high molecular weight polymers. (Co)poly(ether ether ketone)s were readily soluble in common organic solvents and could be cast into tough, transparent and flexible films from chloroform solutions. (Co)poly(ether ether ketone)s exhibited 10% weight loss and glass transition temperatures in the range 429–464 and 152–156 °C, respectively. A representative copoly(ether ether ketone) was crosslinked with 1,1′‐(methylenedi‐1,4‐phenylene)bismaleimide via Diels–Alder reaction to form a crosslinked polymer which showed improved mechanical properties and was recycled twice without significant loss of mechanical properties. Diels–Alder/retro Diels–Alder reaction was demonstrated by studies of sol–gel transformation, solubility tests, DSC and stress–strain measurements. © 2020 Society of Chemical Industry

Poly(acrylic acid) nanocomposites: Design of advanced materials

Poly(acrylic acid) is a synthetic polymer that is polymerized from acrylic acid monomers. Poly (acrylic acid) is a high molecular weight polymer having good water solubility. Poly(acrylic acid) also exists in the cross-linked forms. Poly(acrylic acid) is an important polymer for making polymeric blends and nanocomposites. This state-of-the-art review is an endeavour to define the unique capabilities of poly (acrylic acid) to form high performance nanocomposites. The nanofiller nanomaterials including carbon nanotube, graphene, nanodiamond, and inorganic nanoparticles are promising nanofillers for a poly(acrylic acid) matrix. Consequently, the article discusses the following categories: poly(acrylic acid)/carbon nanotube, poly(acrylic acid)/graphene, poly(acrylic acid)/nanodiamond, and poly(acrylic acid)/inorganic nanoparticle nanocomposites. The nanocomposite characteristics are significantly enhanced with the added nanoparticles. Especially, the nanoparticles influenced the electrical conductivity, thermal stability, strength, biocompatibility, adsorption, and anti-bacterial features of the poly(acrylic acid) nanocomposites. Their high performance was related to the interface interactions between the matrix and the nanofillers. The poly (acrylic acid) derived nanocomposites have been used to form advanced hybrid materials for batteries, sensors, antibacterial, and water filters.

Iron-Based Catalytically Active Complexes in Preparation of Functional Materials

Iron complexes are particularly interesting as catalyst systems over the other transition metals (including noble metals) due to iron’s high natural abundance and mediation in important biological processes, therefore making them non-toxic, cost-effective, and biocompatible. Both homogeneous and heterogeneous catalysis mediated by iron as a transition metal have found applications in many industries, including oxidation, C-C bond formation, hydrocarboxylation and dehydration, hydrogenation and reduction reactions of low molecular weight molecules. These processes provided substrates for industrial-scale use, e.g., switchable materials, sustainable and scalable energy storage technologies, drugs for the treatment of cancer, and high molecular weight polymer materials with a predetermined structure through controlled radical polymerization techniques. This review provides a detailed statement of the utilization of homogeneous and heterogeneous iron-based catalysts for the synthesis of both low and high molecular weight molecules with versatile use, focusing on receiving functional materials with high potential for industrial application.

Investigation of soft and living matter using a micro-extensional rheometer

Rheological properties of a material often require to be probed under extensional deformation. Examples include fibrous materials such as spider-silk, high-molecular weight polymer melts, and the contractile response of living cells. Such materials have strong molecular-level anisotropies which are either inherent or are induced by an imposed extension. However, unlike shear rheology, which is well-established, techniques to perform extensional rheology are currently under development and setups are often custom-designed for the problem under study. In this article, we present a versatile device that can be used to conduct extensional deformation studies of samples at microscopic scales with simultaneous imaging. We discuss the operational features of this device and present a number of applications.

Sugar‐Based Polymers from d‐Xylose: Living Cascade Polymerization, Tunable Degradation, and Small Molecule Release

AbstractEnyne monomers derived from D‐xylose underwent living cascade polymerizations to prepare new polymers with a ring‐opened sugar and degradable linkage incorporated into every repeat unit of the backbone. Polymerizations were well‐controlled and had living character, which enabled the preparation of high molecular weight polymers with narrow molecular weight dispersity values and a block copolymer. By tuning the type of acid‐sensitive linkage (hemi‐aminal ether, acetal, or ether functional groups), we could change the degradation profile of the polymer and the identity of the resulting degradation products. For instance, the large difference in degradation rates between hemi‐aminal ether and ether‐based polymers enabled the sequential degradation of a block copolymer. Furthermore, we exploited the generation of furan‐based degradation products, from an acetal‐based polymer, to achieve the release of covalently bound reporter molecules upon degradation.

Sugar-Based Polymers from d-Xylose: Living Cascade Polymerization, Tunable Degradation, and Small Molecule Release.

Enyne monomers derived from D-xylose underwent living cascade polymerizations to prepare new polymers with a ring-opened sugar and degradable linkage incorporated into every repeat unit of the backbone. Polymerizations were well-controlled and had living character, which enabled the preparation of high molecular weight polymers with narrow molecular weight dispersity values and a block copolymer. By tuning the type of acid-sensitive linkage (hemi-aminal ether, acetal, or ether functional groups), we could change the degradation profile of the polymer and the identity of the resulting degradation products. For instance, the large difference in degradation rates between hemi-aminal ether and ether-based polymers enabled the sequential degradation of a block copolymer. Furthermore, we exploited the generation of furan-based degradation products, from an acetal-based polymer, to achieve the release of covalently bound reporter molecules upon degradation.

Selective Synthesis of Single‐Handed Helical Polymers from Achiral Monomer and a Mechanism Study on Helix‐Sense‐Selective Polymerization

AbstractInspired by the exquisite helices in Nature, fabrication of helical materials with controlled handedness has attracted considerable attention. Herein, we report on precis synthesis of single left‐ and right‐handed helical polyisocyanides through living polymerization of achiral monomers using chiral palladium catalysts under helix‐sense‐selective manner. Mechanism study revealed that the yielded helices with opposite handedness showed different activity of the living chain end. The helix with unfavored handedness was self‐terminated, while the one with favored handedness showed high activity and could undergo chain propagation to form a high molecular weight polymer with maintained single‐handed helicity.

Selective Synthesis of Single-Handed Helical Polymers from Achiral Monomer and a Mechanism Study on Helix-Sense-Selective Polymerization.

Inspired by the exquisite helices in Nature, fabrication of helical materials with controlled handedness has attracted considerable attention. Herein, we report on precis synthesis of single left- and right-handed helical polyisocyanides through living polymerization of achiral monomers using chiral palladium catalysts under helix-sense-selective manner. Mechanism study revealed that the yielded helices with opposite handedness showed different activity of the living chain end. The helix with unfavored handedness was self-terminated, while the one with favored handedness showed high activity and could undergo chain propagation to form a high molecular weight polymer with maintained single-handed helicity.

ОЧИЩЕННЯ АКРИЛАМІДУ ВІД ІНГІБІТОРІВ ПОЛІМЕРИЗАЦІЇ ДЛЯ ВИГОТОВЛЕННЯ ВИСОКОЯКІСНИХ ФЛОКУЛЯНТІВ НА ОСНОВІ ПОЛІАКРИЛАМІДУ

Polyacrylamide and its copolymers are widely used as flocculating agents for the separation of industrial suspensions. The formation of high molecular weight polymers depends on the content of various impurities present in the monomer. The article presents the scientific and practical information on the production of acrylamide by sulfuric acid method of hydration of nitrile acrylic acid in the form of an aqueous solution of different concentrations and a more modern heterogeneously catalytic method of hydration of acrylonitrile using as catalysts with variable valence. Ways to get different impurities in the stages of production of acrylamide with the purpose of applying appropriate methods for its purification. Laboratory studies of the purification of an aqueous solution of acrylamide from iron ions were carried out as an element of inhibition of the premature polymerization process.

Optimization of Conditions of Polymer Separation by Hydrodynamic Chromatography

For the well-known theoretical model of hydrodynamic chromatography, which relates the relative retention of an analyte and the separation efficiency to the characteristic parameter of a system, expressions are proposed that make it possible to find the optimal conditions for analysis. The theoretical model well predicts the relative retention of analytes but greatly overestimates the separation efficiency, especially for high molecular weight polymers. The observed discrepancy is due to the impossibility within one separation to create optimal conditions for all components of the sample and/or the influence of the polydispersity of the studied polymer samples on the separation efficiency.

Towards High Molecular Weight Furan-Based Polyesters: Solid State Polymerization Study of Bio-Based Poly(Propylene Furanoate) and Poly(Butylene Furanoate).

In the era of polymers from renewable resources, polyesters derived from 2,5 furan dicarboxylic acid (FDCA) have received increasing attention due to their outstanding features. To commercialize them, it is necessary to synthesize high molecular weight polymers through efficient and simple methods. In this study, two furan-based polyesters, namely poly (propylene furanoate) (PPF) and poly(butylene furanoate) (PBF), were synthesized with the conventional two-step melt polycondensation, followed by solid-state polycondensation (SSP) conducted at different temperatures and reaction times. Molecular weight, structure and thermal properties were measured for all resultant polyesters. As expected, increasing SSP time and temperature results in polymers with increased intrinsic viscosity (IV), increased molecular weight and reduced carboxyl end-group content. Finally, those results were used to generate a simple mathematical model that prognosticates the time evolution of the materials’ IV and end groups concentration during SSP.

Neutral Nickel(II) Catalysts: From Hyperbranched Oligomers to Nanocrystal-Based Materials

ConspectusPlastics materials are a vital component of modern technologies. They are applied, e.g., in construction, transportation, communication, water supply, or health care. Consequently, polyolefins-the most important plastics by scale-are produced in vast amounts by catalytic polymerization. Effective and selective as the catalysts used may be, their high sensitivity toward any polar compounds limits these methods to hydrocarbon reaction media and monomers like ethylene and propylene, respectively. This can be overcome by less oxophilic late transition metal catalysts, and here particularly neutral nickel(II) catalysts have seen major advances in the past few years. They stand out due to being capable of aqueous catalytic polymerizations. Aqueous polymerizations are benign processes that advantageously yield polymers in the form of particles. Moreover, these catalysts can incorporate polar monomers like acrylates, a realm previously restricted to noble metal catalysts. The introduction of polar moieties can induce properties like compatibility with metals or fibers in high performance composite materials or a desirable degradability.This Account provides a personal account of developments in the past decade. Prior findings are outlined briefly as a background. Aqueous polymerizations afford unique polyethylene morphologies as a result of the unusual underlying particle growth mechanism. Polymer single crystals are formed, which can be composed of a single ultrahigh molecular weight chain. This represents a completely disentangled state of such extremely long polymer chains, which has been long sought-after in order to overcome the difficult processing of high performance ultrahigh molecular weight materials. A key prerequisite for this approach and utilization of these catalysts, in general, is control of polymer branching and molecular weight. This is achieved via remote substituents on the Ni(II)-chelating ligand. Despite their distal position to the active site, weak secondary interactions control whether branching and chain transfer pathways compete very effectively with chain growth or are suppressed entirely. This provides access to hyperbranched oligomers, on the one hand, and enables living polymerizations to strictly linear high molecular weight polymer, on the other hand. Other advanced catalysts provide linear copolymers with in-chain polar monomer repeat units for the first time with non-noble metal active sites. Mechanistic studies further revealed that for copolymerizations with polar vinyl monomers the decisive limiting factor is irreversible termination reactions with neutral Ni(II) catalysts, rather than the well-recognized reversible blocking of coordination sites by the polar functional groups found for other types of catalysts. The mechanistic picture also implies the possibility of free-radical pathways, and their role in the formation of desirable polymer end groups and polymer blends is now being recognized. The area of neutral Ni(II) catalysts has progressed significantly in the entire range from fundamental mechanistic understanding, catalyst performance, and previously inaccessible polymer microstructures, and it is moving forward to materials through unique concepts. The unprecedented ability to incorporate functional groups into linear crystalline polyethylene also provides perspectives for much needed polyolefin materials that will not persist in the natural environment for several decades but that can be degraded by virtue of low levels of functional groups.