Search Results (207)

This study aimed to develop a reliable method for profiling reducing sugars in honey using capillary zone electrophoresis with laser-induced fluorescence detection (CZE-LIF). Reducing sugars were derivatized with 8-aminopyrene-1,3,6-trisulfonic acid (APTS) in the presence of 2-picoline borane, a safer alternative to sodium cyanoborohydride. Key parameters influencing the derivatization efficiency—temperature, pH, incubation time, and reagent concentrations—were systematically optimized. The highest labeling efficiency for glucose, mannose, and maltose was achieved at 50 °C in 0.5 M citric acid with 0.1 M APTS, while fructose showed low reactivity due to its ketose structure. To reduce the background signal from excess reagents, three cleanup strategies were evaluated. Liquid–liquid extraction with ethyl acetate effectively removed unreacted APTS without significant analyte loss, whereas solid-phase extraction and microextraction caused substantial losses of hydrophilic sugars. The method showed good linearity (0.5–10 mM, R² > 0.994), precision (RSD 0.81–13.73%), and accuracy (recoveries 93.47–119.75%). Stability studies indicated that sugar standards should be stored at –20 °C. The method was successfully applied to the analysis of four nectar honeys—rapeseed, acacia, phacelia, and dandelion—revealing differences in glucose and fructose content related to botanical origin. The results confirm the suitability of CZE-LIF for sensitive and selective carbohydrate analyses in complex food matrices. Full article

Phosphine–boranes have garnered growing interest for their potential in catalysis and as building blocks for inorganic polymers. While various synthetic methods exist, flexibility to introduce diverse substituents on the P centers remains limited. Our group reported routes to monoalkylated phosphanylboranes starting from primary phosphanylboranes or sodium phosphide. In this work, we extend these strategies to enable the synthesis of dialkylated phosphanylboranes bearing either identical or different substituents on the P atoms. This expanded methodology provides access to a broader scope of diverse P centers, a key factor influencing the reactivity and applications of phosphine–borane derivatives. Full article

Ammonia borane (AB), with a theoretical hydrogen content of 19.6 wt%, is constrained by its low crystalline density (0.758 g/cm³) and poor thermal stability (decomposing at 100 °C). In this study, AB/ammonium perchlorate (AP) composites were synthesized via freeze-drying at a 1:1 molar ratio. The integration of AP introduced intermolecular interactions that suppressed AB decomposition, increasing the onset temperature by 80 °C. Subsequent vacuum calcination at 100 °C for 2 h formed oxygen/fuel-integrated ammonium perchlorate borane (APB), which achieved decomposition temperatures exceeding 350 °C. The proposed mechanism involved AB decomposing into borazine and BN polymers at 100 °C, which then NH₃BH₂⁺/ClO₄⁻ combined to form APB. At 350 °C, APB underwent the following redox reactions: 4NH₃BH₂ClO₄ → N₂↑ + 4HCl↑ + 2B₂O₃ + N₂O↑ + O₂↑ + 7H₂O↑ + H₂↑, while residual AP decomposed. The composite exhibited improved density (1.66 g/cm³) and generated H₂, N₂, O_2, and HCl, demonstrating potential for hydrogen storage. Additionally, safety was enhanced by the suppression of AB’s exothermic decomposition (100–200 °C). APB, with its high energy density and thermal stability, was identified as a promising high-energy additive for high-burning-rate propellants. Full article

Ionic liquids (ILs) have been explored as a way of improving the performance of ZnO-based optoelectronic devices; however, there are few fundamental studies of the IL/ZnO interface. Here, the adsorption of the IL 1-octyl-3-methylimidazolium tetrafluoroborate [C₈C₁Im][BF₄] on ZnO (0001) and ZnO ($10\overline{1}0$) has been studied using synchrotron-based soft X-ray photoelectron spectroscopy. The results indicate that [C₈C₁Im][BF₄] is deposited intact on the ZnO (0001) surface; however, there is some dissociation of [BF₄]⁻ anions, resulting in boron atoms attaching to the oxygen atoms in the ZnO surface and forming B₂O₃. In contrast, the deposition of [C₈C₁Im][BF₄] on the ZnO ($10\overline{1}0$) surface at −150 °C results in the appearance of more chemical environments in the spectra. We propose that the high temperature of the IL evaporator causes some conversion of [C₈C₁Im][BF₄] to a carbene–borane adduct, resulting in the deposition of both the IL and adduct onto the ZnO surface. The adsorption and desorption of the analogous IL 1-butyl-3-methylimidazolium tetrafluoroborate [C₄C₁Im][BF₄] was investigated on ZnO (0001) using synchrotron-based soft X-ray photoelectron spectroscopy. The results indicate that [C₄C₁Im][BF₄] is deposited largely intact at −150 °C and forms islands when heated to room temperature. When heated to over 80 °C, it begins to react with the ZnO surface and decomposes. This is a much lower temperature than the long-term thermal stability of the pure IL, quoted in the literature as ~400 °C, and of IL on powdered ZnO, quoted in the literature as ~300 °C. This indicates that the ZnO surface may catalyse the thermal decomposition of [C₄C₁Im][BF₄] at lower temperatures. This is likely to have a negative impact on the potential use of ILs in ZnO-based photovoltaic applications, where operating temperatures can routinely reach 80 °C. Full article

Ammonia borane (AB) has attracted much attention in the field of solid-state hydrogen storage due to its high hydrogen storage capacity. Nanoconfinement in UiO-66 can reduce the hydrogen release temperature. In particular, terephthalic acid was used as a linker to further improve the dehydrogenation properties through the modification of -NH₂, -OH, -NO₂, -Br, and -F groups. The hydrogen release content of 0.5AB/UiO-66 was 1.98 wt.%, whereas the hydrogen release content of UiO-66-2OH modified by -OH groups increased to 3.85 wt.%. The non-covalent interaction results show that -NH₂ and -OH preferred adsorption with -BH₃, and the H in -NH₂ and -OH were able to interact directly with the H in AB to modify the dehydrogenation process of AB, whereas -NO₂, -Br, and -F indirectly affected the charge density of hydrogen atoms in AB to alter the dehydrogenation property of AB. The modification of functional groups provides a theoretical basis for the design of high-performance MOF nanoconfinement AB composite hydrogen storage materials. Full article

Ammonia borane (NH₃BH₃, AB) is recognized as a promising hydrogen carrier due to its high hydrogen storage density (146 gL⁻¹, mass fraction 19.6%), safety, non-toxicity, and high chemical stability. The hydrolysis of AB has also become a research hotspot in recent years and offers a viable route for hydrogen production. However, the practical application of AB hydrolysis encounters substantial challenges, including undefined catalytic mechanisms, suboptimal catalytic performance, and intricate issues in AB regeneration. Thus, elucidating catalytic mechanisms, developing highly efficient catalysts, and exploring effective regeneration methods for NH₃BH₃ are critical and urgent. This paper delves into the catalytic hydrolysis process of AB, detailing the mechanisms involved, and simplifies the steps that affect AB hydrolysis activity into the adsorption, activation, dissociation of reactants, and the formation and desorption of H₂. It discusses the structural characteristics of metal catalysts used in recent studies, assessing their performance through metrics such as turnover frequency (TOF), activation energy (E_a), and reusability. On this basis, this paper conducts a relatively comprehensive analysis and summary of the strategies for optimizing the performance of AB hydrolysis catalysts, including three aspects, focusing on optimizing the number and dispersion of active centers, enhancing reactant adsorption and activation, and facilitating hydrogen desorption. In addition, it also addresses strategies for controlled hydrogen release during AB hydrolysis and methods for regenerating AB from spent solutions. Finally, corresponding conclusions and prospects are proposed, to provide a certain reference for the subsequent development of safe and efficient catalysts and research on the catalytic mechanism of AB hydrolysis. Full article

Background: Wound healing is a complex and intricate biological process that involves multiple systems within the body and initiates a series of highly coordinated responses to repair damage and restore integrity and functionality. We previously identified that breathing hydrogen can significantly inhibit early inflammation, activate autologous stem cells, and promote the accumulation of extracellular matrix (ECM). However, the broader functions and downstream targets of hydrogen-induced ECM accumulation and tissue remodeling are unknown in the wound-healing process. Methods: Consequently, this thesis developed a hydrogen sustained-release dressing based on a micro storage material and reveals the mechanism of hydrogen in treating wound healing. Upon encapsulating the hydrogen storage materials, magnesium (Mg), and ammonia borane (AB), we found that SiO₂@Mg exhibits superior sustained-release performance, while SiO₂@AB demonstrates a higher hydrogen storage capacity. We used a C57/BL6 mouse full-thickness skin defect wound model to analyze and compare different hydrogen dressings. Results: It was identified that hydrogen dressings can significantly improve the healing rate of wounds by promoting epithelialization, angiogenesis, and collagen accumulation in wound tissue, and that the effect of slow-release dressings is better than of non-slow-release dressings. We also found that hydrogen dressing can promote transcriptome-level expression related to cell proliferation and differentiation and ECM accumulation, mainly through the Wnt1/β-catenin pathway and TGF-β1/Smad2 pathway. Conclusions: Overall, these results provide a novel insight into the field of hydrogen treatment and wound healing. Full article

The urgent global demand for sustainable green energy solutions has recognized hydrogen (H₂) as a viable green energy carrier. This study explores the efficient production of H₂ as a potential source of sustainable, environmentally friendly, high-energy-density fuel characterized by eco-friendly burning by-products. The research focuses on the photohydrolysis reaction of ammonia borane (AB), utilizing CdO-doped ZnO nanoparticles (NPs) embedded in polyurethane (PU) nanofibers (CdO/ZnO NPs@PU NFs) as a novel photocatalyst. Three different amounts of CdO/ZnO NPs were loaded onto PU NFs. The synthesized CdO/ZnO NPs@PU NFs exhibited good photocatalytic performance under visible light, producing approximately 67 mL of H₂ from 1 mmol of AB in 15 min with the sample containing the highest loading of CdO/ZnO NPs@PU NFs. This impressive photocatalytic performance is attributed to the synergistic effects of CdO and ZnO, which enhance charge carrier separation and broaden bandgap absorption in the visible spectrum. Kinetic studies demonstrated that the reaction exhibited first-order kinetics regarding catalyst dosing and zero-order kinetics concerning AB concentration, with an activation energy (E_a) of 32.28 kJ/mol. The results position CdO/ZnO NPs@PU NFs as effective photocatalysts for H₂ photogeneration under visible light irradiation. Full article

The formation of the siloxane bond is one of the most important reactions used in silicone chemistry and technology. In this paper, a new process for the condensation of alkoxy-functional silanes to form a siloxane bond is presented. The new reaction is catalyzed by a Ge(II)⁺ complex stabilized by pentamethylcyclopentadiene with a weakly coordinated anion, tetrakis(pentafluorophenyl)borane. A mechanistic study of this new condensation process using model alkoxy-functional silanes and propionaldehyde is completed. It is established that the quantitative conversion of alkoxysilanes to the siloxane bond requires stoichiometric amounts of aldehyde. It is also found that paraldehyde can serve as a convenient, higher boiling source of acetaldehyde for the condensation of alkoxysilanes. The results obtained, supported by DFT calculations, allow for us to formulate the mechanism of this reaction. Full article

Porous carbon particles (PCPs) prepared from sucrose via the hydrothermal method and its modified forms with polyethyleneimine (PEI) as PCP-PEI were used as templates as in situ metal nanoparticles as M@PCP and M@PCP-PEI (M:Co, Ni, or Cu), respectively. The prepared M@PCP and M@PCP-PEI composites were used as catalysts in the hydrolysis of NaBH₄ and NH₃BH₃ to produce hydrogen (H₂). The amount of Co nanoparticles within the Co@PCP-PEI structure was steadily increased via multiple loading/reducing cycles, e.g., from 29.8 ± 1.1 mg/g at the first loading/reducing cycles to 44.3 ± 4.9 mg/g after the third loading/reducing cycles. The Co@PCP-PEI catalyzed the hydrolysis of NaBH₄ within 120 min with 251 ± 1 mL H₂ production and a 100% conversion ratio with a 3.8 ± 0.3 mol H₂/(mmol cat·min) turn-over frequency (TOF) and a lower activation energy (Ea), 29.3 kJ/mol. In addition, the Co@PCP-PEI-catalyzed hydrolysis of NH₃BH₃ was completed in 28 min with 181 ± 1 mL H₂ production at 100% conversion with a 4.8 ± 0.3 mol H₂/(mmol cat·min) TOF value and an Ea value of 32.5 kJ/mol. Moreover, Co@PCP-PEI composite catalysts were afforded 100% activity up to 7 and 5 consecutive uses in NaBH₄ and NH₃B₃ hydrolysis reactions, respectively, with all displaying 100% conversions for both hydrolysis reactions in the 10 successive uses of the catalyst. Full article

The utilization of hydrogen in safety conditions is crucial for the development of a hydrogen-based economy. Among all methodologies, solid-state hydrogen release from ammonia borane through thermal stimuli is very promising due to the high theoretical hydrogen release. Generally, carbonaceous or inorganic matrices have been used to tune the reactivity of ammonia borane. Nevertheless, these solutions lack chemical tunability, and they do not allow one to properly tune the complex chemical pathway of hydrogen release from ammonia borane. In this study, we investigated the effect of a bioderived multifunctional polymeric matrix on hydrogen release from ammonia borane, reaching pure hydrogen release of 1.2 wt.% at 94 °C. We also describe new chemical pathways involving the formation of anchored intermediates, namely BxNy species. Full article

Thermally activated delayed fluorescence (TADF) materials with high photoluminescence quantum yields and a fast reverse intersystem crossing (RISC) are of the highest interest for organic light-emitting diodes (OLEDs). In the past decade, triaryl boranes with multiple resonance effect (MR) have captured significant attention. The efficiency of MR-TADF emitters strongly depends on small singlet–triplet energy gaps (ΔE_ST), but also on large reverse intersystem crossing (RISC) rate constants (k_RISC). The latter effect has strongly been focused on very recently and has drawn attention to heavier elements, including sulfur and selenium, the large spin–orbit coupling (SOC) of which accelerates RISC effects. Within the context of MR-TADF emitters, the 5,9-X₂-13b-boranaphtho [3,2,1-de]anthracene scaffold (X-B-X, X = donor heteroatom, e.g., N, O, S, Se) has been recognized as a promising narrowband-emissive TADF material. However, the incorporation of sulfur and selenium as highly SOC-inducing elements has proven to be difficult. Most synthetic strategies apply protocols initially suggested by Hatakeyama to obtain nitrogen- and oxygen-doped materials. We present an alternative route over the established methodology, which affords highly sought-after sulfur- and selenium-doped materials with a high yield and purity. Full article

The electrolysis of water is one of low-cost green hydrogen production technologies. The main challenge regarding this technology is designing and developing low-cost and high-activity catalysts. Herein, we present a strategy to fabricate flexible electrocatalysts based on nickel–iron (NiFe) alloy coatings. NiFe coatings were plated on the flexible copper-coated polyimide surface (Cu/PI) using the low-cost and straightforward electroless metal-plating method, with morpholine borane as a reducing agent. It was found that Ni₉₀Fe₁₀, Ni₈₀Fe₂₀, Ni₆₀Fe₄₀, and Ni₃₀Fe₇₀ coatings were deposited on the Cu/PI surface; then, the concentration of Fe²⁺ in the plating solution was 0.5, 1, 5, and 10 mM, respectively. The morphology, structure, and composition of Ni_xFe_y/Cu/PI catalysts have been examined using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), and inductively coupled plasma–optical emission spectroscopy (ICP-OES), whereas their activity has been investigated for hydrogen evolution (HER) and oxygen evolution (OER) reactions in 1 M KOH using linear sweep voltammetry (LSVs). It was found that the Ni₈₀Fe₂₀/Cu/PI catalyst exhibited the lowest overpotential value of −202.7 mV for the HER, obtaining a current density of 10 mA cm⁻² compared to Ni₉₀Fe₁₀/Cu/PI (−211.9 mV), Ni₆₀Fe₄₀/Cu/PI (−276.3 mV), Ni₃₀Fe₇₀/Cu/PI (−278.4 mV), and Ni (−303.4 mV). On the other hand, the lowest OER overpotential (344.7 mV) was observed for the Ni₆₀Fe₄₀/Cu/PI catalyst, obtaining a current density of 10 mA cm⁻² compared to the Ni₃₅Fe₆₅ (369.9 mV), Ni₈₀Fe₂₀ (450.2 mV), and Ni₉₀Fe₁₀ (454.2 mV) coatings, and Ni (532.1 mV). The developed Ni₆₀Fe₄₀/Cu/PI catalyst exhibit a cell potential of 1.85 V at 10 mA cm⁻². The obtained catalysts seem to be suitable flexible catalysts for HER and OER in alkaline media. Full article

We have investigated the thermodynamic property modification of ammonia borane via nanoconfinement. Two different mesoporous silica scaffolds, SBA-15 and MCM-41, were used to confine ammonia borane. Using in situ Raman spectroscopy, we examined how pore size influences the phase transition temperature from tetragonal (I4mm) to orthorhombic (Pmn21) for ammonia borane. In bulk ammonia borane, the phase transition occurs at around 217 K; however, confinement in SBA-15 (with ~8 nm pore sizes) reduces this temperature to approximately 195 K, while confinement in MCM-41 (with pore sizes of 2.1–2.7 nm) further lowers it to below 90 K. This suppression of the phase transition as a function of pore size has not been previously studied using Raman spectroscopy. The stability of the I4mm phase at a much lower temperature can be interpreted by incorporating the surface energy terms to the overall free energy of the system in a simple thermodynamic model, which leads to a significant increase in the surface energy when transitioning from the tetragonal phase to the orthorhombic phase. Full article

In this study, bimetallic NiCo nanoparticles (NPs) were encapsulated within the mesopores of carboxylic acid functionalized mesoporous silica (CMS) through the chemical reduction approach. Both NaBH₄ and NH₃BH₃ were used as reducing agents to reduce the metal ions simultaneously. The resulting composite was used as a catalyst for hydrolysis of ammonia borane (NH₃BH₃, AB) to produce H₂. The bimetallic NiCo NPs supported on carboxylic group functionalized mesoporous silica, referred to as Ni_xCo_100−x@CMS, exhibited significantly higher catalytic activity for AB hydrolysis compared to their monometallic counterparts. The remarkable activity of Ni_xCo_100−x@CMS could be ascribed to the synergistic contributions of Ni and Co, redox reaction during the hydrolysis, and the fine-tuned electronic structure. The catalytic performance of the Ni_xCo_100−x@CMS nanocatalyst was observed to be dependent on the composition of Ni and Co. Among all the compositions investigated, Ni₄₀Co₆₀@CMS demonstrated the highest catalytic activity, with a turn over frequency (TOF) of 18.95 mol_H2min⁻¹mol_catalyst⁻¹ and H₂ production rate of 8.0 L min⁻¹g⁻¹. The activity of Ni₄₀Co₆₀@CMS was approximately three times greater than that of Ni@CMS and about two times that of Co@CMS. The superior activity of Ni₄₀Co₆₀@CMS was attributed to its finely-tuned electronic structure, resulting from the electron transfer of Ni to Co. Furthermore, the nanocatalyst exhibited excellent durability, as the carboxylate group in the support provided a strong metal–support interaction, securely anchoring the NPs within the mesopores, preventing both agglomeration and leakage. Full article