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Many important chemical processes involve reactivity and dynamics in complex solutions. Gaining a fundamental understanding of these reaction mechanisms is a challenging goal that requires advanced computational and experimental approaches. However, important techniques such as molecular simulation have limitations in terms of scales of time, length, and system complexity. Furthermore, among the currently available solvation models, there are very few designed to describe the interaction between the molecular scale and the mesoscale. To help address this challenge, here, we establish a novel hybrid approach that couples first-principles plane-wave density functional theory with classical density functional theory (cDFT). In this approach, a region of interest described by ab initio molecular dynamics (AIMD) interacts with the surrounding medium described using cDFT to arrive at a self-consistent ground state. cDFT is a robust but efficient mesoscopic approach to accurate thermodynamics of bulk electrolyte solutions over a wide concentration range (up to 2M concentrations). Benchmarking against commonly used continuum models of solvation, such as SMD, as well as experiments, demonstrates that our hybrid AIMD–cDFT method is able to produce reasonable solvation energies for a variety of molecules and ions. With this model, we also examined the solvent effects on a prototype SN2 reaction of the nucleophilic attack of a chloride ion on methyl chloride in the solution. The resulting reaction pathway profile and the solution phase barrier agree well with experiment, showing that our AIMD/cDFT hybrid approach can provide insight into the specific role of the solvent on the reaction coordinate. [ABSTRACT FROM AUTHOR]

Chloride attack severely impacts the performance of reinforced concrete. The total and free chloride ion concentration (CIC) of self-compacting concrete (SCC) prepared with three supplementary cementitious materials (SCM) – fly ash (FA), blast furnace slag (BS) and silica fume (SF) – were measured by accelerated salt immersion tests. The apparent chloride diffusion coefficient (CDC) at any exposure time and erosion depth were calculated using the Boltzmann–Matano method. The influence of the type and content of SCM, the water–binder ratio (W/B) and the type of salt solution on CIC and CDC were investigated. Both the introduction of SCM and the reduction of W/B effectively reduced the CIC. The SCM that most effectively reduced CIC was SF, followed by BS and then FA. Free CIC was reduced to a greater degree than total CIC in FA and BS concrete, but the opposite was true for SF concrete. The presence of calcium chloride in salt solution increased total CIC while reducing free CIC. Apparent free CDC dropped over exposure time and initially increased with erosion depth but eventually stabilised. A model of apparent free CDC considering time–depth dependency was created, which shows that time reduction factors of CDC is greater in SCC containing SCM than in control SCC. [ABSTRACT FROM AUTHOR]

This article discusses a case of a 23-year-old woman who had metabolic alkalosis and hypokalemia. The common causes of metabolic alkalosis are vomiting and diuretic use, but the patient did not have a history of these factors. Further investigation revealed a genetic defect called Gitelman syndrome, which affects the reabsorption of sodium chloride in the kidney. The patient was prescribed potassium chloride and magnesium oxide to manage her electrolyte abnormalities. The article also provides an overview of metabolic alkalosis and its causes, as well as information on how to diagnose and treat the condition. [Extracted from the article]

Developing synthetic molecular devices for controlling ion transmembrane transport is a promising research field in supramolecular chemistry. These artificial ion channels provide models to study ion channel diseases and have huge potential for therapeutic applications. Compared with self‐assembled ion channels constructed by intermolecular weak interactions between smaller molecules or cyclic compounds, metallacage‐based ion channels have well‐defined structures and can exist as single components in the phospholipid bilayer. A naphthalene diimide‐based artificial chloride ion channel is constructed through efficient subcomponent self‐assembly and its selective ion transport activity in large unilamellar vesicles and the planar lipid bilayer membrane by fluorescence and ion‐current measurements is investigated. Molecular dynamics simulations and density functional theory calculations show that the metallacage spans the entire phospholipid bilayer as an unimolecular ion transport channel. This channel transports chloride ions across the cell membrane, which disturbs the ion balance of cancer cells and inhibits the growth of cancer cells at low concentrations. [ABSTRACT FROM AUTHOR]

With an increasingly profound understanding of battery materials, strategies designed for interface protection have become more sophisticated. However, it is inherent that different materials used in electrodes and electrolytes tend to react with each other. To address this issue, this study proposes an "Electrode‐Electrolyte‐In‐One" (EEIO) concept, where a single energy storage material can serve as both electrode and solid‐state electrolyte (SSE) during its different ion storage stages. The EEIO materials of chloride ion batteries and fluorine ion batteries are preliminarily studied, establishing reasonable screening procedures and predicting their operational mechanisms. The analysis of Cl− and F− affinity indicates that the EEIO system in the anion storage batteries comprises the anode and SSE. Through comprehensive evaluation of ion binding capacity, phase transformation mechanism, electrical conductivity, and ion diffusion kinetic properties, several potential EEIO materials are identified. In the EEIO system, the material interface and the conductive‐insulation interface are separated, which solves the material compatibility problem between the anode and SSE. Furthermore, the EEIO system has an inherent correlation between the anode electrochemical reaction and the SSE decomposition reaction, ensuring that the electrochemical voltage of EEIO batteries never exceeds the decomposition voltage of SSE. Therefore, SSE in the EEIO battery has absolute electrochemical stability. [ABSTRACT FROM AUTHOR]

The clinical translation of polysarcosine (pSar) as polyethylene glycol (PEG) replacement in the development of novel nanomedicines creates a broad demand of polymeric material in high‐quality making high‐purity sarcosine N‐carboxyanhydride (Sar‐NCA) as monomer for its production inevitable. Within this report, we present the use of triethyloxonium tetrafluoroborate in Sar‐NCA synthesis with focus on amino acid and chloride impurities to avoid the sublimation of Sar‐NCAs. With a view towards upscaling into kilogram or ton scale, a new methodology of monomer purification is introduced by utilizing the Meerwein's Salt triethyloxonium tetrafluoroborate to remove chloride impurities by covalent binding and converting chloride ions into volatile products within a single step. The novel straightforward technique enables access to monomers with significantly reduced chloride content (<100 ppm) compared to Sar‐NCA derived by synthesis or sublimation. The derived monomers enable the controlled‐living polymerization in DMF and provide access to pSar polymers with Poisson‐like molecular weight distribution within a high range of chain lengths (Xn 25–200). In conclusion, the reported method can be easily applied to Sar‐NCA synthesis or purification of commercially available pSar‐NCAs and eases access to well‐defined hetero‐telechelic pSar polymers. [ABSTRACT FROM AUTHOR]

Short peptide sequences consisting of two cysteine residues separated by three other amino acids display complete change from random coil to α‐helical secondary structure in response to addition of Ag+ ions. The folded CXXXC/Ag+ complex involves formation of multinuclear Ag+ species and is stable in a wide pH range from below 3 to above 8. The complex is stable through reversed‐phase HPLC separation as well as towards a physiological level of chloride ions, based on far‐UV circular dichroism spectroscopy. In electrospray MS under acidic conditions a peptide dimer with four Ag+ ions bound was observed, and modelling based on potentiometric experiments supported this to be the dominating complex at neutral pH together with a peptide dimer with 3 Ag+ and one proton at lower pH. The complex was demonstrated to work as a N‐terminal nucleation site for inducing α‐helicity into longer peptides. This type of silver‐mediated peptide assembly and folding may be of more general use for stabilizing not only peptide folding but also for controlling oligomerization even under acidic conditions. [ABSTRACT FROM AUTHOR]

[Display omitted] Na superionic conductor (NASICON)-structured Na 4 MnCr(PO 4) 3 (NMCP) possessing unique three-electron transfer process renders admirable energy density for sodium ion batteries (SIBs). However, the current issues like its sluggish Na+ diffusion kinetics, deficient intrinsic conductivity, and unsatisfactory structural stability, hinder its practical application. Herein, a selective replacement of O elements in PO 4 group by Cl anions in the NMCP system was developed to significantly enhance its electrochemical performance. The results affirm that the enhanced performance of Cl doped samples can be attributed to the enlargement of cell size, the creation of Na vacancies and the weakness of Na2 O bond after Cl doping. The as-prepared Na 3.85 □ 0.15 MnCr(PO 3.95 Cl 0.05) 3 /C (NMCPC − 15/C) cathode delivers a high capacity (128.0 mAh/g at 50 mA g−1) and excellent rate performance (73.0 mAh/g at 1000 mA g−1) in contrast to NMCP/C that merely provides 105.2 mAh/g at 50 mA g−1 and reduces to 47.4 mAh/g at 1000 mA g−1. Meanwhile, NMCPC − 15/C shows a capacity retention of 60.7 % at 1000 mA g−1 after 500 cycles, while only 37.1 % for NMCP/C in the same test conditions. Moreover, the satisfactory performance and energy density of NMCPC − 15/C||hard carbon (HC) full cell confirm the potential practicality of NMCPC − 15. Therefore, chloride ions doping into NMCP has practical application prospects in the preparation of high-performance cathode materials and our work also offers new inspiration to apply anion doping strategies in promoting the performance of the other NASICON-structured cathodes for SIBs. [ABSTRACT FROM AUTHOR]

Nanomaterials can improve the performance of cement-based materials. This article discusses the influence of graphene with different substitution rates on the performance of concrete. The addition of graphene will have an adverse effect on slump. The zeta-potential test shows that the addition of graphene leads to the adsorption of cations, which leads to the precipitation of particles. Therefore, the water absorption and cation of graphene are the main reasons for the decrease in fluidity. The strength of concrete increases first and then decreases with the increase of substitution rate, but the flexural strength increases all the time. The nanoindentation shows that graphene changes the properties of hydration products. The results of ultrasonic pulse velocity and mercury intrusion porosimetry show that the incorporation of graphene can improve the pore structure of cement-based materials. The chloride ion test shows that graphene can absorb chloride ions, and the addition of graphene can improve the performance of cement-based materials. [ABSTRACT FROM AUTHOR]

Chloride attack severely impacts the performance of reinforced concrete. The total and free chloride ion concentration (CIC) of self-compacting concrete (SCC) prepared with three supplementary cementitious materials (SCM) – fly ash (FA), blast furnace slag (BS) and silica fume (SF) – were measured by accelerated salt immersion tests. The apparent chloride diffusion coefficient (CDC) at any exposure time and erosion depth were calculated using the Boltzmann–Matano method. The influence of the type and content of SCM, the water–binder ratio (W/B) and the type of salt solution on CIC and CDC were investigated. Both the introduction of SCM and the reduction of W/B effectively reduced the CIC. The SCM that most effectively reduced CIC was SF, followed by BS and then FA. Free CIC was reduced to a greater degree than total CIC in FA and BS concrete, but the opposite was true for SF concrete. The presence of calcium chloride in salt solution increased total CIC while reducing free CIC. Apparent free CDC dropped over exposure time and initially increased with erosion depth but eventually stabilised. A model of apparent free CDC considering time–depth dependency was created, which shows that time reduction factors of CDC is greater in SCC containing SCM than in control SCC. [ABSTRACT FROM AUTHOR]

Under ultrasound irradiation in an ethanol solvent, a new coordination complex of Cu(II) was successfully synthesized within a 10-min timeframe through the treatment of an imidazole-based ligand (PDI) with a copper-containing salt. The formation of the complex was verified through elemental (CHN) analysis and FT-IR spectroscopy. Additionally, the supramolecular assembly and packing of atoms in the crystalline units of the copper complex were elucidated using single-crystal X-ray diffraction method. The synthesized compound exhibits an ionic nature, featuring a copper(II) cation inside the coordination sphere and a chloride anion outside of the coordination sphere. The coordination environment around the copper cation is achieved through the bonding of the N-atom of the non-protonated PDI ligands and a chloride ion. To maintain a neutral charge, a second chloride ion serves as a counterion. The bond angles surrounding the Cu(II) ion showed a somewhat deformed square planar geometry of the complex. The non-covalent intermolecular interactions were executed by Hirshfeld surface analysis (HSA), while the theoretical studies were conducted using DFT employing the B3LYP/Def2-TZVP level of theory. The consistency between the theoretical findings and experimental data attested to the reliability of the theoretical conclusions. [ABSTRACT FROM AUTHOR]

Physiological and morphological acclimation capacities of black‐chinned tilapia, Sarotherodon melanotheron were studied from fish to gill cell level when fish are maintained in freshwater, seawater, and hypersaline conditions. Fish osmoregulatory capacity, gill ionocyte morphology, osmo‐respiratory compromise, O2 consumption rate, branchial antioxidative defense, and cell apoptosis were considered. Captive juvenile tilapias were maintained in controlled freshwater conditions (FW: 0.4 ppt; 12 mOsm kg−1) or gradually transferred to seawater (SW: 32 ppt; 958 mOsm kg−1) and concentrated SW (cSW: 65 ppt; 1920 mOsm kg−1). After 15 days in these conditions, blood osmolality and chloride ion concentration were determined. Gill ionocyte density and morphology were measured using immunolabelled histological sections to specifically detect the sodium pump (NKA). Gill osmo‐respiratory compromise was also calculated along with oxygen consumption rates from normoxic to hypoxic conditions from excised gills (indirect respirometry). Finally, catalase and caspase 3/7activities were recorded from gill extracts. Results indicate that elevated salinity induces an osmotic imbalance and a profound morphological change with proliferating and hypertrophied ionocytes. This thickening of the gill interlamellar cell mass and the shortening of the lamellae induce a reduced osmo‐respiratory ratio and reduced respiratory capacity under both normoxic and hypoxic conditions. Although salinity changes do not affect one of the major antioxidative defense mechanism, it strongly affects apoptosis that appears the most elevated in SW. However, in freshwater condition, fish can maintain their osmotic balance with a low ionocyte density, a low apoptotic level and a drastically reduced O2 consumption in normoxic condition that is maintained in hypoxia. Therefore, S. melanotheron presents the typical functional remodeling due to environmental salinity changes ranging from FW to SW. However, elevated seawater induces major cellular stress inducing a profound gill morphofunctional dysfunctioning. While cell apoptosis is reduced, ionocyte proliferation is massively increased with impaired osmotic regulation and reduced O2 consumption both in normoxic and hypoxic conditions. [ABSTRACT FROM AUTHOR]

The first example of a [2]rotaxane shuttle capable of selective optical sensing of chloride anions over other halides is reported. The rotaxane was synthesised via a chloride ion template‐directed cyclisation of an isophthalamide macrocycle around a multi‐station axle containing peripheral naphthalene diimide (NDI) stations and a halogen bonding (XB) bis(iodotriazole) based station. Proton NMR studies indicate the macrocycle resides preferentially at the NDI stations in the free rotaxane, where it is stabilised by aromatic donor‐acceptor charge transfer interactions between the axle NDI and macrocycle hydroquinone moieties. Addition of chloride ions in an aqueous‐acetone solvent mixture induces macrocycle translocation to the XB anion binding station to facilitate the formation of convergent XB⋅⋅⋅Cl− and hydrogen bonding HB⋅⋅⋅Cl− interactions, which is accompanied by a reduction of the charge‐transfer absorption band. Importantly, little to no optical response was induced by addition of bromide or iodide to the rotaxane, indicative of the size discriminative steric inaccessibility of the interlocked cavity to the larger halides, demonstrating the potential of using the mechanical bond effect as a potent strategy and tool in chloride‐selective chemo‐sensing applications in aqueous containing solvent environments. [ABSTRACT FROM AUTHOR]

Growing crops on marginal and salt-affected soils with saline water will be more important for agricultural production in the future. The most prevalent anions in saline soils, chloride (Cl-) and sulfate (SO42-) have distinct effects on plant growth, metabolism, nutrient composition, productivity, and nutrient requirements. In order to ascertain the role of phosphorus in mitigating salinity stress in tomato plants, a pot experiment was conducted in a screen house under two types of saline environments chloride-dominated (Cl-: SO42- = 7:3) and sulfate-dominated (Cl-: SO42- = 3:7), with two comparable ECe levels (non-saline and 6 dS m−1) and four graded phosphorus levels (0, 12.5, 25, 50 mg kg−1soil). The significant increase in yield up to 50 ppm added P indicated that plants require more P under chloride salinity than sulfate salinity. In non-saline, chloride, and sulfate-dominated conditions, increased P from 0 to 50 ppm increased chlorophyll 'a' and 'b' values by 21.4, 19.8 and 23.8% and 10, 20 and 14%, respectively. The reduced photochemical efficiency due to salinity, was increased 32%, 30% and 13% as P level increased from 0 to 50 ppm in non-saline, Cl--6 and SO42—6 conditions, respectively. The TSS, ascorbic acid content and titrable acidity of tomato fruits was improved with mild salinity stress but reduced with added P. The plant N, P and K content increased significantly with each added P level irrespective of types of salinity. The plant composition indicated an antagonism between phosphorus and chloride ions and synergism between phosphorus and sulfate ions. [ABSTRACT FROM AUTHOR]

Oxalate anions (C 2 O 4 2–) intercalation in NiFe layered double hydroxide on nickel foam (NiFe-C 2 O 4 2– LDH/NF) serves as a highly efficient electrocatalyst for oxygen evolution reaction, capable of achieving a large current density of 1000 mA cm−2 with an overpotential of 337 mV and maintaining 500-h electrolytic tolerance in alkaline seawater. [Display omitted] • An anti-corrosion strategy of oxalate anions (C 2 O 4 2–) intercalation in NiFe layered double hydroxide (NiFe LDH) is proposed, where the presence of highly negatively charged C 2 O 4 2– within the interlayers impedes the proximity of Cl– through electrostatic repulsion. • NiFe-C 2 O 4 2– LDH/NF presents excellent oxygen evolution reaction performance, achieving the current density of 1000 mA cm−2 at overpotential of 337 mV in 1 M KOH + seawater. • Long-term stable seawater oxidation for NiFe-C 2 O 4 2– LDH/NF at an industrial-grade current density of 1000 mA cm−2 can be maintained for 500 h. Seawater electrolysis is gaining recognition as a promising method for hydrogen production. However, severe anode corrosion caused by the high concentration of chloride ions (Cl–) poses a challenge for the long-term oxygen evolution reaction. Herein, an anti-corrosion strategy of oxalate anions intercalation in NiFe layered double hydroxide on nickel foam (NiFe-C 2 O 4 2– LDH/NF) is proposed. The intercalation of these highly negatively charged C 2 O 4 2– serves to establish electrostatic repulsion and impede Cl– adsorption. In alkaline seawater, NiFe-C 2 O 4 2– LDH/NF requires an overpotential of 337 mV to gain the large current density of 1000 mA cm−2 and operates continuously for 500 h. The intercalation of C 2 O 4 2– is demonstrated to significantly boost the activity and stability of NiFe LDH-based materials during alkaline seawater oxidation. [ABSTRACT FROM AUTHOR]

In this paper, four water–binder ratios (w/b) of 0.29, 0.33, 0.39, and 0.46 were designed. A variable test temperature was implemented in the drying–wetting cycle test according to the temperature fluctuations in the actual service environment, and the constant temperature test was established as the control group. The mechanical properties and chloride corrosion resistance of concrete with different w/b ratios under variable temperature drying–wetting cycles, as well as the microstructure changes, phase composition, and damage mechanism inside the concrete, were investigated. The results showed that the mechanical properties of concrete increased first and then decreased with drying–wetting cycles increasing, whereas the chloride corrosion resistance continued to decline. A higher w/b exacerbated the deterioration of the concrete performance. A higher w/b increased the porosity, chloride diffusion depth, and chloride content, thus reducing the resistance of chloride corrosion. Compared with w/b = 0.29, the compressive strength, splitting tensile strength, mass, and relative dynamic elasticity modulus of w/b = 0.46 exposed to 60 drying–wetting cycles decreased by 54.50%, 52.44%, 0.96%, and 6.50%, respectively, while the porosity, peak chloride content, and erosion depth increased by 45.12%, 70.45%, and 45.00%. Compared with the drying–wetting cycle with a constant temperature, the cumulative damage caused by the drying–wetting cycle with a variable temperature was greater, resulting in more severe deterioration of concrete performance. The increase in the test temperature significantly accelerated the diffusion rate, penetration depth, and chemical binding capacity of chloride ions. After 60 drying–wetting cycles, the peak chlorine content and erosion depth of w/b = 0.46 under variable temperature cycles were 15.38% and 10.32% higher than those under a constant temperature, while the compressive strength, splitting tensile strength, mass, and relative dynamic elastic modulus were reduced by 7.76%, 14.81%, 0.33%, and 2.40%, respectively. Microscopic analysis confirmed that higher w/b and variable temperature cycles accelerated the decay of mechanical properties and the decline of chloride corrosion resistance. According to the numerical fitting analysis, the w/b should be 0.29~0.39 under the condition that the mechanical properties and chloride corrosion resistance of concrete are met. [ABSTRACT FROM AUTHOR]

The current investigation describes the synthesis of four novel methylene blue (MB) salts of benzene sulfonate derivatives, featuring bulky anionic groups. The process involves treating chloride salt of MB with sodium salts of 4‐aminobenzene sulfonate, 4‐styrenebenzene sulfonate, 3,7‐naphthalene disulfonate, and anthraquinone‐1,5‐naphthalene disulfonate to substitute the chloride ion with benzoate sulfonate anion in MB‐chloride. The synthesis includes quaternizing MB‐chloride with the corresponding benzene sulfonate in minimal aqueous solvent to promote precipitation. The resultant precipitates were subsequently dissolved in an appropriate solvent to enable the crystallization of the ultimate product. The dissolution occurs either at ambient temperature or with heat. The crystals of the resultant salts were characterized using various analytical techniques like UV‐visible, and FT‐IR spectroscopy, TGA, single crystal X‐ray diffraction and powder X‐ray diffraction analysis. The UV‐visible spectroscopic results, frontier molecular orbital, density of states, molecular electrostatic potentials, and HOMO‐LUMO energy gaps were estimated by DFT. Structural analysis revealed that supramolecular structure of compounds achieved stabilization through electrostatic interactions, a diverse range of both conventional and non‐conventional hydrogen bonds, π–π stacking interactions, and other short‐range interactions. The investigation delves into intricate details and offers a thorough discussion of the fundamental principles that contribute to the formation and stabilization of supramolecular structures. [ABSTRACT FROM AUTHOR]

Chloride is a key anion involved in cellular physiology by regulating its homeostasis and rheostatic processes. Changes in cellular Cl- concentration result in differential regulation of cellular functions such as transcription and translation, post-translation modifications, cell cycle and proliferation, cell volume, and pH levels. In intracellular compartments, Cl- modulates the function of lysosomes, mitochondria, endosomes, phagosomes, the nucleus, and the endoplasmic reticulum. In extracellular fluid (ECF), Cl- is present in blood/plasma and interstitial fluid compartments. A reduction in Cl- levels in ECF can result in cell volume contraction. Cl- is the key physiological anion and is a principal compensatory ion for the movement of the major cations such as Na+, K+, and Ca2+. Over the past 25 years, we have increased our understanding of cellular signaling mediated by Cl-, which has helped in understanding the molecular and metabolic changes observed in pathologies with altered Cl- levels. Here, we review the concentration of Cl- in various organs and cellular compartments, ion channels responsible for its transportation, and recent information on its physiological roles. [ABSTRACT FROM AUTHOR]

A new, sustainable polypropylene terephthalate (PPT) coating was synthesized from recycled polyethylene terephthalate (PET) and applied onto a hydraulic concrete substrate to improve its durability. For the first step, PET bottle wastes were ground and depolymerized by glycolysis using propylene glycol (PG) in a vessel-type reactor (20–180 °C) to synthesize bis(2-hydroxypropyl)-terephthalate (BHPT), which was applied as a coating to one to three layers of hydraulic concrete substrate using the brushing technique and polymerized (150 °C for 15 h) to obtain PPT. PET, BHPT, and PPT were characterized by FT-IR, PET, and PPT using TGA, and the PPT coatings by SEM (thickness), ASTM-D3359-17 (adhesion), and water contact angle (wettability). The durability of hydraulic concrete coated with PPT was studied using resist chloride ion penetration (ASTM-C1202-17), carbonation depth at 28 days (RILEM-CPC-18), and the absorption water ratio (ASTM-C1585-20). The results demonstrated that the BHPT and PPT were synthetized (FT-IR), and PPT had a similar thermal behavior to PET (TGA); the PPT coatings had good adhesion to the substrate, with thicknesses of micrometric units. PPT coatings presented hydrophilic hydrophilic behavior like PET coatings, and the durability of hydraulic concrete coated with PPT (2–3 layers) improved (migration of chloride ions decreased, carbonation depth was negligible, and the absorption water ratio decreased). [ABSTRACT FROM AUTHOR]

In order to address the issues of energy depletion, more resources are being searched for in the deep sea. Therefore, research into how the deep-sea environment affects cement-based materials for underwater infrastructure is required. This paper examines the impact of ocean depth (0, 500, 1000, and 1500 m) on the ion interaction processes in concrete nanopores using molecular dynamics simulations. At the portlandite interface, the local structural and kinetic characteristics of ions and water molecules are examined. The findings show that the portlandite surface hydrophilicity is unaffected by increasing depth. The density profile and coordination number of ions alter as depth increases, and the diffusion speed noticeably decreases. The main cause of the ions' reduced diffusion velocity is expected to be the low temperature. This work offers a thorough understanding of the cement hydration products' microstructure in deep sea, which may help explain why cement-based underwater infrastructure deteriorates over time. [ABSTRACT FROM AUTHOR]

As an environmentally friendly natural polymer, citric acid-modified chitosan (CAMC) can effectively regulate the hydration and exothermic processes of cement-based materials. However, the influence of CAMC on the macroscopic properties of concrete and the optimal dosage are still unclear. This work systematically investigates the effects of CAMC on the mixing performance, mechanical properties, shrinkage performance, and durability of concrete. The results indicated that CAMC has a thickening effect and prolongs the setting time of concrete. CAMC has a negative impact on the early strength of concrete, but it is beneficial for the development of the subsequent strength of concrete. With the increase in CAMC content, the self-shrinkage rate of concrete samples decreased from 86.82 to 14.52 με. However, the CAMC-0.6% sample eventually expanded, with an expansion value of 78.49 με. Moreover, the long-term drying shrinkage rate was decreased from 551.46 to 401.94 με. Furthermore, low-dose CAMC can significantly reduce the diffusion coefficient of chloride ions, improve the impermeability and density of concrete, and thereby enhance the freeze–thaw cycle resistance of concrete. [ABSTRACT FROM AUTHOR]

For solid waste-based cementitious materials, most scholars focus their research on the hydration reaction of cementitious materials, but there is still a lack of solid waste design that comprehensively considers mechanical properties and durability. Therefore, this article focuses on exploring the mix of design and the microscopic and macroscopic properties of multi solid waste cementitious materials (MSWCMs), namely steel slag (SS), slag powder (SP), desulfurization gypsum (DG), fly ash (FA), and ordinary Portland cement (OPC). According to the orthogonal experimental results, the compressive strength of MSWCMs is optimal when the OPC content is 50% and the SS, SP, DG, and FA contents are 10%, 20%, 5%, and 15%, respectively. The MSWCMs group with an OPC content of 50% and SS, SP, DG, and FA contents of 5%, 15%, 5%, and 25% was selected as the control group. The pure OPC group was used as the blank group, and the optimal MSWCMs ratio group had a 28-day compressive strength of 50.7 megapascals, which was 14% and 7.6% higher than the control group and blank group, respectively. The drying shrinkage rate and resistance to chloride ions were also significantly improved, with maximum increases of 22.9%, 22.6%, and 8.9%, 9.8%, respectively. According to XRD, TG-DTG, and NMR testing, the improvement in macroscopic performance can be attributed to the synergistic effect between various solid wastes. This synergistic effect produces more ettringite (AFt) and C-(A)-S-H gel. This study provides a good theoretical basis for improving the comprehensive performance of MSWCMs and is conducive to reducing the use of cement, with significant economic and environmental benefits. [ABSTRACT FROM AUTHOR]

In the present work, the influence of a corrosive environment and temperature on the corrosion resistance properties of duplex stainless steel S31803 was evaluated. The corrosive process was carried out using solutions of 1.5% HCl (m/m) and 6% FeCl3 (m/m), at temperatures of 25 and 50 °C. The microstructure of UNS S31803 duplex stainless steel is composed of two phases, ferrite and austenite, oriented in the rolling direction, containing a ferrite percentage of 46.2% in the rolling direction and 56.1% in the normal direction. Samples, when subjected to corrosive media and temperature, tend to decrease their mechanical property values. It was observed, in both corrosive media, that with increasing test temperature, there is an increase in the corrosion rate, both uniform and pitting. The sample in HCl solution obtained a uniform corrosion rate of 0.85% at 25 °C and 0.92% at 50 °C and pitting rates of 0.77% and 1.47% at the same temperatures, respectively. When tested in FeCl3 solution, it obtained uniform corrosion of 0.0006% and 0.93% and pitting of 0.53% and 18.5%, at the same temperatures. A reduction in dissolution potentials is also noted, thus characterizing greater corrosion in the samples with increasing temperature. [ABSTRACT FROM AUTHOR]

Background: The difference between serum sodium and chloride ion concentrations (SCD) may be considered as a surrogate of a strong ion difference and may help to identify patients with a worse prognosis. We aimed to assess SCD as an early prognostic marker among patients with myocardial infarction. Methods: Data of 594 consecutive patients with acute myocardial infarction treated with PCI (44.9% STEMI patients; 70.7% males) was analysed for SCD in relation to their 30‐day mortality. A restricted cubic spline regression model was used to study the relationship between mortality and SCD. Cox regression models were used to assess the association between SCD and the mortality risk. Results: Patients with Killip class ≥3 had lower SCD values in comparison to patients with Killip class ≤2: (32.0 [30.0–34.0] vs. 33.0 [31.0–36.0], p =.006). The overall 30‐day mortality was 7.7% (n = 46). There was a significant difference in SCD values between survivors and non‐survivors groups of patients (median (IQR): (33.0 [31.0–36.0] vs. 31.5 [28.0–34.0] (mmol/L), p =.002). The restricted cubic splines model confirmed a non‐linear association between SCD and mortality. Patients with SCD <30 mmol/L (in comparison to SCD ≥30 mmol/L) had an increased mortality risk (unadjusted HR 2.92, 95% CI 1.59–5.36, p =.001; and an adjusted HR 2.30, 95% CI 1.02–5.19, p =.04). Conclusions: Low SCD on admission is associated with an increased risk of 30‐day mortality in patients with acute myocardial infarction treated with PCI and may serve as a useful prognostic marker for these patients. [ABSTRACT FROM AUTHOR]

[Display omitted] Theoretical assessment of Cl-excessive, mixed-halide grain boundaries in hybrid perovskite thin films demonstrates that ordered 3D/2D interfaces along perovskite (100) crystallographic planes are the most energetically favored among other possible cases. [ABSTRACT FROM AUTHOR]

Due to the limited interface contact and weak interfacial interaction, planar heterojunction perovskite solar cells (PSCs) have space for further improvement. Herein, a structural and chemical crosslinking interface is proposed and constructed by introducing an extra layer, which blends tin dioxide (SnO2) nanoparticles with chloride salts. Since the incorporated materials can be dissolved during the fabrication of perovskite, the quality of perovskite films is improved, leading to larger grain size and reduced trap‐state density. Also, more chloride ions at the SnO2/perovskite interface are observed and the interaction between Cl− and Sn4+ is confirmed. It results in more pronounced n‐type SnO2 with better conductivity and deeper conduction bands, leading to preferable energy level alignment between SnO2 and perovskite. Consequently, the open‐circuit voltage and fill factor of the devices increase, and target cells present better stability, retaining 98% of initial efficiencies after >10 000 h storage in dry air (≈5% relative humidity) and maintaining 85.50% of the initial efficiency after 1000 h of operation under light. This strategy enables the achievement of 25.28% efficiency with a low bandgap (1.53 eV) perovskite composition, and it is confirmed to be universal when other related materials are utilized. [ABSTRACT FROM AUTHOR]

The ionic toxicity induced by salinization has adverse effects on the growth and development of crops. However, researches on ionic toxicity and salt tolerance in plants have focused primarily on cations such as sodium ions (Na+), with very limited studies on chloride ions (Cl−). Here, we cloned the homologous genes of Arabidopsis thaliana AtCLCc, GhCLCc-1A/D, from upland cotton (Gossypium hirsutum), which were significantly induced by NaCl or KCl treatments. Subcellular localization showed that GhCLCc-1A/D were both localized to the tonoplast. Complementation of Arabidopsis atclcc mutant with GhCLCc-1 rescued its salt-sensitive phenotype. In addition, the silencing of the GhCLCc-1 gene led to an increased accumulation of Cl− in the roots, stems, and leaves of cotton seedlings under salt treatments, resulting in compromised salt tolerance. And ectopic expression of the GhCLCc-1 gene in Arabidopsis reduced the accumulation of Cl− in transgenic lines under salt treatments, thereby enhancing salt tolerance. These findings elucidate that GhCLCc-1 positively regulates salt tolerance by modulating Cl− accumulation and could be a potential target gene for improving salt tolerance in plants. [ABSTRACT FROM AUTHOR]

Bismuth halide perovskites have emerged as promising alternatives for sustainable and efficient photocatalysts for light‐induced organic transformations. Caesium bismuth halide perovskites (Cs3Bi2(ClxBr1‐x)9) with different ratios of chloride and bromide were synthesised using a one‐step solution process. These perovskites were then employed as photocatalysts for the photocatalytic oxidative coupling of benzylamine (BZA) to produce N‐benzylidenebenzylamine (BZI) under ultraviolet‐visible light radiation at ambient conditions. The incorporation of bromide ions into the chloride‐based perovskite resulted in a noticeable reduction in the bandgap, leading to an enhancement in the photocatalytic activity. Conversely, the addition of chloride ions within the bromide‐based perovskite was found to be beneficial for the material's photostability while simultaneously maintaining its high photocatalytic activity. The optimal compromise between the stability and photocatalytic activity for the BZI production was achieved using Cs3Bi2(Cl0.8Br0.2)9, being attained a total BZA conversion and the maximum BZI production with 100 % of selectivity after 6 hours of irradiation. The efficiency of this photocatalyst was ascribed to the highest current density observed during the photocurrent experiments, which improves the charge carrier mobility of the resulting material. [ABSTRACT FROM AUTHOR]

In nature, ceramides are a class of sphingolipids possessing a unique ability to self‐assemble into protein‐permeable channels with intriguing concentration‐dependent adaptive channel cavities. However, within the realm of artificial ion channels, this interesting phenomenon is scarcely represented. Herein, we report on a novel class of adaptive artificial channels, Pn‐TPPs, based on PEGylated cholic acids bearing triphenylphosphonium (TPP) groups as anion binding motifs. Interestingly, the molecules self‐assemble into chloride ion channels at low concentrations while transforming into small molecule‐permeable nanopores at high concentrations. Moreover, the TPP groups endow the molecules with mitochondria‐targeting properties, enabling them to selectively drill holes on the mitochondrial membrane of cancer cells and subsequently trigger the caspase 9 apoptotic pathway. The anticancer efficacies of Pn‐TPPs correlate with their abilities to form nanopores. Significantly, the most active ensembles formed by P5‐TPP exhibits impressive anticancer activity against human liver cancer cells, with an IC50 value of 3.8 μM. While demonstrating similar anticancer performance to doxorubicin, P5‐TPP exhibits a selectivity index surpassing that of doxorubicin by a factor of 16.8. [ABSTRACT FROM AUTHOR]

Chlorine ions play an important role in the corrosion of bronzeware. This study employs techniques such as XRD, OM, SEM, EBSD, and electrochemical testing to analyze the microstructure, crystal structure, chemical composition, and corrosion performance of bronze earrings unearthed at the Xindianzi site in Inner Mongolia. The results indicate the presence of work-hardened structures, including twinning and equiaxed crystals, on the earrings' surface. With an increase in chloride ion concentration in NaCl solutions from 10−3 mol/L to 1 mol/L, the corrosion current density of the bronze earrings increased from 2.372 × 10−7 A/cm2 to 9.051 × 10−7 A/cm2, demonstrating that the alloy's corrosion rate escalates with chloride ion concentration. A 3-day immersion test in 0.5% NaCl solution showed the formation of a passivation layer of metal oxides on the earrings' surface. These findings underscore the significance of the impact chloride ions have on the corrosion of copper alloys, suggesting that activating the alloy's reactive responses can accelerate the corrosion process and provide essential insights into the corrosion mechanisms of bronze artifacts in chloride-containing environments. [ABSTRACT FROM AUTHOR]

Herein, we present a photoinduced deconstructive alkoxyamination of alkyl alcohols catalyzed by iron salts. This transformation involves the initiation of alkoxy radicals through chlorine radical‐induced alkoxy radical formation, followed by β‐scission and trapping of the resulting carbon radicals with 2,2,6,6‐tetramethylpiperidin‐1‐yl (TEMPO). This reaction exhibits a broad substrate scope (40 examples), including primary and secondary alcohols that are prone to oxidation by the combination of TEMPO and iron. Mechanistic investigations have revealed that enhanced coordination of the chloride ion with the iron center inhibits the OH oxidation process, thereby enabling the tolerance of primary and secondary alcohols. [ABSTRACT FROM AUTHOR]

The proton conduction behaviour of novel oxalate-based compounds of iron(III) of different nuclearity with various ammonium components, (NH4)2[Fe(H2O)Cl3(C2O4)]·H2O (1), {[NH(CH3)2(C2H5)][FeCl2(C2O4)]·H2O}n (2) and {[N(CH3)(C2H5)3][FeCl2(C2O4)]}n (3), was investigated by impedance spectroscopy in addition to characterization by single-crystal and powder X-ray diffraction and infrared spectroscopy. The discrete mononuclear compound 1 exhibits a very high proton conductivity of 2.17 × 10−3 (Ω cm)−1 at 25 °C and 74% relative humidity (RH), with σDC increased by nearly seven orders of magnitude. The three-dimensional (3D) hydrogen-bonding network of NH4+ cations and water molecules (crystal and coordinated) as hydrogen-bond donors and the bidentate oxalate ligand and chloride ions of the anionic moiety [Fe(H2O)Cl3(C2O4)]2− as hydrogen-bond acceptors plays a crucial role in proton transport; the density of the formed hydrogen-bonds positively impacts the mobility of protons in the nonporous structure of 1. The one-dimensional (1D) compounds 2 and 3, both containing infinite anionic zig-zag chains [FeCl2(C2O4)]nn− and cations (CH3)2(C2H5)NH+ (2) or (CH3)(C2H5)3N+ (3), showed an increase in conductivity of six and five orders of magnitude, reaching values of 2.00 × 10−4 (Ω cm)−1 and 9.17 × 10−6 (Ω cm)−1, respectively, at 25 °C and 93% RH. Compared to compound 3, compound 2 has hydrogen-bonded protonated (CH3)2(C2H5)NH+ cations that exhibit greater hydrophilicity, which is closely related to the affinity for water molecules that significantly affect proton transport and conductivity. [ABSTRACT FROM AUTHOR]

The interaction of dibutyltin(IV) dichloride (DBT) with 1,4-diazacycloheptane (homopiperazine, HP) was investigated. In solutions, the complexes formed a 1:1 complex, its protonated and hydrolyzed forms. The formation constants of the complexes and thermodynamic parameters as ΔH° and ΔS° were estimated. The optimization of the structure of the (Bu)2Sn(HP)Cl2 complex reveals that the tin is six-coordinate in a distorted octahedral geometry, where the two nitrogen atoms of homopiperazine and the two chloride ions are in one plane. The solid (Bu)2Sn(HP)Cl2 complex with homopiperazine was synthesized, and the composition was assigned by elemental micro-analysis and mass spectrum. The complex was investigated by infrared, mass spectra, and thermal measurements. The ligand and its complex were tested against antimicrobial Staphylococcus aureus (+ve), Escherichia coli (−ve), and antifungal Candida albicans and Aspergillus flavus. Anticancer activities of homopiperazine and its dibutyltin(IV) complex were tested against breast cancer cell lines. The molecular docking investigations were performed to know the possible modes of binding to the most active sites of the breast cancer oxidoreductase receptor and those of Escherichia coli. [ABSTRACT FROM AUTHOR]

The purpose of the experiment was to analyze and compare three methods (methyl violet method, molar method, and chloride ion selective electrode method) of measuring feed mixing uniformity, so as to provide a reference for feed enterprises to choose determination methods. Six kinds of feed were selected in the experiment, including piglet early-stage compound feed, suckling pig concentrated feed, medium pig compound feed, broiler early-stage feed, broiler middle-stage feed, and broiler late-stage feed. Two batches of each feed were collected, with a total of 120 samples. The mixing uniformity was determined by methyl violet method, molar method, and chloride ion selective electrode method. The results showed that the mixing evenness CV of six kinds of feeds determined by chloride ion selective electrode method was below 10.00% in the allowable range of national standard, and the results determined by methyl violet method were less than 10.00% except for medium pig compound feed. The mixing evenness of three kinds of pig feed was less than 10.00% by molar method, and the mixing evenness of three kinds of chicken feed was more than 10.00%. The variation coefficient of mixing uniformity of medium pig compound feed measured by methyl violet method was significantly higher than that by chloride ion selective electrode method (P<0.05). The variation coefficient of mixing evenness of broiler early-stage feed, broiler middle-stage feed by molar method were significantly higher than those by methyl violet method and chloride ion selective electrode method (P<0.05). The variation coefficient of mixing uniformity of broiler late-stage feed by molar method was significantly higher than that by methyl violet method and chloride ion selective electrode method (P<0.05), and the mixing uniformity of broiler late-stage feed by methyl violet method was significantly higher than that by chloride ion selective electrode method (P<0.05). The study indicates that the method of chloride ion selective electrode was effective in measuring the mixing uniformity of six kinds of feeds. [ABSTRACT FROM AUTHOR]

A composite solid chloride sensor consisting of two single sensors, i.e., Ag/AgCl working electrode and Mn/MnO2 reference electrode, was developed. The Ag/AgCl electrode was prepared by the anodic polarization method, while the Mn/MnO2 reference electrode was prepared using the powder compaction technique. Then, the electrochemical performances such as stability, reproducibility, and sensitivity of the composite and single sensors were investigated in a saturated Ca(OH)2 solution and mortar specimen. A current density of 0.5 mA/cm2 and polarization time of 2.5 h were the optimal preparation parameters of the Ag/AgCl selective electrode. The Ag/AgCl selective electrode showed a linear potential response with the logarithm of chloride ion content in solution and had good stability, reproducibility, and anti-polarization performances. In addition, the Mn/MnO2 electrode exhibited potential stability after being activated in an alkaline solution for 60 days. The composite sensor demonstrated exceptional sensitivity to the Cl− content, boasting a slope of approximately 51.1 mV/decade, and showcased excellent stability in both solution and mortar specimens. In every measurement, the time needed for the potential of a composite sensor to become stable was less than 30 s. The sensor enables non-destructive in situ monitoring of the chloride ion content in cement mortar, thus realizing early warning of deterioration of reinforcement and guaranteeing long service life of the structure. [ABSTRACT FROM AUTHOR]

One of the most significant damages of reinforced concrete is caused by chloride attacks. Solutions including the use of coatings or special concrete with low permeability have been proposed to promote concrete durability in previous research. Geopolymer mixes is a viable alternative in this context. Notwithstanding the advantages of geopolymer, problems with quick setting, shrinkage, increased cost, etc., may make its use problematic. Using permanent formworks (PFs) will therefore be a solution in this respect. PFs can be used both during the construction and during the repair of the structures. In this study, the considerations of fabricating PFs as well as their on-site implementation are examined. Compressive strength, impact resistance during transportation and installation, chloride ions penetration depth, and capillary absorption (from the seams and bulk) are among the experiments which are carried out to assess the performance of PFs. The significant increase in the service life of structures under chloride attack, the elimination of a part of the molding process in the construction of new structures, and the minimization of the low quality of execution are among the advantages of using PFs. The results reveal that the performance of PFs under harsh environmental conditions is appropriate. Although the use of polyurethane mastic in the seams has favorable results, reducing the number of seams decreases the probability of PFs damage. Although the implementing cost of PFs is slightly higher than conventional concrete (~ 37%), the life cycle cost assessment of the structure shows economic savings if PFs are applied. [ABSTRACT FROM AUTHOR]

Phosphogypsum (PG) is a byproduct of the phosphate fertilizer industry that can be used in cement mortar. However, PG mortar is known to have high water absorption. This paper proposes a new method to address this issue by using superhydrophobic phosphogypsum (SPG). PG was modified using stearic acid and sodium metasilicate. The hydrophobic mortar (H-mortar) was obtained by replacing a portion of the cement with SPG powder. The optimum water contact angle of the H-mortar was measured at 108.3°. Results from the experiment show that the water absorption of H-mortar was 19% lower than that of the reference mortar (Ref-M). Furthermore, the mechanical strength of H-mortar increased compared to Ref-M, as observed through strength testing. The study also investigated the impact of SPG addition rate on mortar corrosion resistance, and found that the addition of SPG reduces water migration and enhances resistance to chloride ion corrosion. The proposed method has the potential to utilize PG waste while improving mortar strength and corrosion resistance, making it suitable for use in marine mortar structures. [ABSTRACT FROM AUTHOR]

Electrochemical properties of magnetite nanoparticles supported on carbon paste electrodes were investigated by means of cyclic voltammetry. The measurements were performed for bare and coated with citrate magnetite nanoparticles in aqueous solutions of various electrolytes: NaCl, NaClO4, and Na2HPO4. Cyclic voltammetry curves obtained on bare and citrate functionalized Fe3O4 nanoparticles are rather similar indicating that the electrochemical properties of the magnetite nanoparticles are not significantly affected by the citrate coating. Cyclic voltammetry scans reveal the formation of metallic iron below −1.2 V. The defective structure of the oxide phases formed by oxidation of metallic iron seems to play an important role in the chemisorption of chloride ions and their subsequent oxidation. [ABSTRACT FROM AUTHOR]

Chloride ions are responsible for triggering severe corrosion in the marine environment. Hence, there is a need to deploy corrosion resistant materials such as hexagonal boron nitride (h-BN) sheet to protect mechanical components operating under such harsh conditions. In this work, a first-principles approach was employed to investigate the effect of fluorine modification on the thermodynamic and kinetic behaviors of oxygen on different kinds of vacancy-defective hexagonal boron nitride (h -BN) in a Cl-containing marine environment. Geometrical and electronic structures were systematically analyzed along with adsorption and diffusion behaviors. The existence of a low energy barrier implies that there is a relatively attenuated ability to inhibit O diffusion for double vacancy V BN - h -BN sheet compared to single vacancy V B - h -BN and V N - h -BN sheets. Interestingly, the fluorine functionalization for three defective h -BN sheet is found to cause an increased energy barrier of O diffusion. The F @ Cl @ V N - h -BN sheet possesses the highest diffusion energy barrier, indicating a superior anti-oxidation property in the marine environment. This study provides some fundamental guidelines for realizing high-performance h -BN sheets for protecting equipment and components used in marine applications. [ABSTRACT FROM AUTHOR]

It is shown that acid activation of ultralong carbon nanotubes synthesis products increases their reactivity during subsequent thermochemical treatment in air at 480 °C. Such an integrated approach of CNTs processing provides high purity and maximum yield of the target product. For example, the non-CNT fraction decreases by 3.2 times, while the residual iron content decreases by 17–24 times in comparison with thermochemical treatment without acid. Raman spectroscopy and low-temperature nitrogen adsorption showed that acid activation does not lead to extra surface defects, which could initiate further oxidation of carbon matrix in air. It is suggested that the increased reactivity of CNT synthesis products after acid activation during thermo-oxidative degradation may be due to the formation of an "adduct" of carboxyl groups on the surface of nanotube carbon matrix with hydrogen chloride. It was shown by thermogravimetric studies coupled with mass-spectra investigation of gas evolved, that under the constant heating, at the temperatures of the beginning of intensive oxidation (500–600 °C), the decomposition of the "adduct" occurs, bypassing the stage of formation of more temperature-resistant phenolic groups, which can inhibit further oxidation. Water released during the decomposition of the "adduct" can also accelerate the process of thermal oxidation. [ABSTRACT FROM AUTHOR]

For corrosive chloride solution, an excellent corrosion-resistant coating is required. In this view, introducing graphene oxide-modified Al 2 O 3 , TiO 2 , and MnO 2 in a nickel matrix is a novel strategy for achieving this goal. Electrodeposition is used for manufacturing these nanocomposite coatings. The microstructure, electrochemical corrosion resistance, composition, and contact angle are then thoroughly investigated. Electrochemical results revealed that Ni-GO-TiO 2 nanocomposite coating has a low corrosion current density of 10.86 μA/cm2 and a high charge transfer resistance of 2328 Ω cm2. Furthermore, the Ni-GO-TiO 2 nanocomposite coating outlasts pure nickel films. The mechanism of GO-TiO 2 -promoted nickel corrosion resistance turns out to be that GO-TiO 2 may impede the growth of nickel crystals and make them finer. Furthermore, this coating improves smoothness and reduces pores and cracks, resulting in less damage by chloride ions. Based on these findings, incorporating GO-TiO 2 into nickel coatings may provide insights into preventing corrosion of steel pipelines exposed to chloride ions. [Display omitted] • Nickel coating was reinforced with graphene oxide doped Al 2 O 3 , TiO 2 , and MnO 2. • Composition, crystal size, morphology, and hydrophobicity were compared. • Electrochemical and immersion tests were performed on all coatings. • Ni-GO-TiO 2 exhibited superior barrier performance due to improved properties. [ABSTRACT FROM AUTHOR]

Here, a cyclometalated Pt(II) clamshell dimer (complex 2) has been synthesized with the primary ligand of dibenzo(f,h)quinoxaline and an ancillary ligand of N,N′-diphenylformamidine. In addition, a mononuclear Pt(II) complex 1a and a binuclear Pt(II) complex 1b were also prepared. Complex 1a was coordinated by one cyclometalated ligand of dibenzo(f,h)quinoxaline, one chloride ion, and one N,N′-diphenylformamidine. Complex 1b was coordinated by one cyclometalated ligand of dibenzo(f,h)quinoxaline, two chloride ions, and two N,N′-diphenylformamidines. All of these three complexes were characterized by nuclear magnetic resonance (NMR) spectroscopy, high-resolution mass spectrometry (HRMS), elemental analyses, and single-crystal X-ray diffraction (XRD). The Pt–Pt distance in complex 2 was 2.8439(2) Å. It also exhibited a near-infrared (near-IR) emission at 887 nm in the pure solid state. On the other hand, complexes 1a and 1b exhibited triplet emission at 589 and 660 nm, respectively, in the pure solid state. Furthermore, in 2 wt% poly(Me methacrylate) (PMMA) films, complex 1a showed a triplet emission at 548 nm (with Φ = 84% and τ = 5.53 μs) and complex 1b showed an emission at 627 nm (with Φ = 79% and τ = 4.07 μs). Due to its great photophysical properties, complex 1b was deposited onto quartz plates for the detection of organic solvent vapors and it showed unique emission quenching for the vapor of tetrahydrofuran. [ABSTRACT FROM AUTHOR]

The title compound, C14H12N4O2⋅0.5HCl⋅H2O or H(C14H12N4O2)2 +⋅Cl- ⋅2H2O, arose from the unexpected cyclization of isonicotinoyl-N-phenyl hydrazine carbothioamide catalysed by cobalt(II) acetate. The organic molecule is almost planar and a symmetric N⋯H+⋯N hydrogen bond links two of them together, with the H atom lying on a crystallographic twofold axis. The extended structure features N--H⋯O and O--H⋯Cl hydrogen bonds, which generate [001] chains. Weak C--H⋯Cl interactions cross-link the chains. The chloride ion has site symmetry 2. The major contributions to the Hirshfeld surface are from H⋯H (47.1%), Cl⋯H/H⋯Cl (total 10.8%), O⋯H/H⋯O (7.4%) and N⋯H/H⋯N (6.7%) interactions. [ABSTRACT FROM AUTHOR]

High‐performance pure red perovskite light‐emitting diodes (PeLEDs) with an emission wavelength shorter than 650 nm are ideal for wide‐color‐gamut displays, yet remain an unprecedented challenge to progress. Mixed‐halide CsPb(Br/I)3 emitter‐based PeLEDs suffer spectral stability induced by halide phase segregation and CsPbI3 quantum dots (QDs) suffer from a compromise between emission wavelength and electroluminescence efficiency. Here, we demonstrate efficient pure red PeLEDs with an emission centered at 638 nm based on PbClx‐modified CsPbI3 QDs. A nucleophilic reaction that releases chloride ions and manipulates the ligand equilibrium of the colloidal system is developed to synthesize the pure red emission QDs. The comprehensive structural and spectroscopic characterizations evidence the formation of PbClx outside the CsPbI3 QDs, which regulates exciton recombination and prevents the exciton from dissociation induced by surface defects. In consequence, PeLEDs based on PbClx‐modified CsPbI3 QDs with superior optoelectronic properties demonstrate stable electroluminescence spectra at high driving voltages, a record external quantum efficiency of 26.1 %, optimal efficiency roll‐off of 16.0 % at 1000 cd m−2, and a half lifetime of 7.5 hours at 100 cd m−2, representing the state‐of‐the‐art pure red PeLEDs. This work provides new insight into constructing the carrier‐confined structure on perovskite QDs for high‐performance PeLEDs. [ABSTRACT FROM AUTHOR]

High‐performance pure red perovskite light‐emitting diodes (PeLEDs) with an emission wavelength shorter than 650 nm are ideal for wide‐color‐gamut displays, yet remain an unprecedented challenge to progress. Mixed‐halide CsPb(Br/I)3 emitter‐based PeLEDs suffer spectral stability induced by halide phase segregation and CsPbI3 quantum dots (QDs) suffer from a compromise between emission wavelength and electroluminescence efficiency. Here, we demonstrate efficient pure red PeLEDs with an emission centered at 638 nm based on PbClx‐modified CsPbI3 QDs. A nucleophilic reaction that releases chloride ions and manipulates the ligand equilibrium of the colloidal system is developed to synthesize the pure red emission QDs. The comprehensive structural and spectroscopic characterizations evidence the formation of PbClx outside the CsPbI3 QDs, which regulates exciton recombination and prevents the exciton from dissociation induced by surface defects. In consequence, PeLEDs based on PbClx‐modified CsPbI3 QDs with superior optoelectronic properties demonstrate stable electroluminescence spectra at high driving voltages, a record external quantum efficiency of 26.1 %, optimal efficiency roll‐off of 16.0 % at 1000 cd m−2, and a half lifetime of 7.5 hours at 100 cd m−2, representing the state‐of‐the‐art pure red PeLEDs. This work provides new insight into constructing the carrier‐confined structure on perovskite QDs for high‐performance PeLEDs. [ABSTRACT FROM AUTHOR]

This study describes the discovery of a unique ionic cocrystal of the active pharmaceutical ingredient (API) ponatinib hydrochloride (pon·HCl), and characterization using single-crystal X-ray diffraction (SCXRD) and solid-state NMR (SSNMR) spectroscopy. Pon·HCl is a multicomponent crystal that features an unusual stoichiometry, with an asymmetric unit containing both monocations and dications of the ponatinib molecule, three water molecules, and three chloride ions. Structural features include (i) a charged imidazopyridazine moiety that forms a hydrogen bond between the ponatinib monocations and dications and (ii) a chloride ion that does not feature hydrogen bonds involving any organic moiety, instead being situated in a "square" arrangement with three water molecules. Multinuclear SSNMR, featuring high and ultra-high fields up to 35.2 T, provides the groundwork for structural interpretation of complex multicomponent crystals in the absence of diffraction data. A 13C CP/MAS spectrum confirms the presence of two crystallographically distinct ponatinib molecules, whereas 1D 1H and 2D 1H–1H DQ–SQ spectra identify and assign the unusually deshielded imidazopyridazine proton. 1D 35Cl spectra obtained at multiple fields confirm the presence of three distinct chloride ions, with density functional theory calculations providing key relationships between the SSNMR spectra and H⋯Cl− hydrogen bonding arrangements. A 2D 35Cl → 1H D-RINEPT spectrum confirms the spatial proximities between the chloride ions, water molecules, and amine moieties. This all suggests future application of multinuclear SSNMR at high and ultra-high fields to the study of complex API solid forms for which SCXRD data are unavailable, with potential application to heterogeneous mixtures or amorphous solid dispersions. [ABSTRACT FROM AUTHOR]

Direct seawater splitting has attracted considerable attention as an alternative to conventional alkaline water electrolysis because the former avoids the use of limited freshwater resources. However, several challenges must be overcome to realize direct seawater electrolysis. Most importantly, electrocatalysts for the anodic oxygen evolution reaction (OER) should exhibit high activity, stability, and selectivity in highly corrosive environments with abundant chloride ions. In this study, we developed high-entropy carbonate (HEC) as a promising electrocatalyst for seawater oxidation. In HECs, physicochemical interactions among different elements can effectively suppress the corrosion of OER active sites, while polyanionic CO32- can act as a corrosion-protective species by repelling negatively charged chloride ions during electrolysis. Consequently, HECs demonstrate outstanding catalytic activity, stability, and selectivity for seawater oxidation, surpassing those of ternary, quaternary, and quinary carbonates and even benchmark IrO2 catalysts. [ABSTRACT FROM AUTHOR]