Molecular Mass Distribution Research Articles

Solution of the inverse problem of forming molecular mass distribution of polymers using heuristic methods

Solution of the inverse problem of forming molecular mass distribution of polymers using heuristic methods

Pressurized hydrogasification and cobalt-catalyzed hydrogasification behaviors of naphthalene as a coal-based model compound

The pressurized hydrogasification/catalytic hydrogasification behaviors of naphthalene as a coal-based model compound were investigated for the first time in a batch reactor. The composition of products was roundly analyzed by gas chromatography (GC), gas chromatography–mass spectrometer (GC-MS) and laser desorption time-of-flight mass spectrometry (TOF-MS). Based on the product analysis results, the detailed reaction pathways for naphthalene hydrogasification and the effects of cobalt on reaction pathways were elucidated. Naphthalene first destabilized during hydrogasification. Subsequently, the destabilized naphthalene either underwent stepwise hydrocracking by active hydrogen atoms to ultimately produce benzene and methane, or formed naphthalene free radicals to initiate condensation. Cobalt can regulate products distribution to boost methane, benzene and toluene yield by facilitating active hydrogen generation, despite it had a limited ability to facilitate the naphthalene destabilization at temperature below 700 °C. Whereas above 750 °C, cobalt can promote naphthalene destabilization, thereby remarkably enhancing the conversion of naphthalene. Furthermore, cobalt intensified condensation leading to a shift of molecular mass distribution of condensation products from 252 ∼ 500 Da to 750 ∼ 2000 Da. These phenomena supported similar findings in coal catalytic hydrogasification. The rise in temperature, initial H2 pressure (P0), and cobalt content all facilitated the cobalt catalyzed naphthalene hydrocracking to gaseous product, with temperature exerting a particularly significant effect. This trend was similar with cobalt catalyzed coal hydrogasification. For example, when temperature increased from 650 ℃ to 750 ℃, naphthalene conversion improved from 21.2 % to 49.6 %, and gas yield rose from 2.6 % to 29.4 % at 1 % Co and 1.3 MPa P₀. The investigation serves to shed light on the molecular-level understanding of the mechanism underpinning coal hydrogasification.

The role of hyperbranched polyesters in acrylamide‐based polymers as thickening agents in aqueous solutions

AbstractAcrylamide polymers are typically used in industrial and healthcare sectors as thickening agents; however, their thickening capabilities rely mainly in their molecular mass. A versatile and simple strategy to improve their performance is the copolymerization with specific monomers or their chemical modification with structures like dendritic or hyperbranched molecules. This study introduces a novel acrylamide‐acrylic acid polymer grafted with minor proportions (≤4.0 wt%) of Boltorn H30, a hyperbranched polyester monomer. The incorporation of Boltorn H30 aims to exploit the hyperbranched architecture's impact on the viscosity and rheological behavior of polymer solutions. Polymers with 0.4 and 4.0 polyester wt% characterized by several analytical techniques displayed improved viscosity in aqueous solution compared against the parent poly(acrylamide‐co‐acrylic acid). Results revealed that while the molecular mass distribution changed between 20% and 94%, the thickening capabilities significantly improved with increments of 2.7 and 3.8 times compared to that of the original polymers. These findings demonstrate that even with a minimal incorporation of hyperbranched polyesters, the abundance of hydroxyl groups fosters extensive hydrogen bonding, resulting in enhanced viscosity properties of the polymer.

Molecular Weight Distribution of Humic Acids Isolated from Calcic Cryosol in Central Yakutia, Russia.

The transition of soils into fallow state has a significant impact on the accumulation and transformation of soil organic matter (SOM). However, the issue of SOM transformation as a result of soil transition to fallow state in cryolithozone conditions is insufficiently studied. The aim of this study is to investigate the molecular weight (MW) distribution of humic acids (HAs) isolated from soils of central Yakutia. Native, fallow and agricultural soils in the vicinity of Yakutsk city were studied. MW distributions of HA preparations were obtained on an AKTAbasic 10 UPS chromatographic system (Amersam Biosciences, Uppsala, Sweden) using a SuperdexTM 200 10/300 GL column (with cross-linked dextran gel, fractionation range for globular proteins 10-600 kDa). The data on the molecular-mass distribution of HAs of fallow and agricultural soils of Central Yakutia were obtained for the first time. According to the obtained data, it was found that the highest carbon content in the structure of HAs was observed in agricultural soils (52.56%), and is associated with soil cultivation and fertilizer application. Among the HAs of fallow soils, we note that those soils that are in the process of self-vegetation have a relatively high carbon content in the HAs (45.84%), but the highest content was observed in fallow soils used as hayfields (49.98%), indicating that the reinvolvement of agriculture in fallow soils leads to an increase in the carbon content of HAs. According to the data of the MW distribution of HAs, it was found that the highest content of a high MW fraction of HAs was recorded in native soil (18.8%); this is due to the early stages of humification and the low maturity of organic matter. The highest content of a low MW fraction of HAs was recorded in agricultural soil (73.3%); this is due to the formation of molecular complexes of a "secondary" nature, which are more stable in the environment than the primary transformation products of humification precursors. The molecular composition of the HAs of fallow soils in the process of self-overgrowing is characterized by values closer to the HAs of native soils, which indicates their transformation towards HAs of native soils. The obtained results indicate that the reinvolvement of fallow soils leads to the transformation of the molecular composition of HAs towards HAs of agricultural soils, and to an increase in the resistance of SOM to biodegradation.

Converting Bulk Sugars into Functional Fibers: Discovery and Application of a Thermostable β-1,3-Oligoglucan Phosphorylase.

Despite their broad application potential, the widespread use of β-1,3-glucans has been hampered by the high cost and heterogeneity associated with current production methods. To address this challenge, scalable and economically viable processes are needed for the production of β-1,3-glucans with tailorable molecular mass distributions. Glycoside phosphorylases have shown to be promising catalysts for the bottom-up synthesis of β-1,3-(oligo)glucans since they combine strict regioselectivity with a cheap donor substrate (i.e., α-glucose 1-phosphate). However, the need for an expensive priming substrate (e.g., laminaribiose) and the tendency to produce shorter oligosaccharides still form major bottlenecks. Here, we report the discovery and application of a thermostable β-1,3-oligoglucan phosphorylase originating from Anaerolinea thermophila (AtβOGP). This enzyme combines a superior catalytic efficiency toward glucose as a priming substrate, high thermostability, and the ability to synthesize high molecular mass β-1,3-glucans up to DP 75. Coupling of AtβOGP with a thermostable variant of Bifidobacterium adolescentis sucrose phosphorylase enabled the efficient production of tailorable β-1,3-(oligo)glucans from sucrose, with a near-complete conversion of >99 mol %. This cost-efficient process for the conversion of renewable bulk sugar into β-1,3-(oligo)glucans should facilitate the widespread application of these versatile functional fibers across various industries.

The Multilayer Nature of Molecular Gas toward the Cygnus Region

We study the physical properties and 3D distribution of molecular clouds (MCs) toward the Cygnus region using the MWISP CO survey and Gaia DR3 data. Based on Gaussian decomposition and clustering for 13CO lines, over 70% of the fluxes are recovered. With the identification result of 13CO structures, two models are designed to measure the distances of the molecular gas in velocity crowding regions. The distances of more than 200 large 13CO structures are obtained toward the 150 deg2 region. Additionally, tens of the identified MC structures coincide well with masers and/or intense mid-IR emission. We find multiple gas layers toward the region: (1) the extensive gas structures composing the Cygnus Rift from 700 pc to 1 kpc across the whole region; (2) the ∼1.3 kpc gas layer mainly in the Cygnus X South region; and (3) the 1.5 kpc dense filament at the Cygnus X North region and many cometary clouds shaped by Cygnus OB2. We also note that the spatial distribution of young stellar object candidates is generally consistent with the molecular gas structures. The total molecular mass of the Cygnus region is estimated to be ∼2.7 × 106 M ⊙ assuming an X-factor ratio XCO=2×1020cm−2(Kkms−1)−1 . The foreground Cygnus Rift contributes ∼25% of the molecular mass in the whole region. Our work presents a new 3D view of the MCs' distribution toward the Cygnus X region, as well as the exact molecular gas mass distribution in the foreground Cygnus Rift.

Correlation between the Chemical Structure of (Meth)Acrylic Monomers and the Properties of Powder Clear Coatings Based on the Polyacrylate Resins.

This paper presents studies on the influence of the chemical structure of (meth)acrylic monomers on the properties of powder coatings based on polyacrylate resins. For this purpose, a wide range of monomers were selected-2-hydroxyethyl methacrylate (HEMA), methyl methacrylate (MMA), n-butyl acrylate (nBA), tert-butyl acrylate (tBA), dodecyl acrylate (DA), ethyl acrylate (EA) and benzyl acrylate (BAZ)-for the synthesis of the polyacrylate resin. The average molecular mass and molecular mass distribution of the synthesized resins were measured by gel permeation chromatography (GPC). The glass transition temperature (Tg) and viscosity of polyacrylate resins were determined by using differential scanning calorimetry (DSC) and a Brookfield viscometer. These parameters were necessary to obtain information about storage stability and behavior during the application of powder clear coatings. Additionally, DSC was also used to checked the course of the low-temperature curing reaction between the hydroxyl group contained in the polyacrylate resin and the blocked polyisocyanate group derived from a commercial agent such as Vestanat B 1358/100. The properties of the cured powder clear coatings were tested, such as: roughness, gloss, adhesion to the steel surface, hardness, cupping, scratch resistance, impact resistance and water contact angle. The best powder clear coating based on the polyacrylate resin L_HEMA/6MMA/0.5nBA/0.5DA was characterized as having good scratch resistance (550 g) and adhesion to the steel surface, a high water contact angle (93.53 deg.) and excellent cupping (13.38 mm). Moreover, its crosslinking density (CD) and its thermal stability was checked by using dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA).

Molecular-mass distribution of alkylphenolformaldehyde oligomers modified by imidazolines

The molecular weight distribution of monoalkyl(C8–C12)phenolformaldehyde oligomers modified with imidazolines based on sunfl ower or corn oil fatty acids and polyamines – diethylenetriamine, triethylenetetraamine, polyethylene polyamines was determined by gel-chromatography. The influence of the component and quantitative composition on the parameters of the number average and weight average molecular weights, as well as on the polydispersity of oligomers, was studied. Regularities have been revealed and assumptions have been made regarding repeating monoalkyl (C8-C12)phenol-formaldehyde fragments in the composition of oligomeric macromolecules.

Characterization of polymer properties and identification of additives in commercially available research plastics

This work reports the analysis of 59 commercially available polymers from 20 different polymer classes for thermal properties, macrostructure, molecular mass distribution, and inorganic and organic additives, highlighting the need to characterize research polymers prior to recycling studies.

The use of a biopeptide with antiviral properties as a functional ingredient for ice cream

Biopeptides are used in food products to give them a functional orientation. The purpose of the study is to characterize and use a biopeptide with antiviral properties for the production of ice cream with functional purpose. The molecular mass distribution of the peptide was evaluated by mass spectrometry and identified by MALDI-TOF and MS mass spectrometry on the MALDI-time-of-flight Ultraflex mass spectrometer (Bruker, Germany). The mass spectra were analyzed using the Mascot program, the Peptide Fingerprint option (Matrix Science, USA) using the Protein NCBI database. The antiviral activity of the peptide was studied on lentiviral particles. The assessment of the physical-chemical parameters of ice cream enriched with a biopeptide was determined according to regulatory documents. As a result of the research, a characteristic of a peptide with antiviral properties is given. It has been established that the peptide consists of 8 amino acids and is classified as an alpha helical cationic antiviral peptide. Ice cream “Vanilla Ice cream 15%” has been developed using synthesized LREGIKNK peptide as a functional ingredient. It is shown that the ice cream meets the requirements of regulatory documentation.

ХАРАКТЕРИСТИКА И ВЛИЯНИЕ МИКРОКАПСУЛЯЦИИ НА СТАБИЛЬНОСТЬ БИОПЕПТИДА В МОДЕЛИ IN VITRO

One of the ways to prevent the development of oxidative stress is the oral use of bioactive peptides. To ensure the targeted release of biologically active substances in the body, they are microcapsulated. The aim of the research is to characterize, predict, evaluate the antioxidant properties of a biopeptide and study the effect of microcapsulation on its stability in a model of the gastrointestinal tract. The molecular mass distribution of the peptide was evaluated by mass spectrometric method. Identification and characterization of the peptide was carried out using Protein NCBI and ARD databases. The antioxidant activity of the peptide was determined by DPPH, ABTS and FRAP methods. The microencapsulation of the peptide was carried out in a pseudo-boiling layer of 10 % maltodextrin solution. As a result of research, a peptide was isolated from trypsin hydrolysate of cow colostrum, its molecular weight, amino acid sequence, charge, hydrophobicity, isoelectric point, two- and three-dimensional structure were determined. Based on the obtained physicochemical characteristics of the peptide, a hypothesis about its antioxidant properties has been proposed, which has been confirmed in in vitro studies. It is proved that the microcapsulation of the peptide into a protective layer of maltodextrin ensures its stability in the model of the oral cavity and stomach and targeted release in the intestine in vitro.

Enzymatic hydrolysis of whey proteins by the combination of Alcalase and Neutrase: Kinetic model and hydrolysis control

A combination of Alcalase and Neutrase was used to hydrolyse whey proteins and the hydrolysis kinetics mechanism was studied to achieve accurate control of the hydrolysis process. By measuring the degree of hydrolysis (DH) at different enzyme concentrations and different substrate concentrations, the hydrolysis kinetic model was established as: DH=6.536Ln[1+(4.687E0S0–0.0007)t]. The results showed that the theoretical and actual values of the model were in good agreement. Subsequently, the molecular mass distribution of the whey proteins hydrolysates at different DH was determined; it was found that the molecular mass components of 5–20 and >20 kDa gradually decreased with the increase of DH, while the percentage of <1 kDa gradually increased. Extensive hydrolysis of whey proteins was achieved when the DH reached 21–25%. The establishment of kinetic model has theoretical guidance for the accurate control of the whey proteins hydrolysis by the combination of Alcalase and Neutrase.

Oxidation Treatments Using Hydrogen Peroxide to Convert Paper-Grade Eucalyptus Kraft Pulp into Dissolving-Grade Pulp

Converting paper-grade bleached Kraft pulp into dissolving pulp using eco-friendly chemicals on-site at the mill is a challenge for the pulp industry. In this study, two oxidation systems are evaluated: the first one is based on the use of hydrogen peroxide at various levels of alkalinity; the second one investigates the use of sodium periodate followed by hydrogen peroxide to convert aldehydes into carboxyls and enhance their hemicelluloses removal. Our results have shown that when using only peroxide, the removal of hemicelluloses was not sufficient to improve the pulp’s dissolving ability. Conversely, the periodate–peroxide system proved to be more efficient. Results regarding the pulp purity, solubility, degradation (pulp viscosity and cellulose molecular mass distribution), brightness, and its potential applications were discussed.

Theoretically predicting the solubility of polydisperse polymers using Flory–Huggins theory

Polydispersity affects physical properties of polymeric materials, such as solubility in solvents. Most biobased, synthetic, recycled, mixed, copolymerized, and self-assembled polymers vary in size and chemical structure. Using solvent fractionation, this variety in molecular features can be reduced and a selection of the sizes and molecular features of the polymers can be made. The significant chemical and physical dispersity of these polymers, however, complicates theoretical solubility predictions. A theoretical description of the fractionation process can guide experiments and material design. During solvent fractioning of polymers, a part of the polydisperse distribution of the polymers dissolves. To describe this process, this paper presents a theoretical tool using Flory–Huggins theory combined with molecular mass distributions and distributions in the number of functional groups. This paper quantifies how chemical and physical polydispersity of polymers affects their solubility. Comparison of theoretical predictions with experimental measurements of lignin in a mixture of solvents shows that multiple molecular features can be described well using a single set of parameters, giving a tool to theoretically predict the selective solubility of polymers.

Synthesis of Polymers with Narrow Molecular Mass Distribution through Interface-Initiated Room-Temperature Polymerization in Emulsion Gels.

Homopolymers of n-butyl acrylate, methyl methacrylate, styrene, and their random copolymers were prepared via interface-initiated polymerization of emulsion gels at 20 °C. The polymerization was conducted in a free radical polymerization manner without inert gas protection. Compared with the polymers synthesized at 60 °C, the polymerization of emulsion gels at 20 °C produced homo- and copolymers with a higher molecular mass and a narrower molecular mass distribution. The polydispersity indices for the polymers synthesized at 20 °C were found to be between 1.12 and 1.37. The glass transition temperatures for the as-synthesized butyl acrylate copolymers agree well with the prediction from the Gordon-Taylor equation. Interface-initiated room-temperature polymerization is a robust, energy-saving polymerization technique for synthesizing polymers with a narrow molecular mass distribution.

Prediction of antimicrobial activity of a food peptide and evaluation of its effectiveness in vitro

Food antimicrobial peptides are increasingly relevant in the treatment of bacterial infections and have a number of advantages in comparison with drugs: slower emergence of resistance in bacterial strains, high activity against antibiotic films and immunomodulatory properties. The physico-chemical properties causing antimicrobial properties include: cationic charge, hydrophobicity, molecular weight and amino acid sequence. Promising sources of antimicrobial peptides are milk proteins, in particular, cow colostrum proteins. The aim of the work is to extract a peptide from the pepsin hydrolysate of cow colostrum, predict its antimicrobial activity using a bioinformatic approach and confirm its effectiveness in vitro. The molecular mass distribution of the peptide was evaluated by mass spectrometric method. The analysis of mass spectra was carried out using the Mascot program, the Peptide Fingerprint option – using the Protein NCBI database. Microsequencing was performed using a MiSeq sequencer. Modeling of the spatial structure of the isolated peptide was carried out using the Schrodinger Maestro molecular modeling program. The antimicrobial activity of the peptide was studied by the disco-diffusion method on gram-positive and gram-negative bacteria. The peptide has been isolated from the pepsin hydrolysate of cow colostrum, which is absent in the known proteomic bases Protein NCBI and AVPdb and, accordingly, its biological activity and functions have not been studied. The resulting peptide belongs to linear alpha-helical peptides consists of 11 amino acid sequences ANRKLRANKSR with a molecular weight of 8.2 kDa, an isoelectric point at 12.79, a charge of +5 (cationic), hydrophilicity (hydrophobicity) +20.84 Kcal*mol-1. As a result of in vitro studies, it was found that the isolated peptide has antimicrobial activity against E. coli ATCC 25922 and B. subtilis and antimicrobial action against C. albicans.

Molecular mass engineering for filaments in material extrusion additive manufacture

Abstract3D printing of thermoplastics through local melting and deposition via material extrusion additive manufacturing provides a simple route to the near net‐shape manufacture of complex objects. However, the mechanical properties resulting from these 3D printed structures tend to be inferior when compared to traditionally manufactured thermoplastics. These unfavorable characteristics are generally attributed to the structure of the interface between printed roads. Here, we illustrate how the molecular mass distribution for a model thermoplastic, poly(methyl methacrylate) (PMMA), can be tuned to enhance the Young's modulus of 3D printed plastics. Engineering the molecular mass distribution alters the entanglement density, which controls the strength of the PMMA in the solid state and the chain diffusion in the melt. Increasing the low molecular mass tail increases Young's modulus and ultimate tensile strength of the printed parts. These changes in mechanical properties are comparable to more complex routes previously reported involving new chemistry or nanoparticles to enhance the mechanical performance of 3D printed thermoplastics. Controlling the molecular mass distribution provides a simple route to improve the performance in 3D printing of thermoplastics that can be as effective as more complex approaches.

Mass dipole contribution to the isotopic Soret effect in molecular mixtures.

Temperature gradients induce mass separation in mixtures in a process called thermal diffusion and are quantified by the Soret coefficient ST. Thermal diffusion in fluid mixtures has been interpreted recently in terms of the so-called (pseudo-)isotopic Soret effect but only considering the mass and moment of inertia differences of the molecules. We demonstrate that the first moment of the molecular mass distribution, the mass dipole, contributes significantly to the isotopic Soret effect. To probe this physical effect, we investigate fluid mixtures consisting of rigid linear molecules that differ only by the first moment of their mass distributions. We demonstrate that such mixtures have non-zero Soret coefficients in contrast with ST = 0 predicted by current formulations. For the isotopic mixtures investigated in this work, the dependence of ST on the mass dipole arises mainly through the thermal diffusion coefficient DT. In turn, DT is correlated with the dependence of the molecular librational modes on the mass dipole. We examine the interplay of the mass dipole and the moment of inertia in defining the isotopic Soret effect and propose empirical equations that include the mass dipole contribution.

New Ways of Controlling the Molecular Mass Characteristics and Distribution of Branches for Polyethylene Synthesized over Supported Catalysts Containing Fe(II) Bis(imino)pyridyl and Ni(II) Bis(imine) Complexes

New Ways of Controlling the Molecular Mass Characteristics and Distribution of Branches for Polyethylene Synthesized over Supported Catalysts Containing Fe(II) Bis(imino)pyridyl and Ni(II) Bis(imine) Complexes

Algorithm for Evaluation of the Molecular Characteristics of a Polymer Product under Conditions of Multipoint Control

Introduction. Under conditions of high demand for rubber products, continuous modernization of technological processes of continuous production is carried out. One of the tools to control the physical and chemical parameters of the resulting product is the technology of multipoint feeding of controlling impurities that can significantly affect the molecular characteristics of polymers. However, it is difficult to experimentally select the technology of multipoint feeding of controlling impurities to achieve the given molecular characteristics of polymers. Aim of the Article. To create a methodology that allows using the tools of model system description to carry out directed regulation and construction of the technological process to achieve a given molecular weight distribution. Materials and Methods. For more accurate mathematical modeling of polymer synthesis processes, two approaches to the model description of the system under study are considered: 1) Kinetic approach. In this case, the developed algorithm is based on the method of moments in combination with numerical methods for solving systems of ordinary differential equations that characterize the change in the material balance for each reaction component. When describing large-tonnage production, a modular principle is proposed, according to which the kinetics model is supplemented by hydrodynamic regularities that depend on the reactor type. 2) Statistical approach (Monte Carlo method). The algorithm for implementing the statistical approach is based on the probabilistic nature of elementary reactions. To describe the process in the reactor cascade, a systematic approach to the organization of calculations is proposed. Results. Using kinetic and statistical approaches new dependences of conversion and characteristic viscosity on polymerizer number were obtained, which showed satisfactory agreement with the values of the experimental results. Comparative analysis of calculated molecular-mass distribution curves of obtained product was carried out. The analysis confirms the significant influence of different modes of regulator feeding on molecular characteristics of polymer. Discussion and Conclusion. The analysis of the molecular chain structure of the copolymerization product under conditions of adding the third control point characterizes the decrease in rigidity and increase in elasticity of the resulting product, and the created digital evaluation tools allow by means of computational experiments to select optimal parameters of the regulator feeding in order to obtain polymers with a given molecular mass.