Deep eutectic solvents (DESs) are a broad class of multicomponent solvents that allow for tuning of properties through informed selection of constituent molecules. A comprehensive assessment of DES intermolecular interactions and their link to macroscopic attributes facilitates component selection. In this work, we employ infrared (IR) action spectroscopy in helium nanodroplets to characterize isolated halide-molecule clusters relevant to DESs. Complexes of urea, ethylene glycol, glycerol, and choline with chloride or bromide were generated by electrospray ionization, isolated in an ion trap, and captured in helium nanodroplets for spectroscopic characterization in the IR fingerprint region. For urea-chloride clusters, halide-molecule rather than molecule-molecule interactions dominate, resulting in a shallow potential energy surface with multiple orientations of the urea molecules differing primarily in their relative positioning. For clusters with strong competition between halide-molecule and intermolecular hydrogen bonding, as in glycerol-halide clusters, the potential energy surface becomes more complex, featuring multiple low-energy configurations with distinct hydrogen-bonding networks. Choline-chloride clusters exhibit possible two-point (OH + CH) and three-point (3CH) halide coordination motifs. Comparison to condensed-phase DES FT-IR spectra reveals distinctions between isolated clusters and bulk solution, highlighting the importance of assessing both intermolecular and halide-molecule interactions to accurately represent macroscopic DES structure.

A simple and milder reaction approach for the formation of C(sp2)-S(thiol) bonds through nucleophilic substitution (ipso mode) of activated aryl halides with aryl/alkyl thiols is reported. Good-to-excellent yields were achieved without any additives (viz. ligands or phase transfer catalysts). Higher yields were observed in the case of activated aryl fluorides relative to aryl chlorides and aryl bromides. This method is very useful in synthesizing pharmaceuticals and sulfur-based materials. The current approach is highly practical and widely adopted as it does not require the use of transition metal catalysts and work for different functional groups in ArX (X = F, Cl, and Br.).

Spns transporters are a mechanistically distinct branch of the major facilitator superfamily that regulate lipid transport, lysosomal homeostasis, immunity and disease, yet how the conserved Spns fold integrates protonation, substrate binding and alternating access to support chemically and directionally diverse transport activities remains unresolved. Here, we combine DEER spectroscopy in lipid nanodiscs with DEER- and AlphaFold-guided modeling to define the conformational landscape of the Mycobacterium smegmatis homolog Ms Spns. Protonation shifts Ms Spns toward an inward-facing state, whereas deprotonation favors a broader outward-facing ensemble through coordinated remodeling of intracellular and extracellular gates. These transitions are governed by membrane-embedded protonation switches and proton-sensing networks, while the substrate-binding cavity shows distinct proton sensitivity and weaker cooperativity. Hydrophilic cationic substrates, capreomycin and ethidium bromide, stabilize the outward-facing state, consistent with efflux antiport, whereas lipophilic compounds, including rifampicin, epicholesterol and selected phospholipids, favor the inward-facing state, suggesting uptake or allosteric stabilization. Thus, conserved proton-coupling elements can power opposing transport modes, revealing the mechanistic versatility of the Spns fold and its therapeutic potential.

A simple heterogeneous copper catalyst was prepared by adsorbing Cu(II) ions from an aqueous CuSO4 solution onto calcium carbonate (CaCO3) and marble waste microfine dust from the Carrara production area. The resulting materials (CaCO3-Cu and Carrara-Cu) were characterized by FTIR, PXRD, SEM-EDX, TGA, and zeta potential measurements, confirming copper uptake while preserving the carbonate framework. The catalytic activity of the materials was evaluated in the copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction. Using glucose as a reducing agent, the reactions were performed in water under ultrasound irradiation at 30 °C, generating the active Cu(I) species in situ. A model three-component reaction between benzyl bromide, sodium azide, and phenylacetylene afforded the corresponding 1,4-disubstituted 1,2,3-triazole in 81% isolated yield after 1 h. The scope of the methodology was evaluated across a range of substituted aryl alkynes and benzyl bromides as reaction partners, affording the corresponding triazoles in moderate to good yields. The catalyst was recovered by simple filtration and reused in subsequent reaction cycles. The use of water as the reaction medium, mild operating conditions, catalyst recyclability, and the successful application of marble waste as a catalyst support make this methodology a practical and sustainable approach for the synthesis of 1,2,3-triazoles.

Sixteen multiparous lactating Holstein cows were used in a randomized complete block design to evaluate the effects of dietary supplementation with a cultivated seaweed-based additive (Synergraze Inc., Calgary, AB, Canada) on feed intake, enteric CH4 emissions, feed efficiency, and lactational performance. The experimental period consisted of a 5-wk treatment period preceded by a 2-wk covariate (pretreatment) period. At the start of the experiment, cows were blocked (8 blocks; 2 cows/block) based on milk yield and DIM, and subsequently adjusted using pretreatment milk yield and enteric CH4 emissions. Within each block, cows were randomly assigned to 1 of 2 dietary treatments: (1) a TMR (63:37 forage:concentrate ratio) without supplementation (control, CTL), or (2) the same TMR supplemented with 0.25% (DM basis) of the seaweed additive (SEA). Cows were fed ad libitum to allow 5% orts (as-fed basis). The SEA supplement was hand-mixed with a portion of the TMR and a commercial protein supplement and offered as a premix before delivery of the diet to ensure complete consumption. Across the experiment, CHBr3 concentration in SEA averaged 4.61 ± 0.187 mg/g DM. Supplementation with SEA markedly reduced enteric CH4 production (g/d) by 45.9%, CH4 yield (g/kg of DMI) by 44.8%, and CH4 emission intensity (g/kg of ECM) by 47.2% compared with CTL. Dry matter intake decreased by 1.5 kg/d (5.62%) with SEA supplementation. Milk yield, 4% FCM, and ECM were not affected by treatment. Milk fat and lactose concentrations were similar between treatments; however, milk protein concentration increased with SEA supplementation. Yields of milk components, MUN concentration, and SCC were not affected by treatment. Feed efficiency, BW, and BCS were also unaffected by SEA supplementation. Bromoform was not detected in milk from SEA-fed cows, and milk iodine and bromide concentrations remained below reported health-based reference values. Results of this study demonstrate the strong potential of SEA to mitigate enteric CH4 emissions (production, yield, and intensity) without negatively affecting animal performance or compromising milk safety.

This study evaluated the effect of stock restraint, mare preparation, ovarian manipulation and/or puncture, sedation and butylscopolamine bromide-metamizole on Heart Rate Variability (HRV), facial expressions and operator - assessed procedural ease during ovum pick up (OPU) in mares. Six healthy adult mares were subjected to the three experimental protocols in a randomized crossover design: sham OPU without sedation, sham OPU with sedation and regular OPU with sedation. Each experimental protocol consisted of five sequential phases: baseline assessment, post-sedation (or saline) assessment, mare preparation, ovarian manipulation or follicular puncture before butylscopolamine bromide-metamizole administration, and a final ovarian manipulation or follicular puncture after butylscopolamine bromide-metamizole administration. HRV, pain-related facial expressions, operator-assessed procedural ease, and the number of rectal peristaltic waves recorded in real time during ovarian manipulation were evaluated. HRV data were analysed using repeated-measures general linear models, whereas facial expression data were analysed using generalized linear mixed models. Operator-assessed procedural ease and peristaltic waves were analysed using paired and unpaired tests, as appropriate. HRV parameters differed primarily according to sedation status, with no additional changes associated with follicular puncture. Non-sedated mares showed higher heart rate (HR) and sympathetic nervous system index (SNSi), and lower parasympathetic nervous system index (PNSi), than sedated mares. Butylscopolamine bromide-metamizole reduced peristaltic waves from 2.2 ± 1.5 to 0 waves (p < 0.012) in non-sedated mares and sedation reduced peristaltic waves from 2.2 ± 1.5 to 0.4 ± 0.9 waves (p = 0.041). The frequency of pain-related facial expressions increased during ovarian manipulation in non-sedated mares compared with sedated mares (p < 0.05), whereas follicular puncture itself did not further increase this parameter. In conclusion, HRV showed limited utility for pain assessment, due to pharmacological effects, whereas facial expressions provided a sensitive identification of discomfort, particularly during ovarian manipulation and puncture. Butylscopolamine bromide-metamizole facilitated ovarian handling and reduced peristaltic activity and discomfort. Follicular puncture did not appear to increase pain beyond ovarian manipulation. These findings support the use of behavioral parameters to evaluate pain and highlight the need to refine analgesic protocols to improve animal welfare during OPU.

Gold nanorods (AuNRs) present a promising alternative to silver nanoparticles (AgNPs) for surface-enhanced Raman spectroscopy (SERS) applications due to their improved biocompatibility, chemical stability, and tunable optical properties. However, the cetyltrimethylammonium bromide (CTAB) surfactant typically required for AuNR synthesis introduces significant spectral and physical interferences that inhibit analyte detection. This study systematically compares reductive and oxidative electrochemical cleaning protocols to remove CTAB from AuNR-modified screen-printed electrodes. Electrochemical cleaning effectively removes CTAB, enabling detection of metabolites such as uric acid (0.15 mM) and nicotinic acid (10.0 mM). Reductive cleaning preserves the AuNR morphology, while oxidative cleaning induces surface restructuring that alters molecular adsorption behaviour on the metal surface. Both cleaning methods retain strong SERS activity originating from the AuNRs, which is improved compared to uncleaned substrates. Oxidative cleaning enhances SERS intensity by increasing surface roughness and hot-spot density, thereby improving electrochemical SERS (EC-SERS) performance relative to AgNP-based platforms.

Two chiral lead bromide hybrids with chainlike structures exhibit markedly different second-harmonic generation (SHG) responses, highlighting supramolecular template modulation as an effective strategy for tuning SHG performance beyond conventional polyhedral-distortion engineering.

Photocatalytic hydrogen production from water, particularly seawater, offers a promising route for converting solar energy into storable chemical fuels. However, despite considerable efforts in photocatalyst design, the influence of seawater ions on photocatalytic processes remains poorly understood. In this study, covalent organic frameworks (COFs) are adopted as a structurally well-defined platform to investigate how representative inorganic ions present in seawater influence photocatalytic hydrogen production. Among the ionic species commonly present in seawater, sodium bromide (NaBr) is identified as the most effective promoter. Mechanistic studies reveal that Br- regulates the catalytic process through multiple pathways. During Pt photodeposition, Br- modulates the electronic structure of Pt nanoparticulate cocatalyst, promoting interfacial charge separation. During the photocatalytic reaction, Br- interacts with photogenerated holes and stabilizes the excited-state charge, thereby prolonging the lifetime of charge carriers. At high concentrations, Br- reduces the number of accessible active sites on the Pt surface, leading to catalyst poisoning. Significantly, the mechanistic insights gained from COF systems can be extended to common semiconductor photocatalysts, offering valuable guidance for ion-regulated photocatalysis under seawater-relevant conditions.

Lead-free organic-inorganic metal halides have emerged as promising candidates for X-ray imaging applications owing to their intrinsic radioluminescence, solution processability, and economic viability. However, their development remains largely empirical, with limited understanding of the structure-property relationships governing radioluminescence efficiency and stability. Herein, we address this challenge using two zero-dimensional (0D) mixed-metal Mn-Zn bromide systems with distinct organic spacers (T = C9H14BrN and D = C6H12N2), enabling controlled modulation of organic spacer length and metal-metal separation. Although both systems exhibit near-unity photoluminescence quantum yields (PLQYs), they display markedly different scintillation responses. The larger metal-metal separation in Mn0.5Zn0.5Br4T, induced by the longer organic cation T, suppresses nonradiative interactions, leading to enhanced radioluminescence efficiency and operational stability. The optimized system, Mn0.5Zn0.5Br4T, achieves a high light yield of 76,000 photons MeV-1, excellent stability, and an ultralow detection limit of 112 nGy s-1-approximately 50 times lower than standard medical diagnostic dose rate (5.5 μGy s-1). Flexible large-area scintillators further demonstrate high-resolution X-ray imaging capability. This work establishes a structure-property relationship linking organic spacer modulation, mixed-metal composition, and scintillation efficiency, enabling a rational design framework for scalable, high-performance X-ray scintillators.

The corrosion-inhibiting properties of the ionic liquid 3-benzyl-1-propyl-imidazolium bromide (RD) for carbon steel were investigated in molar hydrochloric acid. The mass-loss technique was applied to assess the inhibitory properties of the RD and demonstrated significant inhibitory activity, reaching 93.2% at 2 × 10-3 M. Kinetic and thermodynamic studies demonstrated the adsorptive character of the inhibitory process with a high activation energy (E a = 110.69 kJ mol-1) and a large adsorption equilibrium constant (K ads = 19 830 L mol-1). RD was proven to be physically adsorbed onto the surface of the carbon steel (ΔG ads = -35.04 kJ mol-1). The electrochemical analyses demonstrated a mixed-type behavior of RD molecules. This process increases the resistance to charge transfer while reducing the double-layer capacitance at the metal-solution interface. SEM images confirmed the formation and growth of a protective adsorbed layer that achieved a significant level of coverage at the ideal concentration. When inhibitors were effectively absorbed onto the carbon steel's surface, they formed a protective coating. This coating led to a smoother finish on the inhibitor-treated carbon steel, reducing its surface roughness. Additionally, in quantum chemistry, density-functional theory calculations showed excellent agreement with the experimental findings.

Halide perovskite is rising as a promising candidate for lasing applications owing to its excellent luminescence properties and the facile, economical construction of a microcavity. However, developing violet-blue perovskite lasers, which typically rely on bromide-chloride mixed halide systems, has long been hindered by uncontrollable crystallization and high defect density caused by poor crystal quality. Here, we develop an isomerization-driven halide exchange strategy for the growth of chloride mixed wide-band gap perovskite, which is fundamentally distinct from the violent, unregulated processes of traditional methods. This mild and kinetically controlled reaction enables the formation of uniform, highly crystallized violet-blue perovskite films with drastically reduced defect density and suppressed nonradiative recombination. As a result, an ultralow amplified spontaneous emission threshold of 1.4 μJ cm-2 is achieved at 423 nm, which is 5.1 times lower than the best previously reported value. More importantly, a random and single-mode laser threshold of 2.6 and 6.5 μJ cm-2 at 423 nm is achieved. The robust and homogeneous structure enables exceptional operational stability, with a T95 lifetime exceeding 7 × 107 pulses under intense excitation (25× threshold) in ambient conditions without encapsulation. This work establishes a generalizable, universal paradigm for synthesizing high-quality wide-band gap perovskites, which provides a versatile and robust method for the development of advanced violet-blue optoelectronic devices.

This study is influenced by the broad utilization of azo dyes in industry and their persistence in the environment. It investigates the interaction behavior of anionic sunset yellow (SSY) and tartrazine (TAZ) with gemini surfactants GS-5 and GS-6 at 25 °C by conductometric, surface tension, UV-visible, and particle size/zeta potential studies. The dyes considerably decreased the critical micelle concentration (CMC) of both surfactants, from 0.157 to 0.060 mmol L[-1] (SSY) and 0.083 mmol L[-1] (TAZ) for GS-5, and from 0.105 to 0.044 and 0.045 mmol L[-1] for GS-6, respectively, which implies strong dye-surfactant interactions. With increasing dye concentration, the micellar ionization (α = 0.230-0.298) decreased, and the total counterion binding (β = 1.034-1.254) increased owing to the efficient substitution of bromide ions by dye anions at the stern layer. Synergistic mixed-counterion binding was demonstrated using modified Corrin-Harkins and Gibbs-Duhem techniques. GS-6 displayed somewhat stronger interactions with spacer-length effects. UV-Visible experiments indicated increased intrinsic binding and partition constants of TAZ, suggesting more micellar incorporation. Particle size and zeta potential measurements indicated concentration-dependent aggregate expansion (102-285 nm) and a drop in surface charge (+50 to +17 mV), suggesting increased counterion condensation and stable mixed micelle formation. The findings demonstrate that the stability and organization of dye-gemini surfactant mixed systems are jointly modulated by electrostatic attraction, hydrophobic association, cooperative counterion binding and spacer architecture.

This study develops a photocatalytic system based on non-metallic tubular hollow-structured g-C3N4 (HT-CN), which achieves highly selective oxidation of benzylic C-H bonds in alkylbenzenes to ketones by introducing lithium bromide (LiBr) as a dual-functional mediator. Innovatively, the system employs bromine radicals (Br˙) generated via photoinduced dissociation of LiBr for pre-activation of benzylic C-H bonds. Combined with the synergistic oxidation effect of photogenerated singlet oxygen ([1]O2) from HT-CN, this strategy successfully addresses the challenges of poor selectivity, low efficiency, and limited substrate generality in conventional methods under mild conditions: room temperature, visible-light irradiation, and oxygen atmosphere, providing a novel approach for green synthesis of aromatic ketones.