Hydroxyl radical bursts triggered by long-term nitrate accumulation accelerate deep soil organic carbon mineralization.

Electrochemical nitrate reduction (NO3RR) under ambient conditions offers a sustainable route for ammonia (NH3) synthesis; however, its efficiency is restricted by the kinetic mismatch between water dissociation and nitrate hydrogenation. Here, we design Ag/CoNiS heterostructures in which Ag loading density programs interfacial confinement to regulate hydrogen spillover from CoNiS water-activation domains to Ag-associated nitrate/nitrogen oxide (NOx) intermediates, thereby coupling *H generation, relay, and deep nitrate hydrogenation. The optimized AgM/CoNiS achieves an NH3 yield of 22.31mgh-1cm-2 with 99.13% Faradaic efficiency. In situ Raman, distribution of relaxation times (DRT) analysis, hydrogen/deuterium (H/D) isotope experiments, and tert-butanol (TBA) perturbation tests reveal that the confined Ag-CoNiS interface regulates interfacial water and establishes a balanced *H supply-consumption regime, thereby suppressing competing hydrogen evolution. Density functional theory (DFT) calculations further show that Ag facilitates nitrate deoxygenation, whereas excessive Ag coverage weakens Co/Ni-centered water activation, explaining the volcano-type activity trend. Coupling NO3RR with the sulfide oxidation reaction (SOR) further enables a low-voltage NO3RR||SOR electrolyzer, requiring only 0.70V at 50mAcm-2 for energy-saving co-production of ammonia and sulfur.

Far-UVC at 222 nm is a promising alternative to conventionalUVat 254 nm, offering potent antimicrobial efficacy and in situ oxidationvia radical generation from water constituents such as nitrate. However,the role of nitrate-derived reactive species in microbial inactivationremains unclear. This study quantitatively evaluates the impact ofnitrate-driven radical production by Far-UVC on microbial disinfectionusing krypton chloride (KrCl*) excimer lamps. MS2 and T1UV bacteriophageandPseudomonas aeruginosa inactivationwere evaluated at environmentally relevant nitrate concentrations(0–8 mg N L–1). For MS2, 222 nm achievedhigher inactivation rates than 254 nm, with 4 mg N L–1 nitrate significantly enhancing reduction, attributed to radicalproduction from nitrate photolysis. Quenching with tert-butyl alcohol (TBA) confirmed hydroxyl radical (•OH) as thedominant species, while reactive nitrogen species (RNS) contributedminimally. T1UV exhibited high intrinsic sensitivity to 222 nm directphotolysis, and P. aeruginosa showednegligible enhancement from radicals, indicating limited oxidativecontribution. Apparent biomolecular rate constants, quantified forMS2 and T1UV, were 1.60–5.14 × 1010 M–1 s–1 for •OH and 8.79 × 104–1.46 × 105 M–1 s–1 for RNS. Coupled with radical kinetic modeling, these findings demonstratethat •OH governs oxidative effects in Far-UVC/nitrate systemsfor microorganisms, with implications for the treatment of nitrate-containingwastewater and water.

Abstract Cyclohexane (CYH) and tert‐butanol (TBA), as necessary industrial solvents, form an azeotrope that poses significant challenges in traditional distillation separation processes and leads to energy consumption issues. In this study, six deep eutectic solvents (DESs) based on quaternary ammonium salts were prepared to effectively separate TBA and CYH. Through liquid–liquid equilibrium experiments, the distribution coefficient and selectivity of TBA in these DESs were determined. The experimental data exhibited good linear correlation with the fitting results of the Othmer–Tobias equation and Hand equation. Furthermore, the binary interaction parameters in the nonrandom two‐liquid (NRTL) model were fitted using a MATLAB program, verifying the reliability of the model for the experimental data. Finally, by combining quantum chemical calculations with molecular dynamics (MD) simulations, the underlying mechanism of DESs in TBA extraction was thoroughly elucidated at the microscopic level, providing a solid theoretical foundation for the separation of alcohol–alkane azeotropic systems.

ZMQ-1 is a recently discovered aluminosilicate zeolite featuring atomically ordered mesopores (28 × 10-membered rings), providing a unique, intrinsically bimodal micro/mesoporous framework. This study systematically investigates how residual inorganic phosphate species, derived from the biphosphonium organic structure-directing agent, influence the textural and acidic properties of the material. Using argon physisorption, solid-state NMR, in situ FTIR, and DFT calculations, we demonstrate that vacuum calcination or targeted postsynthetic washing (NH4Cl, CsNO3) removes ∼90% of residual phosphorus species, which otherwise severely diminishes Brønsted acid sites density and accessibility. Crucially, the determination of accurate molar extinction coefficients for pyridine and 2,6-di-tert-butylpyridine revealed that residual phosphorus markedly hinders probe molecule accessibility and diminishes acid strength. DFT modeling identifies preferred Al substitution sites that orient Brønsted protons toward the 28-MR mesoporous channels. The catalytic potential of this architecture was interrogated via the sterically demanding alkylation of 2,4-di-tert-butylphenol with tert-butyl alcohol. Phosphorus-free ZMQ-1 achieves a 15.5% yield of the bulky target, 2,4,6-tri-tert-butylphenol─a 31-fold increase over hierarchical USY (0.5%) and vastly outperforming amorphous-walled Al-MCM-41. These findings establish ZMQ-1 as a landmark catalyst bridging the gap between zeolitic acidity and mesoporous accessibility and further push the catalytic operating boundaries of nanoporous solid acid catalysts.

A novel ROS relay strategy for S(IV) catalytic oxidation mediated by Mn-doped porous Carbocatalyst and tert-butyl alcohol

Hydrogen spillover generated and stabilized active Cu Sites for isobutyl alcohol synthesis from syngas over Pd-K promoted CuMgCe catalysts

Chitosan capped Ag0, Fe0 and Fe doped Ag@Fe as persulfate activators for the oxidative degradation of metronidazole in water.

The enzymatic esterification of 5-hydroxymethylfurfural (HMF) with long-chain fatty acids offers a sustainable route for producing biolubricants and other high-value chemicals. This work evaluates the synthesis of 5-hidroxymethylfurfural stearate catalyzed by immobilized lipases in both batch and continuous packed-bed bioreactors, combining molecular dynamics (MD) simulations with experimental validation to identify suitable green solvents. Four solvents were tested: 2-methyl-3-buten-2-ol (2-MB), tert-butanol (TB), 2-methyltetrahydrofuran (2-MeTHF), and cyclopentyl methyl ether (CPME). MD simulations revealed that CPME increased hydrophobic surface exposure and flexibility near the catalytic site, favoring substrate accessibility. In preliminary experimental tests, CPME provided the highest conversion (50%). In batch bioreactor at 40 °C, 30 mM HMF and 250 mM stearic acid achieved 67% conversion with Candida antarctica lipase B (CALB), maintaining full activity (100%) over four reuse cycles. In continuous operation, using a single packed-bed bioreactor at 0.02 mL min⁻¹ yielded conversions above 50% (residence time ≈ 55 min), while connecting two packed-bed bioreactors in series increased conversion to over 90% and productivity to 0.094 h⁻¹, compared with 0.076 h⁻¹ for one column and 0.003 h⁻¹ in batch mode. Deviations from ideal plug flow were observed over time, attributed to substrate or product deposition and in-situ water formation shifting the reaction equilibrium. Overall, CPME proved to be an efficient and sustainable solvent for the enzymatic synthesis of 5-hydroxymethylfurfural stearate, demonstrating the feasibility of continuous operation and highlighting pathways for further optimization through improved immobilization or reactor design.

Isocyanides as hydrogen-bond acceptors are characterized using jet-cooled Fourier transform infrared spectroscopy for the first time. The hydrogen-bonded structures of tert-butyl isocyanide (t-BuNC) and its constitutional isomer pivalonitrile (t-BuCN) with a single H2O or tert-butyl alcohol (t-BuOH) molecule are analyzed. The most stable monohydrate structures differ markedly: t-BuNC adopts a classical σ-type hydrogen bond, whereas t-BuCN favors a dispersion-stabilized orthogonal π-type arrangement. Substitution of H2O with the more polarizable t-BuOH enhances dispersion interaction between the molecules and drives both complexes toward π-type binding motifs. These findings highlight the balance between dispersive and electrostatic interactions in governing noncovalent binding preferences.

High-amylose Lueang Patew Chumphon (LPC) rice, a Thai geographical indication variety, represents an underutilized resource for functional food development. This study investigated sweet fermented LPC rice (SFLPC) compared to conventional sweet fermented glutinous rice (SFGR) through comprehensive microbial, chemical, and nutritional characterization. Starter cakes contained Aspergillus sp., Rhizopus stolonifer, and Pediococcus pentosaceus (>99% similarity by ITS/16S rRNA sequencing and MALDI Biotyper). Both varieties demonstrated comparable fermentation with pH reductions to ~3.5 and lactic acid production (~6 g/L). GC-MS analysis with mass spectral library matching and Linear Retention Index (LRI) comparison tentatively annotated twelve volatile compounds. Absolute peak area analysis revealed distinct variety-specific profiles: SFGR was characterized by significantly higher ethyl palmitate (75.89 ± 19.30 vs. 16.80 ± 7.21 × 106, p = 0.008) and isobutyl alcohol (33.09 ± 3.56 vs. 23.53 ± 1.71 × 106, p = 0.014), exclusive ethyl dodecanoate (44.87 ± 20.60 × 106), and exclusive 2,4-di-tert-butylphenol, while SFLPC showed exclusive ethyl acetate formation. Isoamyl alcohol was the dominant volatile in both varieties, with comparable absolute peak areas (273.91 ± 22.65 vs. 267.54 ± 28.78 × 106, ns). SFLPC demonstrated superior mineral retention (2.1-fold phosphorus, 1.9-fold potassium and magnesium) and enhanced antioxidant capacity (IC50: 3.30 vs. 5.20 μg/mL, representing 36% improvement). Degree of gelatinization analysis validated comparable starch gelatinization (32.5-40.1%) despite different cooking methods, confirming volatile differences arose from rice variety rather than processing. These findings demonstrate high-amylose LPC rice as a promising fermented food substrate offering enhanced nutritional properties and volatile compound profiles through traditional fermentation.

A series of Co, Co–Bi, and Co–Mg/g‐C 3 N 4 (graphitic carbon nitride) composites with 5 wt% metal content were synthesized via a one‐pot thermal polycondensation method using pristine and HNO 3 ‐protonated melamine as precursors for g‐C 3 N 4 . The obtained catalysts were characterized by inductively coupled plasma‐optical emission spectrometry, X‐ray diffraction, transmission electron microscopy, Selected Area Electron Diffraction (SAED), Fourier transform infrared spectroscopy, and Brunauer‐Emmett‐Teller method (BET) techniques. Their catalytic performance was evaluated for peroxymonosulfate (PMS) activation and the degradation of Acid Orange 7 (AO7) and methylene blue (MB) in aqueous solutions under ambient conditions. The Co‐g‐C 3 N 4 composite exhibited significantly higher catalytic activity than bare Co 3 O 4 and pristine g‐C 3 N 4 , which can be attributed to the synergistic interaction between the two components. It was found that the synthesis of g‐C 3 N 4 via pyrolysis of HNO 3 ‐protonated melamine enhances the PMS‐activation capability of the resulting composite catalysts. A further enhancement in catalytic performance was achieved by modifying Co‐g‐C 3 N 4 with MgO and Bi 2 O 3 . The superior performance of Co–Mg‐g‐C 3 N 4 (pm) is attributed to the increased basicity of the catalyst surface. Quenching experiments using ethanol (EtOH) and tert‐butyl alcohol (TBA) as radical scavengers confirmed the generation of sulfate radicals in the investigated systems. In addition, the effects of catalyst dosage, PMS/dye molar ratio, and initial solution pH on the degradation rates of AO7 and MB were also examined.

In this study, bioethanol was produced from Bashkir grape biomass in a laboratory setting. Using a Chromatec-Crystal 5000M mass spectrometer, the composition of the resulting bioethanol was analyzed, revealing 88 % ethanol, 3.2 % water, 5 % butanol, and 3.5 % hexanol, as well as a small amount of impurities (0.3 % by weight). Various fuels were used in the experiment, including hydrotreated gasoline fraction, methyl tert-butyl ether, technical ethanol, and isobutyl alcohol as a stabilizer for the gasoline-ethanol mixture. Further studies included determining detonation resistance and analyzing the composition of vehicle exhaust gases using UIT-85m and VAZ-21129 units and Kolion-1VN and Ecolab Plus gas analyzers.

Abstract This work investigates the applicability of gossypium seed biodiesel (B20) blended with tert‐butyl alcohol (TBA) for improving the performance and emission behavior of diesel engines operating under conditions representative of automotive traction applications. Experimental trials were conducted on a Common Rail Direct Injection (CRDI) engine, focusing on the optimization of injection timing (IT), injection pressure (IP), and TBA blending ratio. A combined optimization strategy employing the Taguchi method and Grey Relational Analysis (GRA) was used to identify the most favorable operating conditions, while an Artificial Neural Network (ANN) model was developed to predict engine responses. The optimization framework identified an injection timing of 27°CA bTDC, a 5% TBA blending ratio, and an injection pressure of 260 bar as the optimal parameter combination. Under these conditions, ANN predictions closely matched experimental results, with limited prediction errors of 6.9% for brake thermal efficiency (BTE), 3.7% for brake‐specific fuel consumption (BSFC), 1% for CO, 0.7% for NOx, and 11% for smoke emissions. In comparison with neat diesel operation, the optimized biodiesel TBA blend exhibited a marginal change in BTE (≈0.9%), while BSFC increased by about 8.7%, primarily attributed to the lower calorific value of the oxygenated fuel. Emission analysis revealed a significant reduction in NOx emissions of approximately 21.8%, along with a nearly 7.4% decrease in CO 2 emissions. Results show cottonseed biodiesel–TBA blends with optimized injection parameters can run effectively in CRDI engines, delivering cleaner emissions with acceptable performance trade‐offs, supporting their viability for sustainable automotive diesel applications.

Analysis of selective extraction of biofuel components from aqueous solution using single-stage membrane solvent extraction (MSE)

Abstract This study investigates the optimization of performance and emissions in a common rail direct injection (CRDI) engine using cottonseed biodiesel combined with ethanol and tert-butyl alcohol. Utilizing the Taguchi-Grey Relational Analysis (GRA) method, the research pinpointed the optimal engine parameters. For ethanol blends, the best results improved brake thermal efficiency (BTE) and lower emissions were achieved with a 15 % ethanol share (ES), 200 bar injection pressure (IP), and an injection timing (IT) of 27° before top dead center (bTDC). For tert-butyl alcohol blends (TBA), the ideal setup was a 5 % alcohol share, 27° bTDC injection timing (IT), and a higher 260 bar injection pressure (IP). Analysis of variance (ANOVA) indicated that the ethanol share (ES) was the most significant factor for brake thermal efficiency (BTE) and brake-specific fuel consumption (BSFC), while injection timing (IT) was paramount for controlling hydrocarbon (HC), carbon monoxide (CO), nitrogen oxides (NOx), carbon dioxide (CO 2 ), and smoke emissions. Conversely, for tert-butyl alcohol blends (TBA), injection pressure (IP) most affected brake thermal efficiency (BTE), the alcohol share governed BSFC, and injection timing (IT) was again the dominant factor for emissions. These findings provide critical guidance for selecting and optimizing alcohol additives in biodiesel-diesel fuel formulations.

Polyethylenimine-glutaraldehyde modification of Novozym® 435 enhances stability and sugar ester synthesis in a xylose-based natural deep eutectic solvent

N-heptane and tert-butyl alcohol azeotrope separation via ionic liquid mixture: molecular insight and process design

It is important to decrease considerable heat loss in buildings and vehicles to establish a low-carbon society. Transparent insulators applicable to windows can effectively reduce such heat loss. Conventional options for transparent insulators are silica aerogels that provide both optical transparency and thermal insulation benefits. However, silica aerogels are prepared via an unscalable supercritical drying process and are mechanically brittle, which restricts their practical use. In this study, we developed transparent and thermally insulating "cryogels" comprising mechanically strong cellulose nanofibers (CNFs). The term cryogels refers to porous structures prepared via practical freeze-drying of wet gels. In the synthesis, the agglomeration of nanofibers in a wet CNF gel during the freezing step was suppressed by rapidly freezing tert-butyl alcohol (t-BuOH)-exchanged wet gels with a stiffened network skeleton. The visible-light transmittance values of the cryogels ranged from approximately 80-90%, and the thermal conductivity reached as low as 0.023 W/m·K. We also extended this approach to chitin nanofibers (ChNFs) to demonstrate its universality. The resulting ChNF cryogels exhibited similar high transparency (∼80%) and low conductivities (0.022 W/m·K). These cryogels, with the potential for scalable production, are suitable as interspace materials for use in double-glazed windows, offering a promising solution for sustainable transparent insulators in energy-efficient building and vehicle applications.

Capturing the vibrational signatures of interfacial molecules is complicated by their low abundance relative to bulk molecules. Molecules at extended flat liquid interfaces can be elegantly singled out and probed by vibrational sum-frequency generation (SFG) spectroscopy as this method is intrinsically surface-specific due to the requirement of broken inversion symmetry. Interfacial molecules in solvation shells at molecular interfaces, on the other hand, exhibit inversion symmetry and vanish in SFG spectroscopy. However, in several cases, the fraction of solvent molecules at such molecular interfaces can be several percent of the total and can be isolated using advanced subtraction methods. Raman-MCR spectroscopy was first developed as a general and accurate method for extracting the Raman spectrum of this fraction of solvent molecules in the solvation shells of solutes. We later adapted the technique to FTIR spectroscopy in the form of ATR spectroscopy. The method is, in essence, a difference spectroscopy, wherein the vibrational spectrum of a solution is considered to be composed of two contributions: (i) that of the bulk solvent, which can be either a pure liquid or a mixture itself, and (ii) that of the solute with its solvation shell, defined as the part of the solvent that is perturbed by the interactions with the solute. In solvation shell spectroscopy, the bulk solvent contribution is removed from the solution spectrum, and the solute-correlated spectrum is then obtained. This solute-correlated spectrum contains the vibrational modes of the solute itself and those of perturbed molecules at the solute-solvent interface, which can reveal information such as the strength and extent of solute-solvent interactions. Here, we discuss advantages and complications of the method in detail using tert-butyl alcohol, a small amphiphilic molecule, as an example, starting in pure water and moving to more complex systems including ionic additives and mixed solvents. We furthermore illustrate how changes in the hydrogen-bond strength in the solvent shell can be quantified. Lastly, we push the spectroscopy to the detection limit and show that solvent interactions can be probed at not only molecular interfaces, but also meso- and even macroscopic interfaces. When done correctly, solvation shell spectroscopy holds great promise to be widely implemented to study solvent interactions in a wealth of different simple and complex systems.