Search Results (536)

The Zhunuo porphyry Cu deposit (2.9 Mt Cu @ 0.48%) in the Gangdese belt, southern Xizang, represents a key Miocene post-collisional system. This study integrates textural, major-, and trace-element analyses of pyrite from distinct alteration zones to unravel its hydrothermal evolution and metal precipitation mechanisms. Our study identifies four distinct pyrite types (Py1-Py4) that record sequential hydrothermal stages: main-stage Py2-Py3 formed at 354 ± 48 to 372 ± 43 °C (based on Se thermometry), corresponding to A and B vein formation, respectively, and late-stage Py4 crystallized at 231 ± 30 °C, coinciding with D-vein development. LA-ICP-MS data revealed pyrite contains diverse trace elements with concentrations mostly below 1000 ppm, showing distinct distribution patterns among different pyrite types (Py1-Py4). Elemental correlations revealed coupled behaviors (e.g., Au-As, Zn-Cd positive correlations; Mo-Sc negative correlation). Tellurium variability (7–82 ppm) records dynamic fO₂ fluctuations during system cooling. A comparative analysis of pyrite from the regional deposits (Xiongcun, Tiegelongnan, Bada, and Xiquheqiao) highlighted discriminative geochemical signatures: Zhunuo pyrite was enriched in Co-Bi-Ag-Pb (galena inclusions); Tiegelongnan exhibited the highest Cu but low Au-As; Xiquheqiao had the highest Au-As coupling; and Bada showed epithermal-type As enrichment. Partial Least Squares Discriminant Analysis (PLS-DA) identified Cu, As, and Bi as key discriminators for deposit types (VIP > 0.8), with post-collisional systems (Zhunuo and Xiquheqiao) showing intermediate Cu-Bi and elevated As versus arc-related deposits. This study establishes pyrite trace-element proxies (e.g., Se/Te, Co/Ni, and As-Bi-Pb) for reconstructing hydrothermal fluid evolution and proposes mineral-chemical indicators (Cu-As-Bi) to distinguish porphyry-epithermal systems in the Qinghai-Tibet Plateau. The results underscore pyrite’s utility in decoding metallogenic processes and exploration targeting in collisional settings. Full article

Pandemic preparedness is a complex of threat-agnostic countermeasures developed in advance which would be efficient against a future outbreak regardless of its causative agent, and broad-spectrum antivirals constitute a critical component of this complex. Plant polyphenols are known to suppress viruses of unrelated families by acting on multiple viral and cellular structures. We therefore searched for broad-spectrum antivirals among polyphenols that have been confirmed as safe to humans. The ellagitannin geraniin and galloylglucose constituents of the drug Rutan (1,2,3,4,6-penta-O-galloyl-β-D-glucose [R5], 3-bis-O-galloyl-1,2,4,6-tetra-O-galloyl-β-D-glucose [R6], 2,4-bis-O-galloyl-1,3,6-tri-O-galloyl-β-D-glucose [R7], 2,3,4-bis-O-galloyl-1,6-di-O-galloyl-β-D-glucose [R8]) were isolated from Geranium sanguineum and sumac (Rhus coriaria), respectively. We revealed their activity towards herpes simplex viruses (HSV-1 and HSV-2), human cytomegalovirus (CMV), and the Epstein–Barr virus (EBV). R5 suppressed HSV-1 and HSV-2 with equal efficiency, while Rutan and R7 were more active against HSV-1, and geraniin against HSV-2. Rutan and R5 also inhibited the intracellular replication of CMV and EBV (contrary to our expectations, geraniin and polyphenols R6–R8 showed no activity). Thus, we have shown for the first time that sumac polyphenols are capable of suppressing—in addition to HIV, influenza virus, and SARS-CoV-2—the reproduction of representatives of all three Orthoherpesviridae subfamilies, meeting the criteria for further development as broad-spectrum antivirals. Full article

La³⁺/Bi³⁺ co-doped BaTiO₃ ceramics were synthesized via ball milling followed by heat treatment at 1200 °C according to the Ba_1−3xLa_2xTi_1−3xBi_4xO₃ formula, with dopant levels ranging from x = 0.0 to 0.006. X-ray diffraction and Rietveld refinement confirmed a ferroelectric tetragonal phase for all compositions, with the highest tetragonality (c/a = 1.009) observed for x = 0.001 exceeding that of pure BaTiO₃ (1.0083). High-resolution electron microscopy analysis revealed faceted particles with mean sizes between 362.5 nm and 488.3 nm. Low-doped samples (x = 0.001 and 0.002) exhibited higher permittivity than undoped BaTiO₃, with the maximum dielectric constant (ε_r = 2469.0 at room temperature and 7499.7 at the Curie temperature) recorded for x = 0.001 at 1 kHz. At x = 0.006, minimal permittivity variation indicated a stable dielectric response. A decrease in the Curie temperature was observed with increasing doping levels, indicating a progressive tendency toward the cubic phase. Critical exponent γ values (0.94–1.56) indicated a sharp phase transition for low-doped samples and a diffuse transition for highly doped BaTiO₃. These results showed that La³⁺/Bi³⁺ co-doping effectively tunes the structural and dielectric properties of BaTiO₃ ceramics. Full article

Polyurea grease (PU) is widely used in the lubrication of heavy machinery, but it can still suffer from structural or performance degradation under extreme conditions such as high temperatures and heavy loads. This study successfully synthesized a hybrid polyurea grease (LiTFSI-PU) by incorporating lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) into polyurea matrix. LiTFSI coordinates with the carbonyl groups (C=O) in the thickener molecules to form weakly Lewis acidic complex, thereby reinforcing the soap fiber network structure. As a result, LiTFSI-PU exhibits increased apparent viscosity under shear. The tribological properties of LiTFSI-PU were evaluated under both ambient and elevated temperature conditions. At a load of 200 N and 150 °C, the average coefficient of friction for the 3 wt% LiTFSI-PU formulation was 0.094, which is 32.3% lower than that of the baseline polyurea grease (PU), while the wear volume was reduced by 77.5%. XPS and FIB-STEM/EDS analyses confirmed that LiTFSI-PU forms a multicomponent protective film in situ during friction, which simultaneously shields the substrate and provides lubrication. The additive strategy proposed in this work offers novel insights for the development of high-performance lubricants suitable for extreme thermomechanical conditions. Full article

This research successfully synthesized a novel n-n heterojunction Bi₂O₂CO₃/AgVO₃ nanocomposite photocatalyst via the in situ chemical deposition process. Characterization results strongly confirmed the formation of a tight heterojunction at the Bi₂O₂CO₃/AgVO₃ interface. The nanocomposite exhibited characteristic XRD peaks and FT-IR vibrational modes of both Bi₂O₂CO₃ and AgVO₃ simultaneously. Electron microscopy images revealed AgVO₃ nanorods tightly and uniformly loaded onto the surface of Bi₂O₂CO₃ nanosheets. Compared to the single-component Bi₂O₂CO₃, the composite photocatalyst exhibited a red shift in its optical absorption edge to the visible region (515 nm) and a decrease in bandgap energy to 2.382 eV. Photoluminescence (PL) spectra demonstrated the lowest fluorescence intensity for the nanocomposite, indicating that the recombination of photogenerated electron–hole pairs was suppressed. After 90 min of visible-light irradiation, the degradation efficiency of Bi₂O₂CO₃/AgVO₃ toward methylene blue (MB) reached up to 99.55%, with photodegradation rates 2.51 and 2.79 times higher than those of Bi₂O₂CO₃ and AgVO₃, respectively. Furthermore, the nanocomposite exhibited excellent cycling stability and reusability. MB degradation was gradually enhanced with increasing the photocatalyst dosage and decreasing initial MB concentration. Radical trapping experiments and absorption spectroscopy of the MB solution revealed that reactive species h⁺ and ·O₂⁻ could destroy and decompose the chromophore groups of MB molecules effectively. The possible mechanism for enhancing photocatalytic performance was suggested, elucidating the crucial roles of charge carrier transfer and active species generation. Full article

Understanding how solvents influence the luminescence behavior of Cu(I) complexes is crucial for designing advanced optical sensors. This study reports the synthesis, structures and photophysical investigation of an 8-hydroxyquinoline-functionalized 1H-imidazo[4,5-f][1,10]phenanthroline ligand, ipqH₂, and its four Cu(I) complexes with diphosphine co-ligands. Photoluminescence studies demonstrated distinct solvent-dependent excited-state mechanisms. In DMSO/alcohol mixtures, free ipqH₂ exhibited excited-state proton transfer (ESPT) and enol-keto tautomerization, producing dual emission at about 447 and 560 nm, while the complexes resisted ESPT due to hydrogen bond blocking by PF₆⁻ anions and Cu(I) coordination. In DMSO/H₂O, aggregation-caused quenching (ACQ) and high-energy O–H vibrational quenching dominated, but complexes 1 and 2 showed a significant red-shifted emission (569–574 nm) with high water content due to solvent-stabilized intra-ligand charge transfer and metal-to-ligand charge transfer ((IL+ML)CT) states. In DMSO/DMF, hydrogen bond competition and solvation-shell reorganization led to distinct responses: complexes 1 and 3, with flexible bis[(2-diphenylphosphino)phenyl]ether (POP) ligands, displayed peak splitting and (IL + ML)CT redshift emission (501 ⟶ 530 nm), whereas complexes 2 and 4, with rigid 9,9-dimethyl-4,5-bis(diphenylphosphino)-9H-xanthene (xantphos), showed weaker responses. The flexibility of the diphosphine ligand dictated DMF sensitivity, while the coordination, the hydrogen bonds between PF₆⁻ anions and ipqH₂, and water solubility governed the alcohol/water responses. This work elucidates the multifaceted solvent-responsive mechanisms in Cu(I) complexes, facilitating the design of solvent-discriminative luminescent sensors. Full article

In the present study three composite materials based on iron in combination with bismuth, copper or lithium carbonates FeNO₃@Li₂CO₃ (SFL), FeNO₃@CuCO₃ (SFC), and FeNO₃@(BiO)₂CO₃ (SFB) were synthesized by coprecipitation. The purpose was to obtain materials that possess targeted adsorbent properties for the recovery of silver ions from aqueous solutions. After synthesis, to emphasize the adsorptive qualities of materials for the recovery of silver ions, the synthesized composite materials, as well as those doped with silver ions following the adsorption process (SFL-Ag, SFC-Ag, and SFB-Ag), were characterized and several adsorption-specific parameters were examined, including temperature, contact time, pH, adsorbent dose, and the initial concentration of silver ions in solution. Subsequently, the ideal adsorption conditions were determined to be as follows: pH > 4, contact time 60 min, temperature 298 K, and solid–liquid ratio (S–L) of 0.1 g of adsorbent to 25 mL of Ag (I) solution for all three materials. The Langmuir model properly fits the experimental equilibrium data of the adsorption process; however, the Ho–McKay model closely represents the adsorption kinetics. The maximum adsorption capacities of the materials, 19.7 mg Ag(I)/g for SFC, 19.3 mg Ag(I)/g for SFB, and 19.9 mg Ag(I)/g for SFL, are comparable. The adsorption mechanism is physical in nature, as evidenced by the activation energies of 1.6 kJ/mol for SFC, 4.15 kJ/mol for SFB, and 1.32 kJ/mol for SFL. The highest Ag(I) concentration used for doping all three materials in the study was 150 mg Ag(I)/L. The process is endothermic, spontaneous, and takes place at the interface between the adsorbent and the adsorbate, according to thermodynamic theory. Subsequently, the antimicrobial activity against Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, and Candida albicans microorganisms was evaluated by rate of inhibition assessment. The SFC-Ag material showed a percentage of 100% inhibition with respect to the positive control for each microorganism. All synthetized materials have better efficiency as antifungal agents. Full article

Previously unobserved (carbamoyl)disulfanyl chlorides were prepared by (i) addition of limiting aromatic secondary amine to (chlorocarbonyl)disulfanyl chloride; (ii) Harris reactions of sulfur dichloride with appropriate O-alkyl N-methyl-N-arylthiocarbamates; and (iii) regiospecific chlorolysis of bis(N-methyl-N-arylcarbamoyl)disulfanes. The newly synthesized unstable species were observed in situ by ¹H NMR and were trapped with alkenes, thiocarbamates, and thiols using methods precedented by the chemistry of analogous (carbamoyl)sulfenyl chlorides. Furthermore, each of the trapped products was synthesized by an alternate route, reinforcing conclusions about their structures. While (N-methyl-N-phenylcarbamoyl)disulfanyl chloride was unstable and decomposed quickly or cyclized intramolecularly, introduction of the N,2,6-trimethylphenyl moiety led to significantly improved stability. As part of this study, an interesting, unexpectedly stable 1,2,4-dithiazinone was discovered and its structure was established by X-ray crystallography. The new heterocycle, with its twisted out-of-plane disulfide bond in a six-membered ring, readily donated a sulfur atom to triphenylphosphine; this reaction resulted in the formation of triphenylphosphine sulfide, along with the corresponding highly stable heterocycle in which the single sulfur that remains is part of a planar five-membered ring, fused to a co-planar aryl moiety. Full article

Background/Objectives: The maintenance of cerebral blood flow (CBF) by managing blood pressure and brain cell activity and avoiding hypocapnia is important when administering anesthesia to patients with dementia. This study aimed to evaluate CBF during general anesthesia in elderly patients with severe dementia while maintaining their physiological parameters within an adequate range. Methods: The patients were anesthetized within a set range of parameters without affecting CBF (mean arterial pressure [MAP] > 50 mmHg; bispectral index [BIS] > 20; percutaneous arterial oxygen saturation [SpO₂] > 95%; end-tidal CO₂ [etCO₂] 35–40 mmHg). The normalized tissue hemoglobin index (nTHI), which reflects CBF, was measured using near-infrared spectroscopy. The parameters were compared between patients with severe dementia (n = 13) and those without cognitive impairment (n = 13). Results: There were no differences in patient background. A similar decline in MAP and BIS values was observed in both groups, but the values remained within the set range. The nTHI decreased significantly to 0.60 in the dementia group and to 0.79 in the non-dementia group after the start of the treatment (p ≤ 0.049). Even when the MAP, BIS, SpO₂, and etCO₂ values were maintained in their adequate ranges during general anesthesia, the nTHI decreased by 40% in the dementia group. Conclusions: These findings indicate that CBF greatly decreases in elderly patients with severe dementia during general anesthesia. Full article

Bismuth-based oxyfluorides (BiO_xF_3−2x) have recently emerged as promising photocatalysts due to their unique electronic structures and tunable physicochemical properties. This review provides a comprehensive overview of these materials, focusing on their crystal structures, band gap characteristics, and photocatalytic performance. Particular attention is given to BiOF, Bi₇O₅F₁₁, and β-BiO_xF_3−2x, highlighting the influence of fluorine’s high electronegativity and internal electric fields on charge separation and light absorption. The potential of Aurivillius-type oxyfluorides is also discussed. Structural modifications, such as the introduction of oxygen vacancies, morphology control, and metal/non-metal doping, are examined for their effects on photocatalytic efficiency. Furthermore, various synthesis techniques and heterojunction engineering strategies involving semiconductors, carbon-based materials, and metal nanoparticles are explored to improve light harvesting and reduce charge recombination. Applications in pollutant degradation and CO₂ photoconversion are reviewed, demonstrating the versatility of these materials. Despite their promise, the challenges associated with phase identification and composition control are also emphasized, underlining the need for rigorous structural characterization. Future directions for optimizing the photocatalytic activity of bismuth-based oxyfluorides are outlined, focusing on strategies to enhance their performance. Full article

Developing highly efficient photocatalysts for CO₂ reduction remains a great challenge. The large band gap and poor charge carrier dynamics are the major factors limiting the performance of Bi₄Ti₃O₁₂ (BTO). Herein, a series of La-doped Bi₄Ti₃O₁₂ (BLa_xTO) nanosheets were synthesized and further modified by NaBH₄ hydrogenation to create surface defect-rich H-BLa_XTO nanosheets. Characterizations and theoretical calculations confirmed that the synergistic effect of La doping and hydrogenation significantly enhanced visible-light absorption, promoted charge separation, and improved the electron reduction capacity. When applied to photocatalytic CO₂ reduction, the H-BLa_0.2TO catalyst achieved a superior CH₃OH production rate of 7.90 μmol·g⁻¹·h⁻¹, which is 5.6 times higher than that of pristine Bi₄Ti₃O₁₂. Moreover, the H-BLa_0.2TO catalyst maintained excellent stability over four consecutive cycles. This study offers an integrated strategy for constructing high-performance bismuth-based photocatalysts through elemental doping and defect engineering. Full article

Perovskite-type CaBiO₂Cl with a unique layered Sillen X1 structure exhibits great potential as an efficient visible-light photocatalyst. In this study, CaBiO₂Cl was synthesized through calcination at 800 °C and subsequently composited with varying amounts of g-C₃N₄ to optimize photocatalytic performance. The prepared catalysts were characterized by multiple techniques to confirm their structural and compositional features. Under visible-light irradiation, the photocatalytic activities toward Rh6G degradation were systematically evaluated using UV–vis PDA and EPR analyses. To further elucidate the degradation mechanism, radical scavenger experiments were conducted to identify the reactive species generated during the photodegradation process. Kinetic analysis revealed that the reaction rate constant (k) of pure CaBiO₂Cl was 0.0525 h⁻¹, while that of pure g-C₃N₄ was 0.0423 h⁻¹. Notably, the CaBiO₂Cl/10 wt% g-C₃N₄ composite exhibited an enhanced k value of 0.0568 h⁻¹, which is 1.1 and 1.3 times higher than those of CaBiO₂Cl and g-C₃N₄, respectively. Furthermore, under ambient conditions (25 °C, 1 atm), the CO₂-to-CH₄ photocatalytic conversion efficiency of the CaBiO₂Cl/10 wt% g-C₃N₄ composite reached 0.5652 μmol g⁻¹ h⁻¹. These findings demonstrate that CaBiO₂Cl-based composite photocatalysts not only achieve superior visible-light photocatalytic activity but also exhibit excellent stability, highlighting their potential for environmental remediation and alignment with the principles of green chemistry. Full article

Developing a highly efficient leveler in acid copper electroplating solution is one of the primary tasks necessary for achieving superconformal filling of microvias and interconnections in printed circuit boards (PCBs). Two triethylenediamine-based Gemini levelers, both with terminal quaternary ammonium groups, are synthesized and named as GL1 (C8) after reaction of triethylenediamine with 1,8-dichlorooctane and GL2 (C6 with two C–O linkages) after triethylenediamine with 1,2-bis(2-chloroethoxy) ethane. Electrochemical experiments indicate that at 100 rpm and 1000 rpm GL2 combines with a suppressor and accelerator to exhibit greater potential difference of 23 mV than GL1 in 9 mV for Cu²⁺ reduction, demonstrating that GL2 has a stronger synergistic convection-dependent adsorption (CDA) effect. Microvias copper electroplating experiments confirm that acid copper electroplating solution containing GL2 achieve more effective superconformal void-free filling as it results in FP = 96.1%, while the solution containing GL1 results in FP = 70%. Theoretical calculations indicate that adsorption energy of GL2 is −1037.54 kJ·mol⁻¹, which is lower than GL1 (−1019.06 kJ·mol⁻¹). GL2 displays lower electron density compared to GL1, which facilitates its displacement by accelerator at the bottom. The lower adsorption energy of GL2 suggests the weaker adsorption ability and the stronger CDA behavior. Full article

High-performance batteries for military and extreme environment applications require alternatives to conventional liquid lithium-ion batteries (LIBs), which suffer from poor low-temperature performance and safety risks. All-solid-state lithium batteries (ASSLBs) offer enhanced safety and superior low-temperature capability. In this work, we designed and fabricated composite solid-state electrolytes using polyvinylidene fluoride (PVDF) and polyacrylic acid (PAA) as polymer matrices, N,N-dimethylformamide (DMF) as the solvent, and lithium bis(trifluoromethane sulfonimide) (LiTFSI) as the lithium salt. Composite solutions with varying PAA mass ratios were prepared. Advanced three-dimensional (3D) printing technology enabled the rapid and precise fabrication of electrolyte membranes. An ionic conductivity of about 2.71 × 10⁻⁴ S cm⁻¹ at 25 °C, high mechanical strength, and good thermal properties can be achieved through component and 3D printing process optimization. Assembled LiCoO₂||PVDF@PAA||Li ASSLBs delivered an initial discharge capacity of 165.3 mAh/g at 0.1 mA cm⁻² (room temperature), maintaining 98% capacity retention after 300 cycles. At 0 °C, these cells provided 157.4 mAh/g initial capacity with 85% retention over 100 cycles at 0.1 mA cm⁻². This work identifies the optimal PAA ratio for enhanced electrochemical performance and demonstrates the viability of 3D printing for advanced ASSLB manufacturing. Full article

The reaction of the bulky ligand 1,2-bis-(di-tert-butylphosphinomethyl)benzene, 1 with [Ni(DME)Cl₂], 3, DME = 1,2-dimethoxyethane, at room temperature over extended periods, affords the new blue Zwitterionic complex [2-(C₆H₄-CH₂P(H)^tBu₂-1-(CH₂P^tBu₂NiCl₃)], 4, which contains a phosphonium group and an anionic nickel trichloride. This complex decomposes in alcohols such as methanol and the solution turns yellow. A discussion of the possible mechanism leading to the observed product is presented. Key to this is identification of the source of the phosphonium proton, which we speculated to arise from trace water in the initial nickel complex. To prove that trace water was present in [Ni(DME)Cl₂], a sample of this precursor was reacted under similar condition with anhydrous DMF alone. In addition to the known complex [Ni(DMF)₆)]²⁺[NiCl₄]²⁻, 5, we identified the trans-diaqua complex [Ni(Cl)₂(H₂O)₂(DMF)₂], 6, which proved the presence of trace water. Interestingly in dimethylformamide, [2-(C₆H₄-CH₂P(H)^tBu₂-1-(CH₂P^tBu₂NiCl₃)] exhibits thermochromic properties: an solution that is pale blue at ambient temperature reversibly changes colour to yellow upon cooling. This behaviour is specific to DMF and is related to the solvato-chromic behaviour exhibited by related DMF–nickel complexes. A discussion of the NMR spectra of compound 4 in a range of solvents is presented. The structures of the previously prepared molybdenum complex, [1,2-(C₆H₄-CH₂P^tBu₂)₂Mo(CO)₄] and the bis-(phosphine sulphide) of the ligand, [1,2-(C₆H₄-H₂P(S)^tBu₂)₂], 5, are described for structural comparative purposes. Full article