Orientation Of Macromolecules Research Articles

Studies of the Physical Structure of Cured Epoxy Resin Composite Modified with Silicon-Containing Additives

Abstract The possibility of regulating the structure and reducing its defectiveness opens great possibilities for controlling the properties of epoxy composite materials. This article reports the results of investigation by X-ray scattering and nuclear magnetic resonance methods and the microstructural changes that occur when silicon-containing additives such as polydimethyl siloxane (PDMS-5) and pyrogenic silica (HDK) are introduced into epoxy resin ED-20. The mechanism of formation of the structure of epoxy binder ED-20 with L-20 curing agent in the presence of complex additives is found. The modifying additive (PDMS-5 + HDK) is located in the epoxy binder because of the chemical interaction of functional polar groups and the developed surface. The additives increase the mobility of the reaction mixture and also facilitate and regulate the spatial orientation of macromolecules during polymerization. This contributes to the formation of a more regular and less defective spatial structure. The epoxy binder is a heterogeneous two-component system, one of which corresponds to a pseudo-crystalline region in which the movement of molecules is suppressed, and the second is found at lower volume fractions and is amorphous. The only maximum in the wide-angle X-ray diffraction pattern of the binder without additives is attributable to the distribution of molecular chains in the para-crystalline lattice. The addition of the HDK additive leads to ordering of the supramolecular structure, in which linear clusters consisting of 5–7 spheres appear. The average size of the spheres is from 8 to 26 nm. The addition of additives in the samples leads to the formation of a more regular and less defective spatial structure because of the interaction of functional polar groups and the surface, which regulate the spatial orientation of macromolecules during polymerization.

The role of the solvent nature in stretching polymer solutions (polyacrylonitrile spinning using different solvents)

We investigated how different solvents' affinity with polyacrylonitrile affects the formation of a jet that leads to stable fiber spinning. The study focused on two concentrations, one near and one above the crossover point where the topological entanglements are formed in the semi-dilute solutions. The role of the physical parameters of the solutions, including solvent-polymer affinity, viscosity, surface tension, and relaxation times, was analyzed. The experiment involved the uniaxial deformation of a solution drop under its weight, observed using a high-speed microscopic camera. The stability of the jet was associated with the relaxation time and solvent-polymer affinity. The continuous fiber spinning is mainly determined by the high enough polymer concentration in the solution, and the solvent nature, or by how the solution state is close to the theta conditions. Bicomponent mixed solvents offer two viable routes to achieve this – evaporating a more volatile component from the mixture to increase the polymer concentration, or modifying the solvent with a combination of solvents of different solvent quality. Both approaches have been experimentally validated, enabling the production of continuous stable fibers in the gel stretching regime. In this case, the jet stretching occurs under conditions Wi > 1. Thereby, the transition to the gel state promotes the necessary conditions for macromolecule orientation during fiber spinning.

Development of multilayer PVA-MMT and PVA-CS film structures by spin coating-assisted layer-by-layer technique: Effect of PVA, CS and MMT nanoclay orientation on oxygen barrier properties

The orientation of biopolymer macromolecules and nanoclay, specifically Montmorillonite (MMT) nanoplatelets, plays a crucial role in controlling the properties of multi-layer film structures. Understanding the impact of macromolecule and nanoclay platelets’ orientation on barrier properties of packaging films is essential. To investigate the influence of hydrogen bonding in multilayer films structures, two polymers, namely polyvinyl alcohol (PVA) and chitosan (CS), were selected and laminated nanocomposite films were fabricated using the spin coating-assisted layer-by-layer (Spin-LbL) assembly technique. This technique facilitates the production of highly oriented nanocomposite films, where polymer chains and nanoclay particles align parallel to the film surface. Multi-directional 2-D wide-angle X-ray diffraction (2D-WADX) was successfully used to accurately assess the orientation and distribution of MMT nanoplatelets. Additionally, the films underwent characterization using X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). The 2D-WADX analysis revealed a parallel alignment of both the PVA chains and MMT clay nanoplatelets parallel to film surface. The XRD results confirmed the formation of intercalated nanolaminate structures, hydrogen-bonding interactions, and adjustments in the crystalline structure of PVA matrix. Through contact angle and oxygen permeability measurements, we observed that all quadri-layer film structures exhibited hydrophobic properties and reduced oxygen permeability compared to neat PVA films. Furthermore, the integration of MMT nanoclay, even at low concentrations, contributed to the development of nanocomposite films with improved oxygen barrier properties. Consequently, the quadri-layer films demonstrate great potential for food packaging applications.

Dielectric polymer composites with ultra-high thermal conductivity and low dielectric loss

Polymer based dielectric materials with simultaneously high thermal conductivity and low dielectric loss are highly desirable in various applications like energy storage, thermal management and electronic packaging. Polymer dielectrics generally benefit from good electrical insulation, high breakdown strength, high toughness and low density but suffer from very low thermal conductivity (0.1–0.5 W m −1 K −1). Herein we propose a new strategy to overcome this compromise; solid-state drawing of ultra-high molecular weight polyethylene (UHMWPE) films doped with a small amount of nanodiamonds (NDs). The resulting orientation of UHMWPE macromolecules and the nanofiller significantly improves the thermal conductivity along the stretching direction, while the dodecane surface functionalization of the NDs endows a robust interface between the matrix and filler, which minimizes the thermal resistance and dielectric loss. Our composites film (2 wt% NDs) shows an ultra-high thermal conductivity of 60 W m −1 K −1 in the drawing direction and very low dielectric loss, both at low and high electric field. More generally, herein we demonstrates that the interfaces introduced by the nanofillers do not necessarily cause an increase in dielectric loss at high electric field and a decrease in thermal conductivity, providing a new direction for the design of novel polymer based dielectric and functional materials.

The Role of Structure in Polymer Rheology: Review.

The review is devoted to the analysis of the current state of understanding relationships among the deformation-induced structure transformations, observed rheological properties, and the occurrence of non-linear effects for polymer liquids (melts, solutions, and composites). Three levels of non-linearity are the base for consideration. The first one concerns changes in the relaxation spectra of viscoelastic liquids, which are responsible for weak non-linear phenomena. The second one refers to the strong non-linearity corresponding to such changes in the structure of a medium that leads to the emergence of a new relaxation state of a matter. Finally, the third one describes the deformation-induced changes in the phase state and/or the occurring of bifurcations and instability in flow and reflects the thermodynamic non-linear behavior. From a structure point of view, a common cause of the non-linear effects is the orientation of macromolecules and changes in intermolecular interaction, while a dominant factor in describing fluid dynamics of polymer liquids is their elasticity. The modern understanding of thixotropic effects, yielding viscoplastic materials, deformation-induced phase transition, and the experimental observations, demonstrating direct correlations between the structure and rheology of polymer liquids, are the main objects for discussion. All these topics are reviewed and discussed mainly on the basis of the latest five-year publications.

Stimuli-Responsive Three-Dimensional DNA Nanomachines Engineered by Controlling Dynamic Interactions at Biomolecule-Nanoparticle Interfaces.

Stimuli-responsive nanomachines are attractive tools for biosensing, imaging, and drug delivery. Herein, we demonstrate that the orientation of macromolecules and subsequent dynamic interactions at the biomolecule-nanoparticle (bio-nano) interfaces can be rationally controlled to engineer stimuli-responsive DNA nanomachines. The success of this design principle was demonstrated by engineering a series of antibody-responsive DNA walkers capable of moving persistently on a three-dimensional track made of DNA functionalized gold nanoparticles. We show that drastically different responses to antibodies could be achieved using DNA walkers of identical sequences but with varying number or sites of modifications. We also show that multiple interfacial factors could be combined to engineer stimuli-responsive DNA nanomachines with high sensitivity and modularity. The potential of our strategy for practical uses was finally demonstrated for the amplified detection of antibodies and small molecules in both buffer and human serum samples. Unlike many DNA-based nanomachines, the performance of which could be significantly hindered by the matrix of serum, our system shows a matrix-enhanced sensitivity as a result of the engineering approach at the bio-nano interface.

Spatially resolved macromolecular orientation in biological tissues using FT-IR imaging

Fourier-transform infrared spectroscopy (FT-IR) in combination with machine learning and chemometrics is an intensively developed, powerful tool for investigation of tissue biochemical composition with simultaneous microscopic visualization. This nondestructive, information rich and label-free technique has been successfully applied in cancer diagnostics. During the development of a disease or inflammatory processes, not only the chemical composition of tissues changes, but also their spatial organization. FT-IR imaging with linear polarization can provide new and useful information about chemically-specific orientation of macromolecules. Here, we present results of spatial macromolecular orientation in human, pancreatic tissue using four-polarization FT-IR method. Despite the much more complex chemical structure of tissue compared to artificial materials such as fibrillar polymers, the obtained orientations of biomolecules in tissue agreed with theoretical prediction.

Recent Advances in Antioxidant Polymers: From Sustainable and Natural Monomers to Synthesis and Applications.

Advances in technology have led to the production of sustainable antioxidants and natural monomers for food packaging and targeted drug delivery applications. Of particular importance is the synthesis of lignin polymers, and graft polymers, dopamine, and polydopamine, inulin, quercetin, limonene, and vitamins, due to their free radical scavenging ability, chemical potency, ideal functional groups for polymerization, abundance in the natural environment, ease of production, and activation of biological mechanisms such as the inhibition of the cellular activation of various signaling pathways, including NF-κB and MAPK. The radical oxygen species are responsible for oxidative damage and increased susceptibility to cancer, cardiovascular, degenerative musculoskeletal, and neurodegenerative conditions and diabetes; such biological mechanisms are inhibited by both synthetic and naturally occurring antioxidants. The orientation of macromolecules in the presence of the plasticizing agent increases the suitability of quercetin in food packaging, while the commercial viability of terpenes in the replacement of existing non-renewable polymers is reinforced by the recyclability of the precursors (thyme, cannabis, and lemon, orange, mandarin) and marginal ecological effect and antioxidant properties. Emerging antioxidant nanoparticle polymers have a broad range of applications in tumor-targeted drug delivery, food fortification, biodegradation of synthetic polymers, and antimicrobial treatment and corrosion inhibition. The aim of the review is to present state-of-the-art polymers with intrinsic antioxidant properties, including synthesis scavenging activity, potential applications, and future directions. This review is distinct from other works given that it integrates different advances in antioxidant polymer synthesis and applications such as inulin, quercetin polymers, their conjugates, antioxidant-graft-polysaccharides, and polymerization vitamins and essential oils. One of the most comprehensive reviews of antioxidant polymers was published by Cirillo and Iemma in 2012. Since then, significant progress has been made in improving the synthesis, techniques, properties, and applications. The review builds upon existing research by presenting new findings that were excluded from previous reviews.

EFFECT OF MAGNETIC FIELD ON RHEOLOGICAL PROPERTIES OF CELLULOSE ETHERS SOLUTIONS

The rheological properties, structure and phase transitions of hydroxypropyl cellulose in ethanol, dimethyl sulfoxide, ethylene glycol solutions and ethylcellulose in dimethylformamide solutions are studied using viscometry, the cloud-point method, polarization microscopy, the optical interferometry and a polarization photoelectric apparatus in the temperature range 280-360 K. The temperature-concentration regions of isotropic and anisotropic phases are determined for all systems. The type of boundary curves of phase diagrams is compared with the chemical structure of macromolecules. It is shown that the constant magnetic field (3.6 kOe) leads to the orientation of macromolecules in solutions. The domain structure arising in solutions is fixed after evaporation of a solvent and shown in orientation of strips of the film relief. It was found that the flow curves of all solutions at 298 K in the range of shear rates from 0 to 15 s-1 are typically for the non-Newtonian liquids. It was found that the magnetic field leads to an increase in the viscosity of isotropic solutions and a decrease in the viscosity of anisotropic solutions. Both effects depend on the direction of the magnetic field lines. When the rotor-rotation axis is parallel to the direction of power lines of the magnetic field the change in the viscosity of solutions is greater than that at perpendicular orientation of the rotor-rotation axis and power lines of the magnetic field. The results are discussed using representations about the changes in the macromolecule conformation and in the size and shape of the supramolecular particles in the solutions during flow under a magnetic field with different orientation of the power lines.

Simplified Approach for Preparing Graphene Oxide TEM Grids for Stained and Vitrified Biomolecules.

In this manuscript, we report the application of graphene oxide (GO) in the preparation of cryo-electron microscopy (cryo-EM) and transmission electron microscopy (TEM) grids. We treated GO with water and organic solvents, such as, methanol, ethanol and isopropanol separately to isolate significantly large GO monolayer flake to fabricate the grids for cryo-EM and TEM study. We implemented a simplified approach to isolate flakes of GO monolayer for constructing the TEM grids, independent of expensive heavy equipment (Langmuir–Blodgett trough, glow-discharge system, carbon-evaporator or plasma-cleaner or peristaltic pumps). We employed confocal microscopy, SEM and TEM to characterize the flake size, stability and transparency of the GO monolayer and atomic force microscopy (AFM) to probe the depth of GO coated grids. Additionally, GO grids are visualized at cryogenic condition for suitability of GO monolayer for cryo-EM study. In addition, GO-Met-H2O grids reduce the effect of preferred orientation of biological macromolecules within the amorphous ice. The power-spectrum and contrast-transfer-function unequivocally suggest that GO-Met-H2O fabricated holey grids have excellent potential for application in high-resolution structural characterization of biomolecules. Furthermore, only 200 movies and ~8000 70S ribosome particles are selected on GO-coated grids for cryo-EM reconstruction to achieve high-resolution structure.

Features of the Behavior of a Polymer Solution Jet in Electrospinning

Using the numerical analysis of the force balance equation and the rheological equation of the model of finitely extensible chains, the dynamics of a charged jet during the electrospinning of a polymer solution and the orientation of macromolecules in the jet are studied. In fairly weak electric fields, the jet always remains rectilinear, while in strong fields the straight section of the jet has a finite length, after which the motion of the jet becomes unstable. This behavior is due to the competition between inertial and viscoelastic forces, with viscoelasticity dominating in strong fields. It is found that polymer chains in the jet are strongly stretched along the flow direction.

Simultaneously achieving self-toughening and self-reinforcing of polyethylene on an industrial scale using volume-pulsation injection molding

It is critical and difficult for production of large polymer parts using injection molding method to simultaneously achieve both good flowability and mechanical properties. Volume-Pulsation Injection Molding (VPIM) technology, exerting a high-amplitude vibration force field during the entire injection molding process, can be exploited to address this challenge, on an industrial scale. Through orientation of macromolecules with vibration forces during injection molding, mechanical properties of polymers can be improved at low cost without sacrificing flowability. In this study, employing VPIM technology, self-toughening and self-reinforcing of high-density polyethylene (HDPE) were realized while maintaining satisfactory flowability. Comparing with those of the convention injection molding (CIM) samples @ 210 °C, impact and yield strengths of the VPIM samples @ 0.7 Hz-210 °C were increased by 782.93% and 14.25%, respectively. According to crystal morphologies, shish-kebabs were formed in intermediate layer, leading to a remarkable enhancement in mechanical properties. Injection temperature and processing frequency had an influence on the shish-kebab structure and the intermediate layer thickness, thereby determining mechanical properties. These analysis results were supported by the evidence from impact-fractured surface morphology, 2D-SAXS, 2D-WAXD, and DSC. The response law of crystal structure and morphology to the vibration flow field was proposed to uncover the influence of processing conditions on material properties.

Hemocompatible Chitin-Chitosan Composite Fibers

Composite chitosan fibers filled with chitin nanofibrils (CNF) were obtained by the wet spinning method. The paper discusses the mechanical properties of such type fibers and their hemocompatibility, as well as the possibility of optimizing these properties by adding chitin nanofibrils. It was shown that low CNF concentration (about 0.5%) leads to an increase in fiber tensile strength due to the additional orientation of chitosan macromolecules. At the same time, with an increase in the content of CNF, the stability of the mechanical properties of composite fibers in a humid medium increases. All chitosan fibers, except 0.5% CNF, showed good hemocompatibility, even on prolonged contact with human blood. The addition of chitin nanofibers leads to decrease in hemoglobin molecules sorption due to the decline in optical density at wavelengths of 414 nm and 540 nm. Nevertheless, the hemolysis of fibers was comparable or even lesser that carbon hemosorbent, which is actively used in clinical practice.

On the Origin of Changes in the Adhesive Interaction between Veneer and Glue under Glue Polarization in Plywood Manufacture

The possibilities of using an electrostatic field in the technology for manufacturing plywood by the example of birch veneer with the use of carbamide–formaldehyde epoxy or polyvinyl acetate glues have been considered. It has been shown that preliminary treatment of the glue in an electric field results in a decrease of the glue viscosity and leads to an increase in the plywood strength under chipping, whereas the polarization of plywood samples in the course of the gluing procedure causes the ultimate strength under chipping to increase. The results can be explained as being due to the orientation of the glue macromolecules owing to an electric field, which leads to hardening of the material. This effect may be caused by a double electric layer occurring at the veneer–glue interface, increasing the adhesion of the glue to the veneer, by lowering glue viscosity and improving veneer surface wettability, as well as by an increase in the free surface energy of glues in the course of polarization thereof.

Chromosome aberration in typical biological systems under exposure to low- and high-intensity magnetic fields

ABSTRACTThe aim of this study was to investigate the response of chromosomes in typical human and plant cells under applied low-frequency magnetic fields at low and high intensities. Neuronal-like cells and roots of Allium sativum and Vicia faba were used to investigate chromosome's response to a static and 50 Hz magnetic fields at intensities ranging from 1 mT to 0.8 T, generated by two Helmholtz coils driven by direct current or alternate current voltage. Vertex spectrometer and Olympus microscope with camera were used. A significant decrease in intensity of the phosphate bands in the DNA infrared region was observed by FTIR spectroscopy analysis after exposure of neuronal-like cells to static and 50 Hz magnetic field at low intensity of 1 mT, which can be explained assuming that uncoiling and unpackaging of chromatin constituents occurred after exposure. This effect was directly observed by microscope in roots of Allium sativum and Vicia faba under exposure to a static magnetic field at high intensity of 0.8 T. These findings can be explained assuming that exposure to both low- and high-intensity magnetic fields of chromosomes in typical human and plant cells induces uncoiling and unpackaging of chromatin constituents, followed by chromosome alignment towards the direction of applied magnetic field, providing further demonstration that magnetic fields can induce the orientation of organic macromolecules even at low-intensity values.

The Influence of Electric Field on the Adhesion Characteristics of the Polychloroprene-Shungite System

The effect of temperature and external electric field on the adhesion characteristics in the polychloroprene-schungite system was investigated. It is shown that an increase in temperature and orientation of macromolecules of polychloroprene in an external electric field significantly increase the bond strength between the studied components. The detected effects are explained from the viewpoint of the possibility of direct chemical interaction ofshungite with polychloroprene macromolecules oriented in a certain way in the region of an adhesive compound formation. This is facilitated by the structural features of schungite (the presence of paramagnetic centers, fullerene-like structures, metal oxides) and polychloroprene in shungite, as well as by the creation of the most optimal modes for implementing this interaction. To assess the strength of the interaction between polychloroprene and the surface of shungite we used a method for determining the stress of exfoliation of a polymer film from the surface of a shungite plate. It was established that the greatest effect in strengthening the bond between polychloroprene and the surface of shungite is achieved when a polymer film is formed from a solution in carbon tetrachloride on a negative electrode (cathode). The strength of the bond between shungite and the polychloroprene film formed on the cathode is more than two times higher than this parameter when forming the same film on the anode. The energy expended during the peeling of a film formed on the cathode is twice the energy of exfoliation from the shungite plate of the film formed on the anode. The analysis of the change in the supramolecular structure of polychloroprene in the polychloroprene-shungite system as a result of the orientational influence of an external electrostatic field was carried out using the temperature dependence of the tangent of the dielectric loss angle of the systems under study. It is shown that a polychloroprene film formed in an electrostatic field has a more ordered structure compared to a similar sample formed without a field. This fact is evidenced by the shift of the maxima toward higher temperatures in the relaxation spectra of the dipole polarization for the system formed without the field, and the system formed on the cathode. The polychloroprene film containing finely dispersed shungite as a filler and formed on the cathode is characterized by an increased value of the tangent of dielectric loss angle and an increased number of peaks of dipole relaxation in the temperature range studied.

Interpolymer interaction in insulin-chitosan complexes

ABSTRACTOur team conducted theoretical calculations and experimental studies of interpolymer interactions in insulin-chitosan complexes based on the spatial orientation of chitosan and insulin macromolecules using Langmuir film balance at various pH values. The most optimal conditions for interpolymer interactions between insulin and chitosan chains occur at pH value of 5.4, which corresponds to the isoelectric point of insulin. For the similar pH values of 4.2 and 6.0, the free energy of coordination between chitosan and insulin was estimated by molecular dynamic simulations as of 1.1 and 5.8 kcal mol−1, respectively.

Hydrodynamic interaction for rigid dumbbell suspensions in steady shear flow

From kinetic molecular theory, we can attribute the rheological behaviors of polymeric liquids to macromolecular orientation. The simplest model to capture the orientation of macromolecules is the rigid dumbbell. For a suspension of rigid dumbbells, subject to any shear flow, for instance, we must first solve the diffusion equation for the orientation distribution function. From this distribution, we then calculate the first and second normal stress differences. To get reasonable results for the normal stress differences in steady shear flow, one must account for hydrodynamic interaction between the dumbbell beads. However, for the power series expansions for these normal stress differences, three series arise. The coefficients for two of these series, (ck, dk), are not known, not even approximately, beyond the second power of the shear rate. Analytical work on many viscoelastic material functions in shear flow must be checked for consistency, in their steady shear flow limits, against these normal stress difference power series expansions. For instance, for large-amplitude oscillatory shear flow, we must recover the power series expansions in the limits of low frequency. In this work, for (ck, dk), we arrive at the exact expressions for the first 18 of these coefficients.

Effects of Graphene Oxide on the Structure and Properties of Regenerated Wool Keratin Films.

Much research has focused on improvement of the structural and mechanical properties of regenerated keratin materials by physical or chemical methods in recent years. In this research, regenerated keratin materials were modified with graphene oxide (GO). The properties of modified keratin films and the mechanism of interaction between GO and keratin macromolecules were studied. The SEM and XRD test results showed that the orientation of keratin macromolecules could be effectively improved by GO, which favored improvement of the keratin material’s crystallinity and made the films more uniform and compact. The thermal stability and mechanical properties of GO-modified keratin films were also improved significantly. At the same time, the reaction mechanism between keratin and GO materials was analyzed by sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE), FT-IR, and Raman spectroscopy. It was shown that there was no chemical reaction between GO and keratin molecules, and the interaction between them was mainly via hydrogen bonding and van der Waals forces.

Macromolecule Orientation in Nanofibers.

Electrospinning is now commercially used for the fabrication of nano/micro fibers. Compared with spider dragline silk, artificial fibers have poor mechanical properties. Unlike natural silk, which has a hierarchical structure with an approximate 3-fold symmetry, the molecular structure of spun fiber has neither folding nor orientation. To date, it is almost impossible to control molecule orientation during the spinning process. Here, we show that macromolecule orientation can be easily controlled using the laminar flow of fluid mechanics. A lasting laminar flow in a long needle can order macromolecules. We find that the orientation of macromolecules can greatly affect the morphology and mechanical properties of fibers. We expect our technology to be helpful for more sophisticated fabrication of fibers with ordered macromolecules and DNA-like twists.