Search Results (1,258)

The voltage-gated proton channel (H_v1) selectively transports protons (H⁺) across biological membranes in response to membrane potential changes. H_v1 is assembled as a dimer, and unlike most voltage-gated ion channels, it lacks a traditional central pore domain; instead, the voltage-sensing domain (VSD) of each monomer facilitates proton conduction via a hydrogen-bond network. H_v1 is widely expressed in various human cell types (e.g., immune cells, sperm, etc.) including tumor cells. In tumor cells, the accumulation of acidic intermediates generated by glycolysis under hypoxic conditions or ROS production leads to significant cytosolic acidification. H_v1 can remove protons from the cytosol rapidly, contributing to the adaptation of the cells to the tumor microenvironment, which may have significant consequences in tumor cell survival, proliferation, and progression. Therefore, H_v1 may be very promising not only as a tumor marker but also as a potential therapeutic target in oncology. Molecules that modulate the proton flux through H_v1 can be divided into two broad groups: inhibitors and activators. H_v1 inhibitors can be simple ions, small molecules, lipids, and peptides. In contrast, fewer H_v1 activators are known, including albumin, NH29, quercetin, and arachidonic acid. The mechanism of action of some inhibitors is well described, but not all. H_v1 modulation has profound effects on cellular physiology, especially under stress or pathological conditions, like cancer and inflammation. The therapeutic application of selective H_v1 inhibitors or activators could be a very promising strategy in the treatment of several serious diseases. Full article

The control of crystal form in chiral active pharmaceutical ingredients (APIs) is a critical challenge in pharmaceutical development, as differences in solid-state structure can significantly influence physical properties and manufacturing performance. Troglitazone, a molecule with two chiral centers, exists as four stereoisomers (RR, SS, RS, SR) that crystallize as two enantiomeric pairs: RR/SS and RS/SR. This study aims to elucidate the relationship between solution-state molecular interactions and crystallization behavior of these diastereomeric pairs. Antisolvent crystallization experiments were conducted for both mixed solutions containing all four isomers and solutions of individual pairs. Crystallization kinetics were monitored by HPLC, and the resulting solids were characterized by PXRD, DSC, TG, and microscopic observation. Nucleation induction times were determined over a range of supersaturation levels. To probe intermolecular interactions in solution, NOESY and targeted NOE NMR experiments were performed, and the results were compared with crystallographic data. The RS/SR crystals(H-form) consistently exhibited shorter induction times and faster crystallization rates than the RR/SS crystals (L-form), even under conditions where RR/SS solutions were more supersaturated. In mixed solutions, H-form crystallized preferentially, with L-form either remaining in solution or being incorporated into H-form crystals as a solid solution. NOESY and NOE analyses revealed intermolecular proximities between protons that are distant in the molecular structure, indicating the presence of ordered aggregates in solution. These aggregates were more structurally compatible with the H-form than with the L-form crystal lattice, as supported by crystallographic distance analysis. The results demonstrate that differences in nucleation kinetics between troglitazone diastereomers are closely linked to solution-state molecular arrangements. Understanding these relationships provides a molecular-level basis for the rational design of selective crystallization processes for chiral APIs. Full article

In this article, the mechanism of relaxation polarization currents occurring at a constant temperature (isothermal process) in crystals with ionic-molecular chemical bonds (CIMBs) in an alternating electric field was investigated. Methods of the quasi-classical kinetic theory of dielectric relaxation, based on solutions of the nonlinear system of Fokker–Planck and Poisson equations (for the blocking electrode model) and perturbation theory (by expanding into an infinite series in powers of a dimensionless small parameter) were used. Generalized nonlinear mathematical expressions for calculating the complex amplitudes of relaxation modes of the volume-charge distribution of the main charge carriers (ions, protons, water molecules, etc.) were obtained. On this basis, formulas for the current density of relaxation polarization (for transient processes in a dielectric) in the k-th approximation of perturbation theory were constructed. The isothermal polarization currents are investigated in detail in the first four approximations (k = 1, 2, 3, 4) of perturbation theory. These expressions will be applied in the future to compare the results of theory and experiment, in analytical studies of the kinetics of isothermal ion-relaxation (in crystals with hydrogen bonds (HBC), proton-relaxation) polarization and in calculating the parameters of relaxers (molecular characteristics of charge carriers and crystal lattice parameters) in a wide range of field parameters (0.1–1000 MV/m) and temperatures (1–1550 K). Asymptotic (far from transient processes) recurrent formulas are constructed for complex amplitudes of relaxation modes and for the polarization current density in an arbitrary approximation k of perturbation theory with a multiplicity r by the polarizing field (a multiple of the fundamental frequency of the field). The high degree of reliability of the theoretical results obtained is justified by the complete agreement of the equations of the mathematical model for transient and stationary processes in the system with a harmonic external disturbance. This work is of a theoretical nature and is focused on the construction and analysis of nonlinear properties of a physical and mathematical model of isothermal ion-relaxation polarization in CIMB crystals under various parameters of electrical and temperature effects. The theoretical foundations for research (construction of equations and working formulas, algorithms, and computer programs for numerical calculations) of nonlinear kinetic phenomena during thermally stimulated relaxation polarization have been laid. This allows, with a higher degree of resolution of measuring instruments, to reveal the physical mechanisms of dielectric relaxation and conductivity and to calculate the parameters of a wide class of relaxators in dielectrics in a wide experimental temperature range (25–550 K). Full article

The applications of electromagnetic (EM) field treatment on water in agriculture have garnered increasing attention as a sustainable method to enhance plant growth, water-use efficiency, and metabolic performance. A growing body of evidence suggests that exposure to EM fields can affect water molecules, possibly by influencing hydrogen bonding dynamics, the structuring of water clusters, and electrokinetic properties of the water molecules. These alterations are thought to correlate with plant physiological performance. The methodology of the study was divided into two parts. The first part focused on the preparation of electromagnetically treated water. The second part involved applying this treated water to spinach plants. The present study investigates the physiological responses of Spinacia oleracea L. to irrigation with electromagnetically treated water (EMTW), focusing on elucidating the potential mechanisms that may underlie the observed effects. EMTW was generated using a solenoid-based system operating in dual-frequency ranges (100–1000 Hz and 10–100 kHz), which has been previously shown to influence both the microbiological and electrokinetic properties of aqueous systems. To evaluate the structural and functional implications of EMTW, a combined methodological approach was employed, integrating proton nuclear magnetic resonance (¹H-NMR) spectroscopy, density functional theory (DFT) modeling of water hydrogen bonds and clusters, and comprehensive plant physiological assessments. Plants were cultivated under both controlled and field conditions to assess consistency across environmental settings. Physiological measurements demonstrated that EMTW irrigation increased photosynthetic rate by ~80%, transpiration by 49–67%, stomatal conductance by 78–129%, intercellular CO₂ concentration by 42–80%, and chlorophyll content by 9.3–9.5% compared to control samples. Additionally, phenoloc and flavonoid contents were elevated by 7.4% and 7.6%, respectively, in field-grown plants. These enhancements were statistically significant (p < 0.001 or p < 0.01) under both laboratory and field conditions, confirming the robustness of the observed effects. Full article

Flow field design in proton exchange membrane fuel cells (PEMFCs) is a critical issue, as it plays an important role in governing reactant transport dynamics and cell performance. In this work, numerical studies of a single Tesla-valve flow field were conducted. The influence of loop radius, channel angle, and channel height on the performance of PEMFCs were fully explored. Then, aiming to maximize the output current density, this study optimized the Tesla-valve flow field configuration through a framework that integrates Gaussian process modeling with a Genetic Algorithm (GA). The approach efficiently identifies the optimal geometric parameters, highlighting effective synergy between the surrogate model and intelligent evolutionary optimization for enhanced performance. Simulation results show that the current density at 0.4 V and the highest power density have been improved by more than 10% compared to the baseline design for both forward and reverse flow. The optimized Tesla valve design has been compared with conventional parallel and serpentine flow fields of the same flow area. Results show that, despite the larger pressure drop for the single channel case—which is due to the insufficient length of the serpentine channel—the Tesla-valve flow field demonstrated superior performance in other metrics, including current and power density, under both flow directions. Full article

Bioelectrochemical systems (BESs) are technologies capable of converting chemical energy into electrical energy or producing value-added compounds. These systems typically employ Nafion membranes as proton exchange separators; however, Nafion is costly and prone to fouling. In this study, mixed-matrix membranes (MMMs) based on chitosan and its derivatives, incorporated with Er- and Al-doped ZnO nanoparticles, were synthesized and evaluated. Key properties assessed included antimicrobial activity, antifouling behavior, chemical stability, water retention, and proton conductivity. The results demonstrated that the chitosan-based membranes doped with Er/Al/ZnO outperformed Nafion in terms of antifouling properties, water retention, and a protective effect on the surface of the membrane against Escherichia coli and Staphylococcus aureus, while exhibiting comparable proton conductivity and chemical stability. Full article

Intermediate-temperature (IT) proton-exchange membranes (PEMs) play vital roles in hydrogen and direct liquid fuel cells, electrolyzers, and other electrochemical membrane reactors at elevated temperatures of higher than 150 °C. This article reports the fabrication and performance assessment of a type of new IT polymer–inorganic composite (PIC) PEMs that were made of cerium ultraphosphate (CeP₅O₁₄-CUP) as the durable solid-state proton conductor and undoped polybenzimidazole (PBI) as the high-temperature (HT) polymeric binder. The proton conductivity and electrochemical performance of the PIC PEMs were characterized at 200 °C with varying membrane thickness, processing parameters, and operating conditions using a single-stack hydrogen fuel cell connected to a fuel cell test station. Experimental results show that the PIC membranes (with CUP of 75 wt.%) carried high mechanical flexibility and strength as well as noticeably reduced water uptake of 4.4 wt.% compared to pristine PBI membranes of 14.0 wt.%. Single-stack hydrogen fuel cell tests at 200 °C in a humidified hydrogen and air environment showed that the proton conductivity of the PIC PEMs was measured up to 0.105 S/cm, and the electrochemical performance exhibited its dependence upon the membrane thickness with the power density of up to 191.7 mW/cm². Discussions are made to explore performance dependence and improvement strategies. The present study expects the promising future of the IT-PIC-PEMs for broad applications in high-efficiency electrochemical energy conversion and value-added chemical production at elevated temperatures of 200 °C or higher. Full article

The development of high-performance sensing materials is critical for advancing bioelectronics. Conductive hydrogels, with their unique flexibility, are promising candidates for biomedical sensors. However, traditional conductive hydrogels often suffer from excessive swelling and undesirable antibacterial activity, limiting their practical use. To overcome these challenges, anti-swelling, antibacterial, and ionically conductive hydrogels were built through free radical polymerization. The preparation was conducted using a monomer mixture comprising acrylic acid (AA), the antibacterial zwitterionic compound [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide (SBMA), and the hydrophobic monomer lauryl methacrylate (LMA). The protonation of SBMA by AA enables electrostatic repulsion, thereby imparting anti-swelling properties to the hydrogel. The introduction of hydrophobic LMA components further enhances the anti-swelling and mechanical performance of hydrogel. The resulting hydrogel exhibits excellent anti-swelling property with a swelling ratio of 59.36% after 120 h and good mechanical performance with a tensile strength of 158 kPa, an elongation at break of 176%, and a compressive strength of 0.37 MPa at 80% strain. In addition, hydrogels possess superior sensing performance for strain sensing with a gauge factor of 1.315 within 40–60% of strain, 330 ms of response time, and 177 ms of recovery time. Furthermore, the hydrogel is capable of monitoring human motion and physiological signals. These attributes make it highly suitable for wearable sensors and biomedical monitoring applications. Full article

High-temperature proton exchange membrane fuel cells (HT-PEMFCs) offer distinct advantages over their low-temperature counterparts. However, their commercial viability is significantly hampered by durability challenges stemming from electrocatalyst support degradation in the corrosive phosphoric acid environment. This review provides a comprehensive analysis of advanced strategies to overcome this critical durability issue. Two main research directions are explored. The first involves engineering more robust carbon-based materials, including graphitized carbons, carbon nanostructures (nanotubes and graphene), and heteroatom-doped carbons, which enhance stability by modifying the carbon’s intrinsic structure and surface chemistry. The second direction focuses on replacing carbon entirely with intrinsically stable non-carbonaceous materials. These include metal oxides (e.g., TiO₂, SnO₂), transition metal carbides (e.g., WC, TiC), and nitrides (e.g., Nb₄N₅). For these non-carbon materials, a key focus is on overcoming their typically low electronic conductivity through strategies such as doping and the formation of multi-component composites. The analysis benchmarks the performance and durability of these advanced supports, concluding that rationally designed composite materials, which combine the strengths of different material classes, represent the most promising path toward developing next-generation, long-lasting catalysts for HT-PEMFCs. Full article

Background: Pituicytomas are rare, low-grade gliomas arising from pituicytes in the posterior pituitary or infundibulum. Due to its rarity and nonspecific clinical and radiological characteristics, it is frequently misdiagnosed as pituitary adenomas or other sellar tumors. Aims: To present an overview of pituicytoma, including clinical presentation, radiological and histopathological characteristics, differential diagnosis and treatment strategies, illustrated by a case report. Methods: A literature review was conducted to contextualize our patient with a sellar tumor, and to highlight key diagnostic and therapeutic considerations. Results/Case report: A 12-year-old boy presented with visual disturbances. MRI revealed a well-defined contrast-enhancing sellar mass, and the patient underwent transsphenoidal surgery. The diagnosis was assumed to be a nonfunctioning pituitary adenoma (NFPA). Two years later a residual tumor was treated with proton irradiation. Six years after the radiotherapy, the patient had epistaxis. Imaging showed a tumor in the sphenoidale sinus, which was surgically resected. The tumor had histopathological features of pituicytoma and immunoreactivity for TTF-1 and S100. The tissue from the first operation was reviewed, showing more characteristics with pituicytoma than NFPA, leading to re-definition of the initial diagnosis. Follow-up has been without any signs of residual tumor. Conclusion: Our case and literature review emphasize the importance of considering pituicytoma in the differential diagnosis among sellar lesions. The diagnosis relies on a combination of preoperative imaging, intraoperative findings and histopathology. Pituitary surgery is the first-line treatment, and the outcome is generally good. Increased awareness of pituicytomas is necessary to improve preoperative diagnostic accuracy and guide appropriate management. Full article

Heme enzymes that bind and reduce O₂ are susceptible to poisoning by NO. The high reactivity and affinity of NO for ferrous heme produces stable ferrous-NO complexes, which in theory should preclude O₂ binding and turnover. However, NO inhibition is often competitive with respect to O₂ and rapidly reversible, thus providing cellular and organismal survival advantages. This kinetic paradox has prompted a search for mechanisms for reversal and hence resistance. Here, I critically review proposed resistance mechanisms for NO dioxygenase (NOD) and cytochrome c oxidase (CcO), which substantiate reduction or oxidation of the tightly bound NO but nevertheless fail to provide kinetically viable solutions. A ferrous heme intermediate is clearly not available during rapid steady-state turnover. Reversible inhibition can be attributed to NO competing with O₂ in transient low-affinity interactions with either the ferric heme in NOD or the ferric heme-cupric center in CcO. Toward resolution, I review the underlying principles and evidence for kinetic control of ferric heme reduction via an O₂-triggered ferric heme spin crossover and an electronically-forced motion of the heme and structurally-linked protein side chains that elicit electron transfer and activate O₂ in the flavohemoglobin-type NOD. For CcO, kinetics, structures, and density functional theory point to the existence of an analogous O₂ and reduced oxygen intermediate-controlled electron-transfer gate with a linked proton pump function. A catalytic cycle and mechanism for CcO is finally at hand that links each of the four O₂-reducing electrons to each of the four pumped protons in time and space. A novel proton-conducting tunnel and channel, electron path, and pump mechanism, most notably first hypothesized by Mårten Wikström in 1977 and pursued since, are laid out for further scrutiny. In both models, low-energy spin-orbit couplings or ‘spintronic’ interactions with O₂ and NO or copper trigger the electronic motions within heme that activate electron transfer to O₂, and the exergonic reactions of transient reactive oxygen intermediates ultimately drive all enzyme, electron, and proton motions. Full article

NiTi alloy has emerged as a promising bipolar plate (BP) material for proton exchange membrane fuel cells (PEMFCs), combining Ti-like corrosion resistance with Ni-like electrical conductivity through its intermetallic characteristics. However, its performance faces greater challenges under aggressive operating conditions (70 °C, F⁻-containing acidic solution with air bubbling). This study demonstrates that Nb alloying effectively enhances NiTi while preserving its balanced properties. The developed NiTiNb alloy exhibits improved performance with 26% lower corrosion current density (i_c) and 29% reduced interfacial contact resistance (ICR) compared to conventional NiTi, effectively overcoming the conventional corrosion–conductivity trade-off in metallic BPs. The alloy also shows superior electrochemical stability and microhardness relative to pure Ti and Ni. These enhancements stem from a unique dual-phase microstructure comprising a NiTi (B2) matrix with continuous β-Nb grain boundary networks. During operation, this structure enables in situ formation of protective TiO₂-Nb₂O₅ films while maintaining conductive Nb/Nb₂O₅ pathways and metallic Ni domains. The findings establish Nb alloying as a viable optimization strategy for NiTi-based BP substrate in demanding PEMFC applications. Full article

In this study, MnO₂-CNTs composite support was prepared by citric acid reduction method, and then, Pt nanoparticles were loaded on the surface by ethylene glycol reduction method to obtain a series of Pt/xMnO₂-CNTs catalysts. Structural characterization (TEM, XRD, HRTEM) showed that Pt nanoparticles were uniformly dispersed on the surface of the catalyst with an average particle size of 3.6 nm. Electrochemical tests show that when the content of MnO₂ is 20 wt.%, the Pt/_20wt.%MnO₂-CNTs catalyst has the best methanol oxidation performance, and its mass activity and long-term stability are 4.0 times and 5.41 times that of commercial Pt/C, respectively. The in situ FTIR results showed that MnO₂ promoted the dissociation of water through synergistic effect, generated abundant OH species, accelerated the oxidation of CO intermediates, and inhibited the poisoning of Pt sites. In this study, it is clear that the excellent performance of Pt/xMnO₂-CNTs is due to multiple synergistic effects. Modified carbon nanotubes facilitate proton conduction, Pt nanoparticles effectively activate methanol, and MnO₂ modulates reaction intermediates via its bifunctional mechanism. This comprehensive mechanism understanding provides a theoretical basis for the design of high-performance catalysts for direct methanol fuel cells. Full article

Phosphates pollution, primarily from agricultural runoff and wastewater discharge, is a major contributor to water eutrophication, adversely affecting aquatic ecosystems. This study reports the synthesis, characterization, and phosphates adsorption performance of a MgAlFe-layered double hydroxide (MgAlFe-LDH) with a 2:1:1 cationic ratio. The material was prepared via co-precipitation and characterized using digital microscopy, XRD, BET, XPS, and FTIR. Adsorption experiments were conducted at pH 3 and 9 to investigate equilibrium, kinetics, and reusability. The MgAlFe-LDH exhibited a high maximum adsorption capacity (q_max ≈ 215 mg/g) largely independent of pH, with adsorption well described by the Langmuir model. Kinetic studies revealed a pseudo-first-order mechanism, indicating that adsorption is dominated by surface diffusion and electrostatic interactions. Phosphate removal occurs through a dual mechanism involving rapid electrostatic attraction at protonated surface sites and slower ion exchange in the LDH interlayers. The material retained over 75% of its adsorption capacity after five consecutive adsorption–desorption cycles, highlighting its potential for sustainable phosphate recovery. Overall, the MgAlFe-LDH represents a promising, reusable adsorbent for phosphorus removal from wastewater, supporting circular economy strategies. Full article

A CO₂-responsive TMPDA–SDS–SiO₂ gel system was developed and evaluated through formulation optimization, structural characterization, rheological testing, and core flooding experiments. The optimal formulation was identified as 7.39 wt% SDS, 1.69 wt% TMPDA, and 0.1 wt% SiO₂, achieving post-CO₂ viscosities above 10³–10⁴ mPa·s. Spectroscopic and microscopic analyses confirmed that CO₂ protonates TMPDA amine groups to form carbamate/bicarbonate species, which drive the micellar transformation into a wormlike network, thereby enhancing gelation and viscosity. Rheological tests showed severe shear-thinning behavior, excellent shear recovery, and reversible viscosity changes under alternating CO₂/N₂ injection. The gel demonstrated rapid responsiveness, reaching stable viscosities within 8 min, and maintained good performance after 60 days of thermal aging at 90 °C and in high-salinity brines. Plugging tests in sand-packed tubes revealed that a permeability reduction of 98.9% could be achieved at 0.15 PV injection. In heterogeneous parallel core flooding experiments, the gel preferentially reduced high-permeability channel conductivity, improved sweep efficiency in low-permeability zones, and increased incremental oil recovery by 14.28–34.38% depending on the permeability contrast. These findings indicate that the CO₂-responsive TMPDA–SDS–SiO₂ gel system offers promising potential as a novel smart blocking gel system for improving the effectiveness of CO₂ flooding in heterogeneous reservoirs. Full article