Search Results (68)

Fluoroalkyl-substituted organoboron compounds are valuable building blocks for organic synthesis and for the development of functional molecules in medicinal chemistry, agrochemicals, and materials science. Building on our previous work on difluoromethyl-substituted borates, we report the synthesis and structural characterization of trifluoromethylated borates, 2-aryl-4,4,5,5-tetramethyl-2-(trifluoromethyl)-1,3,2-dioxaborolan-2-uide salts ([pinB(Aryl)CF₃]⁻). Treatment of pinB–Aryl boronates (pinB = 4,4,5,5-tetramethyl-1,3,2-dioxaborolane) with trimethyl(trifluoromethyl)silane (Ruppert–Prakash reagent) in the presence of potassium tert-butoxide and 18-crown-6 ether (18-C-6) afforded the corresponding trifluoromethylated borates as isolable crystalline compounds. Compared with the related difluoromethylated borates, the CF₃ substituent increases the tendency of [pinB(Aryl)CF₃]⁻ to exhibit hygroscopic behavior, as supported by a hydrated crystal structure and the formation of a hygroscopic product. The isolable trifluoromethylborates can serve as reservoirs of electrophilic trifluoromethyl radicals upon oxidation. Full article

The Iulia Felix is a 2nd-century AD Roman shipwreck that was discovered off the coast of Grado in 1986. Following its recovery, the hull was dismantled and treated with high concentrations of PEG 4000 at elevated temperatures. This process was completed in 2003. The elements were then stored for over 20 years. During this prolonged storage period, salt efflorescence developed on some surfaces, raising concerns about ongoing degradation and prompting an investigation into the composition of the wood and how environmental conditions influence it. The efflorescence was analysed using scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS), X-ray powder diffraction (XRPD) and Fourier transform infrared spectroscopy (FTIR). To evaluate the impact of environmental factors, samples were exposed to controlled humidity levels of 35% and 85% until equilibrium was achieved. The analyses identified iron- and sulphur-based compounds, including hydrated ferrous sulphates, calcium sulphate and hydrated iron oxides. These findings suggest a corrosion-related degradation process that originates in a marine burial environment and progresses in humid, oxygen-rich conditions after recovery. The presence of PEG within the efflorescence indicates that environmental conditions after treatment promoted its gradual migration to the surface. Climate testing revealed that PEG 4000 significantly reduced hygroscopic exchange with the environment. Under dry conditions, dimensional changes were minimal, with less than 1% variation in mass and surface area. In contrast, prolonged exposure to high humidity resulted in a 11% increase in mass due to moisture uptake, as well as a roughly 5% increase in surface area. This was accompanied by minor cracking and, in some cases, structural failure. This study highlights the long-term conservation challenges posed by waterlogged archaeological wood treated with high-molecular-weight PEG. It emphasises the importance of continuous environmental monitoring to mitigate degradation processes and preserve structural integrity, providing valuable insights for future museum conservation strategies. Full article

Rapid growth in fossil-fuel consumption has amplified the severity of global climate issues, making the deployment of renewable energy solutions increasingly imperative. Among candidate approaches, adsorption-based technologies are attractive; however, the limited adsorption capacity and kinetic performance of traditional adsorbents constrain composite-cycle efficiency and hinder large-scale implementation. In this work, we develop and evaluate a new class of composite adsorbents prepared by impregnating metal–organic frameworks (MOFs) with hygroscopic chloride salt solutions (LiCl, CaCl₂, and MgCl₂). Owing to their enhanced sorption characteristics, the resulting materials support an integrated adsorption cycle in which one device can simultaneously realize refrigeration, space heating, seawater desalination, and power generation. Under standard operating conditions, experiments demonstrate that MOF–vermiculite composites deliver a cooling coefficient of performance (COP) of 0.71, a heating COP (COP_h) of 1.30, a specific power-generation output of 27.2 kJ/kg, and a desalination yield of 0.71 g/g. Collectively, these metrics outperform the majority of previously published results, indicating that composite adsorbents can substantially improve the efficiency and practicality of renewable energy conversion systems. Full article

Atmospheric aerosols modulate Earth’s radiation balance through direct effects and through their role as cloud condensation nuclei (CCN), contributing to variability in near-surface temperature (NST). Galactic cosmic rays (GCRs) further influence aerosol–cloud interactions by enhancing particle formation and growth, but combined aerosol optical depth (AOD)–GCR effects on NST remain poorly constrained across climates. Using satellite and reanalysis data, we examine joint influences on NST anomalies at three neutron-monitoring stations, Oulu, Newark, and Hermanus, during 2000–2022. The sites share similar geomagnetic cutoffs but contrasting climates, enabling separation of ionization from geomagnetic shielding. Multiple linear regression (MLR) captures AOD effects and their modulation by GCR flux. Adding an interaction term (AOD × GCR) improves fit, raising adjusted R² from 0.22→0.31 (Oulu), 0.37→0.52 (Newark), and 0.69→0.78 (Hermanus). ECMWF reanalysis shows hydrophilic organic matter aerosol (OMA) dominates (0.19, 0.29, 0.41 µg kg⁻¹ at Oulu, Newark and Hermanus), with sulphate elevated at Oulu/Newark and coarse sea salt at Hermanus. Elevated OMA and sulphate at Oulu/Newark imply GCR-enhanced fine CCN and cooling, whereas humid, sea-salt-rich Hermanus favors ion-mediated growth of larger hygroscopic particles that increase longwave trapping and warming. Findings provide site-specific evidence that GCR ionization modulates aerosol processes and contributes to regional NST variability, informing improved parameterizations in climate models. Full article

Atmospheric water harvesting, as an emerging water collection technology, is expected to mitigate water resource crises. Adsorption-based atmospheric water harvesting technology offers distinct advantages, including geographical independence and reduced reliance on ambient humidity levels. Herein, a thermoresponsive gel (PNIPAM/TO-CNF) integrated with lithium chloride was constructed to achieve accelerated moisture sorption and rapid desorption capabilities. In the designated PNIPAM/TO-CNF/LiCl gel, PNIPAM provided a temperature-responsive hydrophilic–hydrophobic transition network; the hydrophilicity and structural strength were enhanced by TO-CNF, the moisture absorption capacity was dramatically elevated by hygroscopic salt LiCl, and pore-forming agent polyethylene glycol created a favorable porous structure. This synergistic design endows the gel with an optimized hydrophilic network, temperature-responsive behavior, and a porous architecture conducive to water vapor transportation, thereby achieving rapid moisture absorption and desorption. Under 60% relative humidity, the gel exhibited a water vapor adsorption capacity of 144% within 1 h, reaching its maximum absorption capacity of 178% after 140 min. The gel exhibited an even more superior desorption performance: when heated to 70 °C, its moisture content rapidly decreased to 16% of its initial weight within 1 h, corresponding to the desorption of 91% of the total absorbed water. A simplified pore-forming methodology that enables the integration of temperature-responsive properties with efficient moisture transfer channels was reported in this paper, providing a viable design pathway for achieving accelerated adsorption–desorption cycles in atmospheric water harvesting. Full article

In response to the growing impact of the climate crisis, many countries are accelerating efforts to develop sustainable and carbon-free energy solutions. This has led to increasing interest in advanced energy storage and conversion technologies, particularly the development of high-temperature molten salt energy systems. Among these, chloride salt-based molten salt systems, which offer excellent thermal properties such as high thermal conductivity, low melting points, and favorable chemical stability, are emerging as strong candidates for thermal energy storage and heat-transfer applications. This study focuses on deriving key thermophysical properties essential for selecting suitable molten salt heat-transfer fluids by examining their eutectic points and thermal stability with respect to various salt compositions. Three chloride mixtures—NaCl-MgCl₂, NaCl-KCl-MgCl₂, and NaCl-KCl-ZnCl₂—were evaluated for potential use in high-temperature molten salt energy systems. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were employed to measure the melting points and thermal stability of molten salts with various compositions near their eutectic regions. Experimental results were compared with predicted eutectic points to assess the thermal performance of each salt mixture. The findings indicate that the NaCl-KCl-MgCl₂ mixture exhibits the most promising characteristics, including a low melting point below 400 °C and superior thermal stability, making it highly suitable as a heat-transfer fluid in high-temperature molten salt energy systems. In contrast, NaCl-KCl-ZnCl₂ was found unsuitable for such applications due to its high hygroscopicity and poor thermal stability. This study provides essential data for selecting optimal molten salt compositions for the efficient and reliable operation of high-temperature molten salt energy systems. Full article

The mechanical performance of poly(methyl methacrylate) (PMMA) is highly sensitive to moisture absorption, which induces plasticization and softening. In this study, we investigated the ductilization mechanism of PMMA by incorporating various metal salts with different cations (Li⁺ and Mg²⁺) and controlling water absorption through hygroscopic interactions. A nonequilibrium constitutive model is introduced, in which localized water domains around salt-rich regions gradually diffuse into the PMMA matrix during tensile deformation. The stress–strain behavior is described by combining rigid (dry) and soft (hydrated) matrix components, connected through an internal kinetic variable governed by the strain-dependent diffusion rate. The model successfully reproduces experimental tensile data and captures the transition from brittle to ductile behavior as a function of the moisture content. Notably, Mg salts exhibit stronger water binding and slower moisture redistribution than Li salts, resulting in distinct mechanical responses. These findings provide a mechanistic framework for tailoring the ductility of hygroscopic polymer systems via ion–water–polymer interactions. Full article

Irbesartan (IRB) is a commonly used BCS Class II antihypertensive drug requiring dissolving capacity enhancement to address oral bioavailability limitations. In this work, seven new IRB salts were successfully synthesized, including one carboxylate (IRB-MAL) and six sulfonate salts (IRB-TOSA, IRB-BSA, IRB-4-CBSA, IRB-2, 5-CBSA, IRB-MSA, and IRB-CPSA). Their vitro dissolution, intrinsic dissolution rates (IDRs), thermal/hygroscopic stability (via thermal analysis, dynamic vapor sorption, and accelerated stability tests), and phase transition process (monitored by in situ Raman spectroscopy) were evaluated. The results revealed that IRB-TOSA, IRB-MAL, IRB-BSA, IRB-4-CBSA, and IRB-MSA salts exhibited IDRs of 0.3194–0.7383 mg/(cm²·min), all significantly higher than IRB, with dissolution concentrations increased by 14.9–113.6%. IRB-TOSA and IRB-4-CBSA salts demonstrated excellent hydrothermal stability. Single crystal structure analysis confirmed proton transfer from coformers’ sulfonic/carboxylic acids (deprotonation site, H-out) to IRB’s diazaheterocycles (protonation site, H-in) in IRB salts. Six sulfonate salts exhibited N_H-in–H···O_H-out and N_non-H-in–H···O_H-out hydrogen bonds, with the former absent in IRB-MAL. Furthermore, supramolecular synthon studies revealed distinct hydrogen-bonding patterns (e.g., bifurcated bonds in 2,5-CBSA and CPSA salts) that correlate with moisture resistance. Quantitative analysis of IRB salts suggested hydrogen bond strengths may influence their melting points (decomposition temperatures). This study demonstrates that IRB salts hold promise for advanced pharmaceutical applications. Full article

The moisture content in a building material has a negative impact on its technical parameters. This problem applies in particular to highly porous materials, including those based on aerogel. This paper presents moisture tests on a new generation of alkali-activated materials (AAMs) with different aerogel contents. Silica aerogel particles were used as a partial replacement for the lightweight sintered fly ash-based aggregate at levels of 10, 20, and 30 vol%. The experiment included four formulations: R0 (without the addition of aerogel) and the recipes R1, R2, and R3, with an increasing content of this additive. The level at which moisture stabilizes in a material in contact with the environment of a given humidity and temperature depends on whether the equilibrium state is reached in the process of moisture absorption by a dry material or in the process of the drying out of a wet material. The equilibrium states achieved in these processes are described by sorption and desorption isotherms, determined at a given temperature, but at different levels of relative humidity. The SSS (saturation salt solution) method has been used for years to determine them. Unfortunately, measurements carried out using this method are difficult and highly time-consuming. For this reason, a more accurate and faster DVS (dynamic vapor sorption) method was used in this study of R0–R3 composites. The research program assumed 10 step changes in humidity in the sorption processes and 10 step changes in humidity in the desorption processes. As a result, the course of the sorption and desorption isotherms of each of the four composites was accurately reproduced, and the hysteresis scale was assessed, which was most evident in the cases of the R0 composite (made without the addition of aerogel) and R1 composite (made with the lowest aerogel content). Studies have shown that the increased addition of aerogel resulted in an increase in the amount of water absorbed. This was true for all ten relative humidity levels tested. As a result, the highest values in the entire hygroscopic range were observed in the course of the sorption isotherm determined for the R3 composite with the highest aerogel content, and the lowest values were for the sorption isotherm of the R0 composite without the addition of aerogel. Full article

Urbanization in hot and humid regions such as southern China has increased the demand for comfortable indoor environments. In order to design a material for efficient passive indoor humidity regulation, this study investigates a composite material that combines the hygroscopic properties of salt and the adsorption capacity of diatomaceous earth (DE). Firstly, we prepared DE and boehmite into moisture-absorbing porous materials. Then, the initial DE-based sample was innovatively doped with SiO₂ nanomaterials and loaded with LiCl to enhance the humidity regulation ability of the composite, especially in the adsorption and desorption ability of water vapour. The microstructure and phase composition of the composite samples were analysed, and we observed an increase in porosity, filling performance and capillary condensation upon the introduction of SiO₂ nanoparticles. The hygroscopic salt loaded into the pores can absorb more water when exposed to the ambient humidity. This synergic effect can effectively improve the hygroscopic performance of the composite material while maintaining the stability of the physical and chemical properties. The optimized samples showed a moisture absorption rate of 28% in high-humidity environments, meeting moisture buffer value evaluation standards. The study’s findings lay the foundation for the future integration of these materials through advanced manufacturing technologies. Full article

In this study, the electrochemical coupling of nitrosoarenes with ammonium dinitramide is discovered, leading to the facile construction of the nitro-NNO-azoxy group, which represents an important motif in the design of energetic materials. Compared to known approaches to nitro-NNO-azoxy compounds involving two chemical steps (formation of azoxy group containing a leaving group and its nitration) and demanding expensive, corrosive, and hygroscopic nitronium salts, the presented electrochemical method consists of a single step and is based solely on nitrosoarenes and ammonium dinitramide. The dinitramide salt plays the roles of both the electrolyte and reactant for the coupling. Despite the fact that many side reactions can be expected due to the redox-activity of both the reagents and target products, under optimized conditions the synthesis is performed in an undivided cell under constant current conditions with high current density and can be easily scaled up without a reduction in the product yield. Moreover, the synthesized nitro-NNO-azoxy compounds are discovered to be potent fungicides active against a broad range of phytopathogenic fungi. Full article

To determine the link between hygroscopicity and the constituent chemical composition of real biomass-burning atmospheric particles, we collected and analyzed aerosols during wheat-straw (April–May), rice-straw (October–November), and no-burning periods (August–September) in 2008 and 2009 in Patiala, Punjab. A hygroscopicity tandem differential mobility analyzer (HTDMA) system was used to measure hygroscopicity at ~5 to ~95% relative humidity (RH) of aerosolized 100 nm particles generated from the water extracts of PM_0.4 burning and no-burning aerosol samples. The chemical analyses of the extracts show that organic carbon and water-soluble inorganic-ion concentrations are 2 to 3 times higher in crop-residue burning aerosol samples compared to no-burning aerosols, suggesting the substantial contribution of biomass burning to the carbonaceous aerosols at the sampling site. We observed that aerosolized 100 nm particles collected during the crop-residue burning period show higher and more variable hygroscopic growth factor (g(RH)) ranging from 1.21 to 1.68 at 85% RH, compared to no-burning samples (1.27 to 1.33). Interestingly, crop-residue burning particles also show considerable shrinkage in their size (i.e., g(RH) < 1) at lower RH (<50%) in the dehumidification mode. The increased level of major inorganic ions in biomass-burning period aerosols is a possible reason for higher g(RH) as well as the observed particle shrinkage. Overall, the measured g(RH), together with the correlation observed between aerosol water content and ionic-species volume fraction, and the study of the abundance of individual constituent ionic species suggests that inorganic salts and their proportion in aerosol particles primarily governed the aerosol hygroscopicity. Full article

Atmospheric water harvesting (AWH) is considered a promising strategy for sustainable freshwater production in landlocked and arid regions. Hygroscopic salt-based composite sorbents have attracted widespread attention for their water harvesting performance, but suffer from aggregation and leakage issues due to the salting-out effect. In this study, we synthesized a PML hydrogel composite by incorporating zwitterionic hydrogel (PDMAPS) and MIL-101(Cr) as a host for LiCl. The PML hydrogel was characterized using various techniques including X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FTIR), and thermogravimetric analysis (TGA). The swelling properties and water vapor adsorption-desorption properties of the PML hydrogel were also assessed. The results demonstrate that the MIL-101(Cr) was uniformly embedded into PDMAP hydrogel, and the PML hydrogel exhibits a swelling ratio of 2.29 due to the salting-in behavior. The PML hydrogel exhibited exceptional water vapor sorption capacity of 0.614 g/g at 298 K, RH = 40% and 1.827 g/g at 298 K, RH = 90%. It reached 80% of its saturated adsorption capacity within 117 and 149 min at 298 K, RH = 30% and 90%, respectively. Additionally, the PML hydrogel showed excellent reversibility in terms of water vapor adsorption after ten consecutive cycles of adsorption-desorption. The remarkable adsorption capacity, favorable adsorption-desorption rate, and regeneration stability make the PML hydrogel a potential candidate for AWH. This polymer-MOF synergistic strategy for immobilization of LiCl in this work offers new insights into designing advanced materials for AWH. Full article

As a global freshwater shortage is imminent, solar-powered adsorption-based atmospheric water harvesting technology is gradually attracting people’s attention due to its environmental friendliness and many other advantages. Among the many adsorbents used in this technology, MOF-801 has a large adsorption capacity in a wide range of humidity. In the current field, carbon materials are usually added to improve the photothermal properties of MOF-801, but hybrid adsorbents made in this way usually weaken the adsorption performance of MOF-801. If the MOF-801/carbon material adsorbent is used as a base and mixed with hygroscopic salt, which also has good adsorption properties, the hygroscopic properties of MOF-801 can be improved and the drawback of hygroscopic salt, which is prone to be lost after absorbing water, can be ameliorated. In this study, a hybrid adsorbent combining MOF-801 with carbon black (CB) and LiCl was prepared, and the effects of carbon black and LiCl on the performance of the MOF-801 adsorbent were compared. The experiments showed that the adsorption capacity of the hybrid adsorbent obtained a significant enhancement after the addition of LiCl, which increased by 38.2% versus 112.3% compared with MOF-801 and MOF-801/CB. Full article

Solid hygroscopic materials are extensively utilized in diverse fields, including adsorption heat transfer, adsorption heat storage, atmospheric water harvesting (AWH), and air conditioning dehumidification. The efficacy and energy efficiency of these materials in practical applications are significantly influenced by their adsorption and desorption properties. Yet, the introduction of inorganic salts to boost adsorption performance can result in issues like salt leakage. In this research, we prepared a polyacrylamide hydrogel through free radical polymerization, and its water-absorbing capabilities were improved by incorporating the hygroscopic salt lithium chloride. We compared it to a salt-based porous adsorbent, AlFum-LiCl, which also exhibited strong water adsorption properties and the potential for large-scale production. While AlFum-LiCl suffered from limited pores and salt leakage during high water uptake, the optimized PAM-LiCl displayed superior water sorption capabilities, showing no salt leakage even at water uptake of up to 3.5 g/g. At 25 °C, PAM-LiCl achieved equilibrium water uptake of 1.26 g/g at 30% RH and 3.15 g/g at 75% RH. In this context, utilizing 20 g of PAM-LiCl for the AWH experiment yielded daily water outputs of 8.34 L/kg at 30% RH and 16.86 L/kg at 75% RH. The salt-optimized PAM-LiCl hydrogel offers the benefit of application in higher relative humidity environments without the risk of deliquescence, underscoring its promise for atmospheric water harvesting. Full article