Concentration Dependence Research Articles

Local swelling effect of flexible entangled polymer chains in athermal solvents

Solutions of flexible, entangled polymer chains dissolved in athermal solvents have been widely studied; however, the influence of the local swelling effects on the overall dynamics of such systems remains incompletely understood. In this study, we performed coarse-grained simulations to compute the concentration dependence of plateau modulus of such systems. Initially, we examined the concentration dependence of entanglement length, denoted as Ne, through simulations. Our findings revealed a concentration scaling relationship for Ne, demonstrating Ne=AΦ−5/4+B, where A and B are chain length independent constants, and Φ is polymer concentration. To account for the local swelling effects, we employed the concept of blobs to represent the chains confined in athermal solvents. Each blob was characterized by a diameter ξ, a number of connected beads g, and a volume Ωb∼ξ3. Our simulations showed that the blob diameter followed the excluded volume relationship, with ξ∼g3/5. By combining the local swelling effect and the non-zero constant B, we derived a concentration scaling relationship for the plateau modulus G of solutions of flexible polymer chains in athermal solvents: G∼Φ(Ne/g)Ωb∼Φ2.30. This scaling exponent aligns with experimental observations ranging from dilute to highly concentrated systems, as well as our simulations, where values of 2.0–2.3 were observed.

Combustion in a chamber furnace with a tangentially swirling vortex

Relevance. The need to analyze the furnace processes in boiler units with vertical vortex when arranging pulverized coal combustion with the enhancement of environmental parameters through the installation of tertiary blast nozzles. Despite the carbon-free policy in modern power engineering coal remains one of the main sources of energy, so the reconstruction of boiler units in order to reduce harmful emissions is very relevant. Aim. To study aerodynamics and combustion processes of pulverized coal fuel in the furnace chamber of a boiler unit with a tangential arrangement of burner devices using a combustion scheme with tertiary air blowing. Methods. The Eulerian–Lagrangian approach was applied to numerical study of flow characteristics, heat transfer and combustion in a furnace with a tangential burner arrangement. Also, k-ε model of gas turbulence, particle-turbulence interaction, diffusion model of particle dispersion, P-1 radiation modeling method and pulverized coal particle combustion model based on global particle kinetics and experimental data were used for numerical calculations. Results. Based on numerical calculations and analysis, the dependences of combustion product concentrations, temperature, hydrodynamics at combustion of Kuznetsky coal grade D in the furnace chamber with tangential arrangement of burners for brown coal, as well as at installation of tertiary blast nozzles have been obtained. Insufficient redistribution of air between burners and tertiary nozzles is revealed, as for maintenance of stable twist of vertical vortex and accordingly presence of high values of velocities at the outlet of burner devices it is not possible to increase the portion of tertiary air without reconstruction of burners. It is also established that the volume of the furnace chamber below the burners is poorly involved in heat exchange.

Features and Advantages of the Recurrent Approximation of Retention Times in Reversed-Phase High-Performance Liquid Chromatography

Background: Recurrent approximation of retention parameters in reversed-phase HPLC is effective for revealing anomalies that are otherwise difficult to detect, namely, the reversible hydration of analytes. This was demonstrated previously for restricted sets of analytes with acetonitrile–water eluents. Expanding the number of analytes and eluents seems to be a topical problem. Two kinds of derivatives of aromatic carbonyl compounds were characterized: unsubstituted hydrazones and oximes. Methods: If analyte demonstrates no anomalies in dependences of retention times vs. concentration of organic modifier, the recurrent approximations of these dependences are linear. To explain the features of recurrent approximations, the numerical experiments were proposed and considered. The artificial shifting of one, two, or more points allows for the modeling the different kinds of deviations of approximations from linearity. Results: It was shown that hydrazones are the class of analytes having no anomalies of retention parameters. On the contrary, several anomalies were detected for oximes. Downward deviations of points in the plots of recurrent approximations of retention times are the signs of reversible hydration. This effect for methanol–water eluents was detected for the first time. Some of oximes underwent hydrolysis. Conclusions: Recurrent approximation of retention times allows detecting chemical transformations of analytes during RP HPLC analysis.

Ion Conductivity in Salt-Doped Polymers: Combined Effects of Temperature and Salt Concentration.

We construct a coarse-grained molecular dynamics model based on poly(ethylene oxide) and lithium bis(trifluoromethane)sulfonimide salt to examine the combined effects of temperature and salt concentration on the transport properties. Salt doping notably slows the dynamics of polymer chains and reduces ion diffusivity, resulting in a glass transition temperature increase proportional to the salt concentration. The polymer diffusion is shown to be well represented by a modified Vogel-Fulcher-Tamman (M-VFT) equation that accounts for both the temperature and salt concentration dependence. Furthermore, we find that, at any temperature, the concentration dependence of the conductivity is well described by the product of its infinite dilution value and a correction factor accounting for the reduced segmental mobility with increasing salt concentration. These results highlight the important role of polymer segmental mobility in the salt concentration dependence of ion conductivity for temperatures near and above the glass transition.

Elucidating the mechanisms of formononetin in modulating atherosclerotic plaque formation in ApoE-/- mice

BackgroundAtherosclerosis(AS) poses a pressing challenge in contemporary medicine. Formononetin (FMN) plays a crucial role in its prevention and treatment. However, the detailed impact of FMN on the stability of atherosclerotic plaques and its underlying mechanisms remain to be elucidated.MethodsAn intervention consisting of FMN was given along with a high-fat food regimen in the ApoE-/- mouse model. The investigation included the evaluation of the degree of atherosclerotic lesion, the main components of the plaque, lipid profiles, particular markers indicating M1/M2 macrophage phenotypes, the quantities of factors related to inflammation, the infiltration of macrophages, and the identification of markers linked to the α7nAChR/JAK2/STAT3 axis effect molecules.ResultsThe evaluation of aortic morphology in ApoE-/-mice revealed that FMN significantly improved the plaque area, fibrous cap protrusion, lipid deposition, and structural alterations on the aortic surface, among other markers of atherosclerosis,and there is concentration dependence. Furthermore, the lipid content of mouse serum was assessed, and the results showed that the low-, medium-, and high-dosage FMN groups had significantly lower levels of LDL-C, ox-LDL, TC, and TG. The results of immunohistochemical staining indicated that the low-, medium-, and high-dose FMN therapy groups had enhanced CD206 expression and decreased expression of CD68 and iNOS. According to RT-qPCR data, FMN intervention has the potential to suppress the expression of iNOS, COX-2, miR-155-5p, IL-6, and IL-1β mRNA, while promoting the expression of IL-10, SHIP1, and Arg-1 mRNA levels. However, the degree of inhibition varied among dosage groups. Western blot investigation of JAK/STAT signaling pathway proteins and cholinergic α7nAChR protein showed that p-JAK2 and p-STAT3 protein expression was suppressed at all dosages, whereas α7nAChR protein expression was enhanced.ConclusionsAccording to the aforementioned findings, FMN can reduce inflammation and atherosclerosis by influencing macrophage polarization, blocking the JAK/STAT signaling pathway, and increasing α7nAChR expression.

Concentration Dependence of Elastic and Viscoelastic Properties of Aqueous Solutions of Ficoll and Bovine Serum Albumin by Brillouin Light Scattering Spectroscopy.

The cellular environment is crowded with macromolecules of different shapes and sizes. The effect of this macromolecular crowding has been studied in a variety of synthetic crowding environments: two popular examples are the compact colloid-like Ficoll macromolecule and the globular protein bovine serum albumin (BSA). Recent studies have indicated that a significant component of bound or surface-associated water in these crowders reduces the available free volume. In this work, Brillouin light scattering experiments were performed on aqueous solutions of Ficoll 70 and Ficoll 400 with concentrations ranging from 1 to 35 wt % and BSA with concentrations of 1 to 27 wt %. From the dependence of spectral peak parameters on polymer concentration, we determined fundamental solution properties: hypersound velocity, adiabatic bulk modulus and compressibility, apparent viscosity, and hypersound attenuation. The existing theory that ignores intermolecular interactions can capture only the observed linear trends in the frequency shift up to a threshold concentration, beyond which a quadratic term accounting for intermolecular interactions is necessary. This likely indicates a transition from the dilute to semidilute regime. In the Ficoll solutions (but not BSA), we see evidence for a central mode, which is indicative of relaxation in the hydration shell of Ficoll.

Magnesium-lithium thin films for neurological applications–An in vitro investigation of glial cytocompatibility and neuroinflammatory response

Lithium (Li), a widely used drug for bipolar disorder management, is associated with many side effects due to systemic exposure. The localized delivery of lithium through implants could be an approach to overcome this challenge, for which biodegradable magnesium (Mg)-based materials are a promising choice. In this study, we focus on Mg-Li thin film alloys as potential Li-releasing implants. Therefore, we investigated the in vitro short-term corrosion behavior and cytocompatibility of two alloys, Mg-1.6wt%Li and Mg-9.5wt%Li. As glial cells are the key players of foreign body responses to implants, we used human glial cell lines for cytocompatibility studies, and a murine brain slice model for a more holistic view at the neuroinflammatory response. We found that Mg-1.6wt%Li corrodes approximately six times slower than Mg-9.5wt%Li. Microscopic analysis showed that the material surface (Mg-1.6wt%Li) is suitable for cell adhesion. The cytocompatibility test with Mg-1.6wt%Li and Mg-9.5wt%Li alloy extracts revealed that both cell types proliferated well up to 10 mM Mg concentration, irrespective of the Li concentration. In the murine brain slice model, Mg-1.6wt%Li and Mg-9.5wt%Li alloy extracts did not provoke a significant upregulation of glial inflammatory/ reactivity markers (IL-1β, IL-6, FN1, TNC) after 24 h of exposure. Furthermore, the gene expression of IL-1β (up to 3-fold) and IL-6 (up to 16-fold) were significantly downregulated after 96 h, and IL-6 downregulation showed a Li concentration dependency. Together, these results indicate the acute cytocompatibility of two Mg-Li thin film alloys and provide basis for future studies to explore promising applications of the material. Statement of significanceWe propose the idea of lithium delivery to the brain via biodegradable implants to reduce systemic side effects of lithium for bipolar disorder therapy and other neurological applications. This is the first in vitro study investigating Mg-xLi thin film degradation under physiological conditions and its influence on cellular responses such as proliferation, viability, morphology and inflammation. Utilizing human brain-derived cell lines, we showed that the material surface of such a thin film alloy is suitable for normal cell attachment. Using murine brain slices, which comprise a multicellular network, we demonstrated that the material extracts did not elicit a pro-inflammatory response. These results substantiate that degradable Mg-Li materials are biocompatible and support the further investigation of their potential as neurological implants.

Viscous flow and structural properties in water-ethanol-urea systems

The structural features of water-ethanol, water-urea and water-ethanol-urea systems were studied on the basis of experimental estimates of kinematic viscosity at different temperatures and concentra-tions. For this purpose, the concentration dependences of the Gibbs energy of activation of the viscous flow, the enthalpy of activation of the viscous flow and the entropy of activation of the viscous flow of the studied systems were analyzed. The results show that ethanol has a structuring and then de-structive effect on water up to a concentration of 0.15 molar, and urea has a destructive effect on the structure of water, starting from such small concentrations. The addition of urea to the ethanol-water system does not affect the inversion point.

Synthesis and self-assembly behaviors of α-galactosyl ceramide (1,2)-polysaccharide analogue

α-Galactosyl ceramide (GalCer) as a glycolipid has been long used as a standard reference for positive control in natural killer T cell studies. The (1,2)-disaccharide analogue of GalCer attracts a special attention in the study of lysosomal glycolipid processing. This paper describes the synthesis and self-assembly behaviors of GalCer 1,2-polysaccharide analogue (PolyGalCer), having considered the 1,2-disaccharide analogue as a structural motif. The synthesis of PolyGalCer is performed via one-pot glycosidation technique of 1,2-linked oligogalactan exploiting chain polymerization of galactose-based cyclic sulfite as a monomer initiated with ceramide-based alcoholic aglycon. Through the concentration dependence of PolyGalCer solutions in water or in MeOH on the turbidity, it is found that PolyGalCer forms associates in both media. From the intersection points, the critical aggregation concentration (CAC) values of PolyGalCer in water and MeOH were estimated. To know the self-assembly and the thermal transition behaviors, we performed dynamic light scattering (DLS) analysis of the associates comprising PolyGalCer in water. The transmission electron microscopy observations of the aqueous sample solution indicate that the solution of PolyGalCer includes large spherical associates. The results clarify that the 1,2-galactan moiety of PolyGalCer skeleton contributes on the kinetic inhibition of large associate formation and the metamorphosis of associates.

Effect of progressive substitution of spin-3/2 by spin-7/2 on the magnetocaloric properties of a mixed spin binary alloy system: A Monte Carlo study

Using Monte Carlo simulation the concentration dependency of the cooling exponent (n) of a binary alloy AxB1-x mixed spin system (7/2, 3/2) was studied rigorously. For low magnetic field (h) the entropy change (ΔS), excellently follows the relation ΔS∝hn. The exponent n hardly changes with x within the region 0.5 < x < 0.75. But for further increment of x > 0.75, n sharply drops down. The exponent n is strongly affected by the exchange interaction energy (ε). Due to the decrement of the antiferromagnetic interactions n value rapidly decreases. For the increment of x or the number of A(spin-7/2) atom the magnetization M as well as the magnetic entropy change ΔS increases. The phase transition temperature (i.e. Curie temperature) tC linearly decreases for the increase of x.

Kinetic evidence for multiple aggregation pathways in antibody light chain variable domains.

Aggregation of antibody light chain proteins is associated with the progressive disease light chain amyloidosis. Patient-derived amyloid fibrils are formed from light chain variable domain residues in non-native conformations, highlighting a requirement that light chains unfold from their native structures in order to aggregate. However, mechanistic studies of amyloid formation have primarily focused on the self-assembly of natively unstructured peptides, and the role of native state unfolding is less well understood. Using a well-studied light chain variable domain protein known as WIL, which readily aggregates in vitro under conditions where the native state predominates, we asked how the protein concentration and addition of pre-formed fibril "seeds" alter the kinetics of aggregation. Monitoring aggregation with thioflavin T fluorescence revealed a distinctly non-linear dependence on concentration, with a maximum aggregation rate observed at 8 μM protein. This behavior is consistent with formation of alternate aggregate structures in the early phases of amyloid formation. Addition of N- or C-terminal peptide tags, which did not greatly affect the folding or stability of the protein, altered the concentration dependence of aggregation. Aggregation rates increased in the presence of pre-formed seeds, but this effect did not eliminate the delay before aggregation and became saturated when the proportion of seeds added was greater than 1 in 1600. The complexity of aggregation observed in vitro highlights how multiple species may contribute to amyloid pathology in patients.

Nitrogen Concentration Dependence of Two‐Step Photocurrent Generation by Below‐Gap Excitation in GaPN Alloys

Two‐step photocurrent generation and its dependence on nitrogen concentration in GaPN alloys using two‐wavelength excited photocurrent (TWEPC) measurements are investigated. External quantum efficiency (EQE) measurements show an increase in the two‐step absorption of below‐gap excitation light through tail states at longer wavelengths and that the quasi‐direct gap redshifts as the nitrogen concentration increases. The improvement in the EQE at longer wavelengths is explained by the increased density of the tail states in GaPN with higher nitrogen concentrations. In contrast, the EQE decreases at shorter wavelengths with increasing nitrogen content. TWEPC results show that differential photocurrent density , which shows the synergy effect of multiple‐wavelength light, reduces with the addition of nitrogen. It is found from rate–equation analysis that the decrease in the EQE at shorter wavelengths and in is mainly due to the increased nonradiative recombination in GaPN with higher nitrogen concentration. The use of lattice‐matched alloys and a p‐type GaP capping layer as well as the optimization of the growth conditions can improve the EQE at shorter wavelengths and .

Kinetics of polaron capture by traps in a lithium niobate crystal

The problem of reversible transformation and trapping of small-radius polarons in a lithium niobate crystal is considered within the framework of the integral encounter theory which is binary in the concentration of reatants. Analytical solutions are obtained for the relaxation kinetics of polarons, their lifetimes, and the rate constants of the corresponding channels of a multistage reaction controlled by polaron mobility. The temperature and concentration dependences of the observed quantities are analyzed. It is shown that at low temperatures polarons accumulate in a bound state characterized by an anomalously low relaxation rate.

Passivating Blunt‐Ended Helices to Control Monodispersity and Multi‐Subunit Assembly of DNA Origami Structures

Deoxyribonucleic acid (DNA) origami enables the synthesis of bespoke nanoscale structures suitable for diverse applications. Effective design requires preventing uncontrolled aggregation, while still facilitating directed multi‐subunit assembly. Uncontrolled aggregation is often caused by base‐stacking interactions between arrays of blunt‐ended helices, a problem which is typically mitigated by incorporating disordered single‐stranded DNA (ssDNA) (like scaffold loops or poly‐thymine brushes) at the end of double‐stranded DNA (dsDNA) helices. Such disordered regions are ubiquitous in DNA origami structures yet their optimal design requirements in various chemical environments remains unclear. This study systematically investigates scaffold loops and poly‐nucleotide brushes for aggregation prevention and control of multi‐subunit assembly, examining length, sequence, and MgCl2 concentration dependencies. Additionally, a novel strategy is introduced using orthogonal double‐stranded DNA helices to create a steric shield against base stacking. The results reveal key considerations. Poly‐thymine brushes excel in achieving monodispersity across diverse conditions whereas scaffold loops aid directed multi‐subunit assembly. Orthogonal DNA helices remove the need for disordered regions altogether, preventing aggregation over a broad range of MgCl2 concentrations and facilitating controlled multi‐subunit assembly. This study expands the toolbox for DNA origami design and enables a more informed approach for achieving control of monodispersity and multi‐subunit assembly in DNA origami structures.

Structures and Properties of High-Concentration Doped Th:CaF2 Single Crystals for Solid-State Nuclear Clock Materials.

Thorium-doped vacuum ultraviolet (VUV) transparent crystals is a promising candidate for establishing a solid-state nuclear clock. Here, we report the research results on high-concentration doping of 232Th:CaF2 single crystals. The structures, defects, and VUV transmittance performances of highly doped Th:CaF2 crystals are investigated by theoretical and experimental methods. The defect configurations formed by Th and the charge compensation mechanism (Ca vacancy or interstitial F atoms) located at its first nearest neighbor position are mainly considered and studied. The preferred defect configuration is identified according to the doping concentration dependence of structural changes caused by the defects and the formation energies of the defects at different Ca or F chemical potentials. The cultivated Th:CaF2 crystals maintain considerable high VUV transmittance levels while accommodating high doping concentrations, showcasing an exceptional comprehensive performance. The transmittances of 1-mm-thick samples with doping concentrations of 1.91 × 1020 and 2.76 × 1020 cm-3 can reach ∼62% and 53% at 150 nm, respectively. The VUV transmittance exhibits a weak negative doping concentration dependence. The system factors that may cause distortion and additional deterioration of the VUV transmittance are discussed. Balancing and controlling the impacts of various factors will be of great significance for fully exploiting the advantages of Th:CaF2 and other Th-doped crystals for a solid-state nuclear optical clock.

To What Extent Do Iodomethane and Bromomethane Undergo Analogous Reactions?

Iodomethane and bromomethane (CH3I/CH3Br) are common chemicals, but their chemistry on nanometals is not fully understood. Here, we analyze the reactivity of Rhn+ (n = 3-30) clusters with halomethanes and unveil the spin effect and concentration dependence in the C-H and C-X bond activation. It is found that the reactions under halomethane-rich conditions differ from those under metal-rich conditions. Both CH3I and CH3Br undergo similar dehydrogenation on the Rhn+ clusters in the presence of small quantity reactants; however, different reactions are observed in the presence of sufficient CH3I/CH3Br, showing dominant Rh(CH3Br)x+ (x = 1-4) products but a series of RhnCxHyIz+ species (x = 1-4, y = 1-12, and z = 1-5) pertaining to H2, HI, or CH4 removal. Density functional theory calculations reveal that the dehydrogenation and demethanation of CH3Br are relatively less exothermic and will be deactivated by sufficient gas collisions if helium cooling takes away energy immediately; instead, the successive adsorption of CH3Br gives rise to a series of Rh(CH3Br)x+ species with accidental C-Br bond dissociation.

Research of CdS/L-cystein colloid solutions using the method of mathematical planning

In the work, the additive effect of the content of crystal-forming ions Сd2+ and S2- and the stabilizer L-Cys using the method of mathematical planning of the experiment on the process of formation of CdS/L-Cys nanoparticles in potentially oxidizing conditions (without deaeration of precursor solutions) and the optical properties of colloidal solutions were investigated. obtained under conditions of pH = 7 and temperature of 220C. By statistical processing of the results, equations were obtained and diagrams of concentration dependences of the wavelength of the optical absorption edge of colloidal solutions of CdS semiconductor nanoparticles in the Сd2+ – L-Cys – S2- system were constructed.&#x0D;

A Unified Description of Salt Effects on the Liquid-Liquid Phase Separation of Proteins.

Protein aggregation via liquid-liquid phase separation (LLPS) is ubiquitous in nature and is intimately connected to many human diseases. Although it is widely known that the addition of salt has crucial impacts on the LLPS of proteins, full understanding of the salt effects remains an outstanding challenge. Here, we develop a molecular theory that systematically incorporates the self-consistent field theory for charged macromolecules into the solution thermodynamics. The electrostatic interaction, hydrophobicity, ion solvation, and translational entropy are included in a unified framework. Our theory fully captures the long-standing puzzles of the nonmonotonic salt concentration dependence and the specific ion effect. We find that proteins show salting-out at low salt concentrations due to ionic screening. The solubility follows the inverse Hofmeister series. In the high salt concentration regime, protein continues salting-out for small ions but turns to salting-in for larger ions, accompanied by the reversal of the Hofmeister series. We reveal that the solubility at high salt concentrations is determined by the competition between the solvation energy and translational entropy of the ion. Furthermore, we derive an analytical criterion for determining the boundary between the salting-in and salting-out regimes, which is in good agreement with experimental results for various proteins and salt ions.

Study of the free carrier characteristics and surface morphology of AlGaAs/GaAs thin films deposited using MOCVD

Ultra-low loss optical thin films find broad applications in fields such as vertical-cavity surface-emitting lasers and optical atomic clocks. The main optical losses in AlGaAs/GaAs distributed Bragg reflectors (DBRs) prepared using metal-organic chemical vapor deposition (MOCVD) arise from absorption loss caused by free carriers within the layers and scattering loss caused by surface roughness. In this study, we fabricated AlGaAs and GaAs single-layer thin films with varying Al compositions on substrates of three crystal orientations and under different V/III ratios. The dependence of carrier concentration and surface morphology on different substrates and growth conditions was investigated. Thin films grown on substrates with three different crystal orientations exhibited three distinct growth modes (step-flow mode, SK mode, and FM mode). The impact of the V/III ratio on the growth mode was found to be complex. Higher V/III ratios resulted in poorer morphology for films grown on (100) substrates, while better morphology was observed on (211) B substrates. Furthermore, the surface morphology of films grown on (100) 15° off substrates showed less sensitivity to changes in the V/III ratio. With increasing Al composition, the carrier concentration of the films significantly increased. Elevating the V/III ratio proved effective in suppressing the incorporation of carbon, thereby reducing the carrier concentration of AlGaAs films. GaAs films exhibited a low carrier concentration at an appropriate V/III ratio. Additionally, the distinct abilities of different substrates to adsorb impurities exerted a significant impact on the carrier concentration of the films. This study demonstrates that, under optimal conditions, it is feasible to fabricate AlGaAs/GaAs Bragg mirrors with low carrier concentration and relatively small roughness on (100) 15° off substrates.

Reliable electrical performance of β-Ga2O3 Schottky barrier diode at cryogenic temperatures

Electrical and trap characteristics of a large-size (2 × 2 mm2) β-Ga2O3 Schottky barrier diode (SBD) from 50 to 350 K have been reported. The ideality factor (n) decreases from 1.34 to nearly unity as temperature rises from 50 to 350 K, demonstrating near-ideal Schottky characteristics. The leakage current at cryogenic temperature (100 K) was significantly suppressed, indicating excellent off-state blocking performance at low temperatures. The weak temperature dependence of the carrier concentration (NS) and Schottky barrier height (ΦB) infers stable electrical characteristics of the β-Ga2O3 SBD. The stressed current density-voltage (J-V) and on-the-fly measurements reveal reliable dynamic performance under harsh low temperature conditions. Via deep-level transient spectroscopy, an electron trap, which is related to the dynamic performance instability and Lorentzian hump in low frequency noise spectra, is revealed for a β-Ga2O3 epilayer. The study reveals enormous potential of the utilization of a large-size β-Ga2O3 SBD for extreme temperature environments.