Search Results (587)

Functionalizing agents enhance the photophysical properties of nanomaterials, thereby broadening their applications. Among these agents, cysteamine (SH-(CH₂)₂-NH₂) is unique because of its free thiol (-SH) and amino (-NH₂) groups. The presence of free -SH or -NH₂ groups significantly enhances the functionalization of highly stable nanomaterials. These stable nanomaterials, which contain free -SH or -NH₂ groups, can effectively bind with biomedical, biomolecular, and environmental analytes, improving sensor performance and making them valuable materials. In this context, cysteamine-functionalized nanoparticles (NPs), quantum dots (QDs), nanoclusters (NCs), nanocomposites, and other nanostructures have been demonstrated to be useful for quantifying biomedical, biomolecular, and environmental analytes. To date, no review has outlined the functionalizing ability of cysteamine or the application of cysteamine-functionalized nanomaterials in biomedical, biomolecular, and environmental analyte monitoring. This review emphasizes the role of cysteamine in producing stable nanomaterials and detecting specific biomedical, biomolecular, and ecological analytes. It also covers general protocols for functionalizing with cysteamine, the mechanistic basis of analyte detection, and their advantages, limitations, and prospects. Full article

This work presents the HX-responsiveness of the following heteroleptic donor–M–acceptor dithiolene complexes: Bu4N[MII(L1)(L2)] [M = Ni(1), Pd(2), Pt(3)], where L1 is the chiral acceptor ligand [(R)-α-MBAdto = chiral (R)-(+)α-methylbenzyldithio-oxamidate] and L2 is the donor ligand (tdas = 1,2,5-thiadiazole-3,4-dithiolato). Addition of hydrohalic acids induces a strong bathochromic shift and visible color change, which is fully reversed by ammonia (NH₃). Moreover, the sensing capability of 1 was further evaluated by deposition on a cellulose substrate. Exposure to HCl vapors induces an evident color change from purple to green, whereas successive exposure to NH₃ vapors fully restores the purple color. Remarkably, cellulose films of 1 were revealed to be excellent optical sensors against the response to triethylamine, which is a toxic volatile amine. Moreover, the HCl-responsiveness of the nonlinear optical properties of complexes 1, 2, and 3 embedded into a poly(methyl methacrylate) poled matrix was demonstrated. Reversible chemical second harmonic generation (SHG) switching is achieved by exposing the poled films to HCl vapors and then to NH₃ vapors. The SHG response ratio HCl–adduct/complex is significant (around 1.5). Remarkably, the coefficients of the susceptibility tensor for the HCl–adduct films are always larger than those of the respective free-complex films. Density Functional Theory (DFT) and time-dependent DFT calculations help in highlighting the structure–properties relationship. Full article

The durability of cement-based materials can be reduced by the invasion of water and ions from external environments. This can be alleviated by reducing the surface wettability. To evaluate the anti-wetting performances of different graphene-based materials, a molecular dynamics simulation was performed to investigate the wetting behaviors of water and NaCl droplets on a tobermorite surface coated with graphene and functionalized graphene (G-NH₂ and G-CH₃). The results demonstrate that functionalized graphene displays weak surface binding with water and ions, significantly weakening droplet wettability. Moreover, functionalized graphene surfaces exhibit reduced ion immobilization capacity compared with a pristine tobermorite surface. It obviously increases the number of free ionic hydration shells, thus amplifying the influence of ionic cage restriction. Specifically for the G-CH₃ surface, the contact angle of the NaCl droplet reaches 94.8°, indicating significant hydrophobicity. Furthermore, the adhesion between functionalized graphene and tobermorite is attributed to the interlocking characteristics of these materials. Hopefully, this study can provide nanoscale insights for the design of functionalized graphene coatings to improve the durability of cement-based materials under harsh environments. Full article

Leghemoglobin (LegH), a plant-derived hemoprotein, is engineered for the first time as a standalone biocatalyst for carbene N–H insertion. Through semi-rational design, the K65P mutation in the heme pocket significantly enhances catalytic efficiency. Under mild aqueous conditions (PBS buffer, 25 °C), the K65P variant achieves 92% yield in the model reaction between benzylamine and ethyl α-diazoacetate—surpassing wild-type LegH by >1.6-fold in initial reaction rate. The mutant also exhibits markedly improved thermostability. This work establishes engineered LegH as a high-performance, cofactor-free biocatalyst for C–N bond formation, providing a sustainable platform for synthesizing chiral amine derivatives. The catalytic proficiency and inherent stability of the K65P mutant demonstrate the potential of plant hemoproteins in non-natural carbene transfer reactions without requiring immobilization supports. Full article

In this study, benzophenone compounds substituted with electron-withdrawing groups (-NO₂, -F, and -Cl) and electron-donating groups (-OH, -CH₃, -NH₂, and -OCH₃) were employed as voltage stabilizers for crosslinked polyethylene (XLPE) insulation materials. At B3LYP/6-311+G(d,p) level, reaction Gibbs free potential energy data for eleven reaction channels and molecular characteristics, including electron affinity EA(s), ionization potential IP(s), and HOMO-LUMO gap (E_g) of benzophenone derivatives, were obtained. The effects of electron-donating and electron-withdrawing functional groups were systematically evaluated. The calculated results indicate that benzophenones exhibit the lowest Gibbs free energy barrier for grafting onto polyethylene among the investigated molecules. With the introduction of electron-donating groups, the reaction Gibbs free energy barrier increases. It is worth noting that 2-Nitrobenzophenone is considered to possess superior electrical resistivity, attributed to its highest electron affinity among the studied compounds. This investigation is expected to provide reliable insights for the development of modified polyethylene-based insulating materials for high-voltage cables. Full article

Ammonia (NH₃) is a promising carbon-free fuel for internal combustion engines, but its low reactivity and poor ignition properties present significant challenges for stable operation. This study presents the development and experimental validation of a spark-ignited combustion process that enables stable engine operation using 100% liquid NH₃ as a single fuel. A modified single cylinder research engine, equipped with NH₃ port fuel injection and a high-energy capacitive ignition system was used to investigate combustion behavior under various load conditions. The results show that stable, knock-free combustion with pure NH₃ is feasible at every operating point without any ignition aids like diesel fuel or hydrogen (H₂). The full load conditions of a diesel engine can be represented with an indicated efficiency of 50% using this combustion process. The emission measurements show nitrogen oxides (NO_x) and NH₃ emissions in a 1:1 ratio, which is advantageous for a passive SCR system. Increased nitrous oxides (N₂O) formation occurs at low loads and cold combustion chamber temperatures. This work demonstrates the technical viability of carbon-free NH₃ combustion in spark-ignited (SI) engines and represents a promising step towards net-zero combustion. Full article

Spiky Au-Ag nanostars offer intense plasmonic enhancement due to their sharp-tipped morphology, enabling powerful surface-enhanced Raman scattering (SERS). Here, we report a liquid-phase SERS platform that addresses current limitations in cancer biomarker detection, such as low sensitivity and dependence on Raman reporters. Nanostar concentration was tuned by simple centrifugation (10, 30, and 60 min), and their SERS performance was evaluated using methylene blue (MB) and mercaptopropionic acid (MPA) as probe molecules. Signal intensity scaled with nanostar content, enabling sensitive detection. Optimized nanostars were functionalized with MPA, 1-Ethyl-3-(3-dimethylamino1-Ethyl-3-(3dimethylaminopropyl1) carbodiimide (EDC), and N-Hydroxy succinimide (NHS) for covalent attachment of monoclonal anti-α-fetoprotein antibodies (AFP-Ab), facilitating the detection of AFP antigens across 167–38 ng/mL (antibody) and 500–0 ng/mL (antigen) ranges. The limit of detection (LOD) for the antigens was determined to be 16.73 ng/mL. Unlike conventional SERS systems, this aqueous, surfactant-free platform exploits the intrinsic vibrational modes of AFP, enabling sensitive and rapid biomarker detection with strong potential for early cancer diagnostics. Full article

Lead-free perovskite variants have emerged as promising candidates due to their self-trapped exciton emission. However, in ASnX₃ systems, facile oxidation of Sn(II) to Sn(IV) yields A₂SnCl₆ vacancy-ordered derivatives. Paradoxically, despite possessing a direct bandgap, these variants exhibit diminished photoluminescence (PL). Doping engineering thus becomes essential for precise optical tailoring of A₂SnX₆ materials. Herein, through integrated first-principles calculations and spectroscopic analysis, we elucidate the luminescence mechanism in Te⁴⁺-doped (NH₄)₂SnCl₆ lead-free perovskites. Density functional theory, X-ray diffraction (XRD) patterns and X-ray photoelectron spectroscopy (XPS) confirm Te⁴⁺ substitution at Sn sites via favorable chemical potentials. Spectral interrogations, including absorption and emission profiles, reveal that the intense emission originates from the triplet STE recombination (³P₁ → ¹S₀) of Te centers. Temperature-dependent PL spectra further demonstrate strong electron–phonon coupling that induces symmetry-breaking distortions to stabilize STEs. Complementary electronic band structure and molecular orbital calculations unveil the underlying photophysical pathway. Leveraging these distinct thermal responses of PL intensity and peak position, 0.5%Te:(NH₄)₂SnCl₆ emerges as a highly promising candidate for non-contact, dual-parameter optical thermometry over an ultra-broad range (100–400 K). This work provides fundamental insights into the exciton dynamics and thermal engineering of optical properties in this material system, establishing its significant potential for advanced temperature-sensing applications. Full article

The continuous increase in solid waste poses a significant environmental challenge. Pyrolysis represents a crucial technology for the valorization of solid waste. As the primary product, biochar has found applications in numerous fields and garnered significant scientific interest. This study investigated the potential of NH₄Cl and FeCl₃ for modifying biochar. The resultant modified biochar achieved over 70% sulfamethoxazole (SMX) degradation within 30 min. The incorporation of NH₄Cl and FeCl₃ facilitated the formation of pyridinic nitrogen (N), graphitic nitrogen (N), and Fe(II) 1/2p, while the concomitant increase in persistent free radicals facilitated enhanced electron transfer rates. Notably, NH₄Cl/FeCl₃-modified biochar demonstrated superior efficacy compared with alternative activation techniques for real wastewater treatment. This study presents a novel material for persulfate (PDS)-based advanced oxidation processes, while also offering a cost-effective strategy for solid waste disposal. Full article

As internal combustion engines (ICEs) remain dominant in maritime transport, reducing their greenhouse gas (GHG) emissions is critical to meeting IMO’s decarbonization targets. Ammonia (NH₃) has gained attention as a carbon-free fuel due to its zero CO₂ emissions and high hydrogen density. However, its low flame speed and high ignition temperature pose combustion challenges. This study investigates the combustion and emission performance of NH₃-diesel dual-fuel engines, applying Response Surface Methodology (RSM) for multi-objective optimization of key operating parameters: ammonia fraction (AF: 0–30%), engine speed (1200–1600 rpm), and altitude (0–2000 m). Experimental results reveal that increasing AF led to a reduction in Brake Thermal Efficiency (BTE) from 39.2% to 37.4%, while significantly decreasing NO_x emissions by 82%, Total hydrocarbon emissions (THC) by 61%, and CO₂ emissions by 36%. However, the ignition delay increased from 8.2 to 10.8 crank angle degrees (CAD) and unburned NH₃ exceeded 6500 ppm, indicating higher incomplete combustion risks at high AF. Analysis of variance (ANOVA) confirmed AF as the most influential factor, contributing up to 82.3% of the variability in unburned NH₃ and 53.6% in NO_x. The optimal operating point, identified via desirability analysis, was 20% AF at 1200 rpm and sea level altitude, achieving a BTE of 37.4%, NO_x of 457 ppm, and unburned NH₃ of 6386 ppm with a desirability index of 0.614. These findings suggest that controlled NH₃ addition, combined with proper speed tuning, can significantly reduce emissions while maintaining engine efficiency in dual-fuel configurations. Full article

Purpose: Evaluation of predictors and outcomes in NSCLC patients treated with an immune checkpoint inhibitor (ICI) following a severe immune-related adverse event (irAE). Methods: We included all NSCLC patients receiving ≥1 ICI cycle and corticosteroids for CTCAE Grade ≥3 irAEs between 2017 and 2023 from three UK NHS teaching hospitals. Progression-free survival (PFS) and overall survival (OS) after the 1st irAE, best overall response (BOR) to ICI, and predictors of clinical benefit were evaluated. Kaplan–Meier, Cox and logistic regression models, and Wilcoxon tests were used. Results: We screened 1658 NSCLC patients and identified 80 eligible subjects. The majority of patients had metastatic (n = 50, 63%) vs. localized (n = 30, 37%) NSCLC. Most patients developed a single ≥Grade 3 irAE on 1st line ICI (n = 71, 89%). Overall, 14 (18%) patients developed 2nd irAEs, 7 after rechallenge with ICIs. In the complete cohort, median OS after 1st irAE was 15.84 months (95% CI, 12.45–26.91). Lower neutrophil-to-lymphocyte ratio (NLR), patients receiving >4 cycles of ICI or median duration of ICI of >2.76 months before 1st irAE were associated with improved OS (p < 0.05), the latter two with PFS (p < 0.05). Age, gender, stage, KRAS mutation, PD-L1 and ICI type were not associated with PFS or OS. Pneumonitis as 1st irAE had the worst PFS and OS (p < 0.05). Median starting corticosteroid dose of ≤60 mg for 1st irAE had an improved OS (p = 0.04). Post 1st irAE response associated with better PFS and OS (p < 0.05). Number and duration of irAEs and additional immunosuppressive agents (14% of patients) were not associated with PFS or OS. Conclusions: In ≥Grade 3 irAEs patients managed with corticosteroids, lower baseline NLR, longer ICI use, response to ICI after 1st irAE, and a ≤60 mg corticosteroid dose had promising outcomes. Full article

Uric acid (UA) detection is critical for human health monitoring, necessitating the development of electrochemical sensing electrodes suitable for physiological environments. This study evaluated four 2D conductive metal–organic frameworks (2D c-MOFs), namely Cu-HHTP, Ni-HHTP, Cu-HAB, and Ni-HAB, which share identical graphene-like 2D sheet structures but differ in π-conjugation extent and catalytic active centers [MX₄] (M = Cu or Ni; X = O or NH) as electrosensing electrodes. Electrochemical sensing performance was compared by detecting UA in phosphate-buffered saline (PBS). Herein, the Ni-HHTP electrode demonstrated superior sensitivity (6.79 μA·μM⁻¹·cm⁻²), the lowest oxidation potential (0.272 V), and the lowest detection limit (0.44 μM). Langmuir adsorption isotherm analysis revealed that the Ni-HHTP electrode possesses the highest surface coverage (Γ_A) (5061.16 pmol cm⁻²) and the most favorable Gibbs adsorption free energy (ΔG°) (−18.775 kJ mol⁻¹), indicating its strongest UA adsorption capacity and molecular interaction. This enhanced performance is attributed to the optimal synergy between [NiO₄] catalytic centers and extended ligand π-conjugation, facilitating greater analyte adsorption and electron transfer efficiency. This work establishes clear structure–performance relationships for 2D c-MOF electrodes in UA detection, providing key insights for designing advanced electrosensing materials. Full article

Despite increasing evidence that cigarette smoke is a significant source of indoor fine particulate matter (PM_2.5), quantitative emission factors (EFs) for PM_2.5 and its toxic chemical composition in mainstream (MS) and sidestream (SS) smoke are still not well defined. In this study, we employed a custom-designed chamber to separately collect MS (intermittent puff) and SS (continuous sampling) smoke from eleven cigarette models, representing six brands and two product types, under controlled conditions. PM_2.5 was collected on quartz-fiber filters and analyzed for carbon fractions (using the thermal–optical IMPROVE-A protocol), nine water-soluble inorganic ions (by ion chromatography), and twelve trace elements (via ICP-MS). SS smoke exhibited significantly higher mass fractions of total analyzed species (84.7% vs. 65.9%), carbon components (50.6% vs. 44.2%), water-soluble ions (17.1% vs. 13.7%), and elements (17.0% vs. 7.0%) compared to MS smoke. MS smoke is characterized by a high proportion of pyrolytic organic carbon fractions (OC₁–OC₃) and specific elements such as vanadium (V) and arsenic (As), while SS smoke shows elevated levels of elemental carbon (EC1), water-soluble ions (NH₄⁺, NO₃⁻), and certain elements like zinc (Zn) and cadmium (Cd). The toxicity-weighted distribution indicates that MS smoke primarily induces membrane disruption and pulmonary inflammation through semi-volatile organics and elements, whereas SS smoke enhances oxidative stress and cardiopulmonary impairment via EC-mediated reactions and secondary aerosol formation. The mean OC/EC ratio of 132.4 in SS smoke is an order of magnitude higher than values reported for biomass or fossil-fuel combustion, indicative of extensive incomplete combustion unique to cigarettes and suggesting a high potential for oxidative stress generation. Emission factors (µg/g cigarette) revealed marked differences: MS delivered higher absolute EFs for PM_2.5 (422.1), OC (8.8), EC (5.0), Na⁺ (32.6), and V (29.2), while SS emitted greater proportions of NH₄⁺, NO₃⁻, Cl⁻, and carcinogenic metals (As, Cd, Zn). These findings provide quantitative source profiles suitable for receptor-oriented indoor source-apportionment models and offer toxicological evidence to support the prioritization of comprehensive smoke-free regulations. Full article

Nitrogen (N) availability significantly influences plant metabolism and productivity. The aim of this study was to assess the effects of low N stress and subsequent N supplementation on key enzymes of nitrogen metabolism, nitrogen metabolism-related substances, and chlorophyll a fluorescence kinetic parameters in rice genotypes with different nitrogen utilization efficiencies. We used the Jijing 88 (low-N tolerant) and Xinong 999 (low-N sensitive) as test materials. During the seedling, tillering, and booting stages, the 1/2N and 1/4N treatments were restored to the 1N treatment level. Nine treatments were used in this experiment: CK (1N), A1 (1/2N), A2 (1/2N restored to 1N during the seedling stage), A3 (1/2N restored to 1N during the tillering stage), A4 (1/2N restored to 1N during the booting stage), B1 (1/4N), B2 (1/4N restored to 1N during the seedling stage), B3 (1/4N restored to 1N during the tillering stage), and B4 (1/4N restored to 1N during the booting stage). Key physiological responses, nitrogen compounds, enzymes activities, and chlorophyll a fluorescence kinetics were analyzed. Under low nitrogen conditions, the growth and nitrogen assimilation of rice were inhibited. Compared to XN 999, JJ 88 maintains higher levels of dry matter, nitrate reductase activity (NR), glutamine synthetase activity (GS), glutamate oxaloacetate transaminase activity (GOT), glutamate pyruvate transaminase activity (GPT), as well as nitrate (NO₃⁻) and ammonium (NH₄⁺) nitrogen contents. After N supplementation during the early growth stage, both JJ 88 and XN 999 exhibit recovery capabilities. However, in the late growth stage, JJ 88 demonstrates superior recovery capabilities. In addition to enhancing nitrogen metabolism levels, there is also an increase in the content of osmotic regulation substances such as soluble sugars, free amino acids, and proline, along with responses in chlorophyll fluorescence kinetic parameters. This was primarily manifested in the enhancement of performance index (PI_ABS, PI_total), and quantum yield (φ_EO, φ_RO, ψ_EO), which maintain photosynthetic performance and electron transport efficiency. The research findings indicated that reducing N supply during the early growth stage and restoring N levels in the later stage are beneficial for the recovery of low-nitrogen-tolerant rice varieties. Therefore, in the context of sustainable agricultural production, the breeding of low-nitrogen-tolerant rice varieties and the optimization of N fertilizer management are crucial. Full article

This study evaluated the inhibitory efficacy of sulphur dioxide, hydrogen peroxide, copper sulphate pentahydrate, chlorine-based formulations, a chlorine-free formulation, ethanol, and acetic acid against Cladosporium cladosporioides, Aspergillus niger, and Penicillium expansum. An in vitro inhibition test was employed to investigate the inhibitory properties. The results demonstrated different sensitivities of filamentous fungi to the inhibitors. All tested substances displayed fungicidal properties. Sulphur dioxide (40% NH₄HSO₃ solution) inhibited growth at a 4% v/v concentration. No minimum effective concentration was established for H₂O₂; only a 30% w/v solution inhibited P. expansum. CuSO₄·5H₂O completely inhibited fungal growth at 5% w/v solution, with 2.5% w/v also proving effective. For the chlorine-based product, 40% w/v solution (48 g∙L⁻¹ active chlorine) had the most substantial effect, though it only slowed growth, and NaClO solution completely inhibited growth at 2.35 g NaClO per 100 g of product (50% w/v solution). FungiSAN demonstrated fungicidal effects; however, the recommended dose was insufficient for complete inhibition. Ethanol exhibited the lowest efficacy, while the inhibitory threshold for CH₃COOH was found to be a 5% v/v solution. The findings of this study may serve as a basis for informed decision-making when selecting the most suitable product, depending on specific application conditions. Full article