Search Results (893)

Graphene quantum dots (GQDs) obtained by microwave-induced pyrolysis of glutamic acid and triethylenetetramine (trien) are fairly stable, emissive, water-soluble, and positively charged nano-systems able to interact with negatively charged meso-tetrakis(4-sulfonatophenyl) porphyrin (TPPS₄). The stoichiometric control during the preparation affords a supramolecular adduct, GQDs@TPPS₄, that exhibits a double fluorescence emission from both the GQDs and the TPPS₄ fluorophores. These supramolecular aggregates have an overall negative charge that is responsible for the condensation of cations in the nearby aqueous layer, and a three-fold acceleration of the metalation rates of Cu²⁺ ions has been observed with respect to the parent porphyrin. Addition of various metal ions leads to some changes in the UV/Vis spectra and has a different impact on the fluorescence emission of GQDs and TPPS₄. The quenching efficiency of the TPPS₄ emission follows the order Cu²⁺ > Hg²⁺ > Cd²⁺ > Pb²⁺ ~ Zn²⁺ ~ Co²⁺ ~ Ni²⁺ > Mn²⁺ ~ Cr³⁺ >> Mg²⁺ ~ Ca²⁺ ~ Ba²⁺, and it has been related to literature data and to the sitting-atop mechanism that large transition metal ions (e.g., Hg²⁺ and Cd²⁺) exhibit in their interaction with the macrocyclic nitrogen atoms of the porphyrin, inducing distortion and accelerating the insertion of smaller metal ions, such as Zn²⁺. For the most relevant metal ions, emission quenching of the porphyrin evidences a linear behavior in the micromolar range, with the emission of the GQDs being moderately affected through a filter effect. Deliberate pollution of the samples with Zn²⁺ reveals the ability of the GQDs@TPPS₄ adduct to detect sensitively Cu²⁺, Hg^2+, and Cd²⁺ ions. Full article

Rapid socio-economic development and the impact of human activities have exerted tremendous pressure on the groundwater system of the Dawen River Basin (DRB), the largest tributary in the middle and lower reaches of the Yellow River. Hydrochemical studies on the DRB have largely centered on the upstream Muwen River catchment and downstream Dongping Lake, with some focusing solely on karst groundwater. Basin-wide evaluations suggest good overall groundwater quality, but moderate to severe contamination is confined to the lower Dongping Lake area. The hydrogeologically complex mid-reach, where the Muwen and Chaiwen rivers merge, warrants specific focus. This region, adjacent to populous areas and industrial/agricultural zones, features diverse aquifer systems, necessitating a thorough analysis of its hydrochemistry and origins. This study presents an integrated hydrochemical, isotopic investigation and EWQI evaluation of groundwater quality and formation mechanisms within the multiple groundwater types of the central DRB. Central DRB groundwater has a pH of 7.5–8.2 (avg. 7.8) and TDSs at 450–2420 mg/L (avg. 1075.4 mg/L) and is mainly brackish, with Ca²⁺ as the primary cation (68.3% of total cations) and SO₄²⁻ (33.6%) and NO₃⁻ (28.4%) as key anions. The Piper diagram reveals complex hydrochemical types, primarily HCO₃·SO₄-Ca and SO₄·Cl-Ca. Isotopic analysis (δ²H, δ¹⁸O) confirms atmospheric precipitation as the principal recharge source, with pore water showing evaporative enrichment due to shallow depths. The Gibbs diagram and ion ratios demonstrate that hydrochemistry is primarily controlled by silicate and carbonate weathering (especially calcite dissolution), active cation exchange, and anthropogenic influences. EWQI assessment (avg. 156.2) indicates generally “good” overall quality but significant spatial variability. Pore water exhibits the highest exceedance rates (50% > Class III), driven by nitrate pollution from intensive vegetable cultivation in eastern areas (Xiyangzhuang–Liangzhuang) and sulfate contamination from gypsum mining (Guojialou–Nanxiyao). Karst water (26.7% > Class III) shows localized pollution belts (Huafeng–Dongzhuang) linked to coal mining and industrial discharges. Compared to basin-wide studies suggesting good quality in mid-upper reaches, this intensive mid-reach sampling identifies critical localized pollution zones within an overall low-EWQI background. The findings highlight the necessity for aquifer-specific and land-use-targeted groundwater protection strategies in this hydrogeologically complex region. Full article

A 12-membered pyridinophane scaffold containing two pyridine and two tertiary amine residues is examined as a prototype ligand (^tBuN4) for supporting nitrene transfer to olefins. The known [(^tBuN4)M^II(MeCN)₂]²⁺ (M = Mn, Fe, Co, and Ni) and [(^tBuN4)Cu^I(MeCN)]⁺ cations are synthesized with the hexafluorophosphate counteranion. The aziridination of para-substituted styrenes with PhI=NTs (Ts = tosyl) in various solvents proved to be high yielding for the Cu(I) and Cu(II) reagents, in contrast to the modest efficacy of all other metals. For α-substituted styrenes, aziridination is accompanied by products of aziridine ring opening, especially in chlorinated solvents. Bulkier β-substituted styrenes reduce product yields, largely for the Cu(II) reagent. Aromatic olefins are more reactive than aliphatic congeners by a significant margin. Mechanistic studies (Hammett plots, KIE, and stereochemical scrambling) suggest that both copper reagents operate via sequential formation of two N–C bonds during the aziridination of styrene, but with differential mechanistic parameters, pointing towards two distinct catalytic manifolds. Computational studies indicate that the putative copper nitrenes derived from Cu(I) and Cu(II) are each associated with closely spaced dual spin states, featuring high spin densities on the nitrene N atom. The computed electrophilicity of the Cu(I)-derived nitrene reflects the faster operation of the Cu(I) manifold. Full article

The water level of Lake Neuchâtel (Switzerland) was lowered 150 years ago, initiating soil formation and colonization by riparian forests of the previously submerged areas. Although the soils of the whole area are young and have probably quite similar parent material (lacustrine sediments and moraine), the present soils show a large diversity of horizon structures and contents. The aim of this study is to describe the respective processes of accumulation, integration, and stabilization of organic matter and assess the soil variables influenced by these processes in the various types of riparian forests with different moisture levels. The investigation employed a semi-quantitative, holistic approach that combined field observations, laboratory analyses, and micromorphological examination of soil thin sections. The results indicate that the accumulation and stabilization of organic matter are primarily governed by physicochemical factors associated with the parent material, particularly soil texture and calcium cation saturation. Soil moisture and groundwater elevation were found to mainly influence biological activity and vegetation types. Additionally, the incorporation of organic matter is affected by both soil texture and bioturbation processes. Overall, this study underscores the complexity of the mechanisms regulating organic matter dynamics in young soils. Full article

To enhance the specific energy and rate performance of lithium primary batteries, the development of advanced cathode materials with superior electrochemical properties is essential. Fluorides, composed of light fluorine elements and multivalent cations, exhibit multi-electron reaction characteristics, possess a high theoretical voltage, and demonstrate high discharge-specific energy. However, owing to fluorine’s high electronegativity, which leads to the formation of strong ionic bonds with other elements, most fluorides exhibit poor electronic conductivity, thereby constraining their electrochemical performance when used as cathode materials. Copper fluoride (CuF₂) exhibits a high theoretical specific capacity and discharge voltage but is constrained by its large bandgap, poor electronic conductivity, and difficulties in synthesizing anhydrous CuF₂ materials, which significantly limit its electrochemical activity. In this study, zinc (Zn) was chosen as a dopant for copper fluoride. By combining theoretical calculations with experimental validation, the impacts of Zn doping on the structural stability and electrochemical performance of copper fluoride were comprehensively analyzed. The resultant highly active Zn-doped copper fluoride achieved a discharge specific capacity of 528.6 mAh/g at 0.1 C and 489.1 mAh/g at 1 C, showcasing superior discharge-specific energy and good rate performance. This material holds great potential as a promising cathode candidate for lithium batteries, providing both high specific energy and power density. Full article

Transient receptor potential classical or cation channels (TRPCs) are integral to tumor biology, particularly in maintaining Ca²⁺ homeostasis within cancer cells. TRPC5, a pH-sensitive member of this family, may act as a signaling molecule in the altered microenvironment of solid tumors, which are characterized by an inverted pH-gradient—with decreased extracellular and increased intracellular pH—that promotes tumor progression. This study addresses a gap in the field, as there is currently limited research on TRPC5, particularly regarding its potential role as a tumor marker. While TRPCs are known to be involved in cancer biology, the specific role of TRPC5 in solid tumors, including its potential role as a diagnostic marker, remains largely unexplored. This study is the first to examine TRPC5 expression profiles in common skin cancers, including basal cell carcinoma (BCC), squamous cell carcinoma (SCC), malignant melanoma (MM), and nevus cell nevi (NCN). Our findings reveal that the frequency of TRPC5 expression in BCC is significantly lower compared to SCC and epidermal portions of NCN and MM. These results suggest that TRPC5 could serve as an immunohistochemical marker to distinguish SCC from BCC. Additionally, this study lays the groundwork for future research into the role of TRPC5 in tumor progression and metastasis, especially since BCCs, which rarely metastasize, are predominantly negative for TRPC5. Full article

Previous investigations into lithology-driven weathering processes have largely emphasized large-scale spatial assessments, while studies targeting small watershed scales remain scarce. This study investigated two adjacent watersheds (Chengjia: CJ; Datan: DT) under comparable climatic conditions in Guangdong, China, using hydrochemistry and stable carbon isotopes. The CJ watershed exhibited low-TDS (20–66 mg/L) HCO₃-Na·Ca-type waters dominated by silicate weathering, whereas the DT watershed displayed high-TDS (70–278 mg/L) HCO₃-Ca-type waters, indicative of mixed carbonate–silicate weathering. Results of carbon isotope composition of dissolved inorganic carbon confirmed that H₂CO₃-driven weathering was the dominant mechanism in both watersheds. In the CJ watershed, 79.5% of dissolved cations in surface water originated from silicate weathering, yielding a CO₂ consumption rate (CCR) of 0.28 × 10⁶ mol/km²/yr, while carbonate weathering was negligible. Conversely, in the DT watershed, 86.4% of dissolved cations were derived from carbonate weathering, yielding a CCR of 1.94 × 10⁶ mol/km²/yr, whereas silicate weathering contributed only 10.3% of cations with a CCR of 0.23 × 10⁶ mol/km²/yr. The chemical weathering rate of carbonate can be up to 10 times that of silicate, resulting in a larger CCR. This study demonstrated the key impact of lithology on hydrochemical characteristics and CO₂ consumption at small watershed scales. Full article

The new mineral achyrophanite (K,Na)₃(Fe³⁺,Ti,Al,Mg)₅O₂(AsO₄)₅ was found in high-temperature sublimates of the Arsenatnaya fumarole at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. It is associated with aphthitalite-group sulfates, hematite, alluaudite-group arsenates (badalovite, calciojohillerite, johillerite, nickenichite, hatertite, and khrenovite), ozerovaite, pansnerite, arsenatrotitanite, yurmarinite, svabite, tilasite, katiarsite, yurgensonite, As-bearing sanidine, anhydrite, rutile, cassiterite, and pseudobrookite. Achyrophanite occurs as long-prismatic to acicular or, rarer, tabular crystals up to 0.02 × 0.2 × 1.5 mm, which form parallel, radiating, bush-like, or chaotic aggregates up to 3 mm across. It is transparent, straw-yellow to golden yellow, with strong vitreous luster. The mineral is brittle, with (001) perfect cleavage. D_calc is 3.814 g cm^–3. Achyrophanite is optically biaxial (+), α = 1.823(7), β = 1.840(7), γ = 1.895(7) (589 nm), 2V (meas.) = 60(10)°. Chemical composition (wt.%, electron microprobe) is: Na₂O 3.68, K₂O 9.32, CaO 0.38, MgO 1.37, MnO 0.08, CuO 0.82, ZnO 0.48, Al₂O₃ 2.09, Fe₂O₃ 20.42, SiO₂ 0.12, TiO₂ 7.35, P₂O₅ 0.14, V₂O₅ 0.33, As₂O₅ 51.88, SO₃ 1.04, and total 99.40. The empirical formula calculated based on 22 O apfu is Na_1.29K_2.15Ca_0.07Mg_0.34Mn_0.01Cu_0.11Zn_0.06Al_0.44Fe³⁺_2.77Ti_1.00Si_0.02P_0.02S_0.14V_0.04As_4.90O₂₂. Achyrophanite is orthorhombic, space group P222₁, a = 6.5824(2), b = 13.2488(4), c = 10.7613(3) Å, V = 938.48(5) ų and Z = 2. The strongest reflections of the PXRD pattern [d,Å(I)(hkl)] are 5.615(59)(101), 4.174(42)(022), 3.669(31)(130), 3.148(33)(103), 2.852(43)(141), 2.814(100)(042, 202), 2.689(29)(004), and 2.237(28)(152). The crystal structure of achyrophanite (solved from single-crystal XRD data, R = 4.47%) is unique. It is based on the octahedral-tetrahedral M-T-O pseudo-framework (M = Fe³⁺ with admixed Ti, Al, Mg, Na; T = As⁵⁺). Large-cation A sites (A = K, Na) are located in the channels of the pseudo-framework. The achyrophanite structure can be described as stuffed, with the defect heteropolyhedral pseudo-framework derivative of the orthorhombic Fe³⁺AsO₄ archetype. The mineral is named from the Greek άχυρον, straw, and φαίνομαι, to appear, in allusion to its typical straw-yellow color and long prismatic habit of crystals. Full article

Complex antimony pyrochlores Bi_2.7M_0.46Ni_0.70Sb₂O_10+Δ (M = Zn, Mg) were synthesized from oxide precursors, using the solid-state reaction method. For each composition variant, the pyrochlore phase formation process was studied during solid-state synthesis in the range of 500–1050 °C. The influence of zinc and magnesium on the phase formation process was established. The interaction of oxide precursors occurs at a temperature of 600 °C and higher, resulting in the formation of bismuth stibate (Bi₃SbO₇) as a binary impurity phase. Oxide precursors, including bismuth(III) and antimony(III,V) oxides, are fixed in the samples up to 750 °C, at which point the intermediate cubic phase Bi₃M_2/3Sb_7/3O₁₁ (sp. gr. Pn-3, M = Zn, Ni) is formed in the zinc system. Interacting with transition element oxides, it is transformed into pyrochlore. An intermediate phase with the Bi_4.66Ca_1.09VO_10.5 structure (sp. gr. Pnnm) was found in the magnesium system. The unit cell parameter of pyrochlore for two samples has a minimum value at 800 °C, which is associated with the onset of high-temperature synthesis of pyrochlore. The synthesis of phase-pure pyrochlores is confirmed by high-resolution Raman spectroscopy. The data interpretation showed that the cations in Ni/Zn pyrochlore are more likely to be incorporated into bismuth positions than in Ni/Mg pyrochlore. The nickel–magnesium pyrochlore is characterized by a low-porosity microstructure, with grain sizes of up to 3 μm, according to SEM data. Zinc oxide has a sintering effect on ceramics. Therefore, the grain size in ceramics is large and varies from 2 to 7 μm. Full article

Phenylene-based bis-oxamate polydentate ligands offer a unique opportunity for creating a large variety of coordination compounds, in which paramagnetic metal ions are strongly magnetically coupled. The employment of imino nitroxyl (IN) radicals as supplementary ligands confers numerous benefits, including the strong ferromagnetic interaction between Ni and IN. Furthermore, the chelating IN can act as a capping ligand, thereby impeding the formation of coordination polymers. In this study, we present the molecular and crystal structure and experimental and theoretical magnetic behavior of an exceptional neutral trinuclear complex [Ni(L³⁻)₂(IN)₃]∙5CH₃OH (1) (L is N,N′-1,3-phenylenebis-oxamic acid; IN is [4,4,5,5-tetramethyl-2-(6-methylpyridin-2-yl)-4,5-dihydro-1H-imidazol-1-yl]oxidanyl radical) with a cyclic triangular arrangement. Moreover, in this compound three Ni²⁺ ions are linked by the two bis-oxamate ligands playing a rare tritopic function due to an unprecedented triple deprotonation of the related meta-phenylene-bis(oxamic acid). The main evidence of such a deprotonation of the ligand is the neutrality of the cluster, since there are no anions or cations compensating for its charge in the crystals of the compound. Despite the presence of six possible magnetic couplings in the trinuclear cluster 1, its behavior was reproduced with a high degree of accuracy using a three-J model and ZFS, under the assumption that the three different Ni-IN interactions are equal to each other, whereas only two equivalent-in-value Ni-Ni interactions were taken into account, with the third one being equated to zero. Our study indicates the presence of two opposite-in-nature types of magnetic interactions within the triangular core. DFT and CASSCF/NEVPT2 calculations were completed to support the experimental magnetic data simulation. Full article

Layered transition metal oxide (LTMO) cathode materials for sodium-ion batteries (SIBs) have attracted extensive attention due to their unique structural stability and excellent electrochemical performance. However, their poor stability in air has significantly impeded their practical application, as exposure to moisture and carbon dioxide can lead to Na⁺ loss, phase transitions, and decreased electrochemical performance. This paper reviews the application of high-entropy strategies in sodium-ion LTMO cathode materials, focusing on the optimization of air stability and electrochemical performance through approaches including high-entropy cation regulation, P2/O3 dual-phase synergistic structures, and fluorine ion doping. Studies have shown that high-entropy design can effectively inhibit phase transitions, alleviate Jahn–Teller distortion, enhance oxygen framework stability, and markedly enhance the cycle life and rate performance of materials. Furthermore, future research directions are proposed, including the use of advanced characterization techniques to reveal failure mechanisms, the integration of machine learning to optimize material design, and the development of high-performance mixed-phase structures. High-entropy strategies provide new perspectives for the development of SIBs cathode materials with enhanced air stability, potentially promoting the practical application of SIBs in large-scale energy storage systems. Full article

The genus Musa L. is one of the most important genera worldwide due to its use in food as a source of carbohydrates. A morphological characterization was performed to evaluate the potential of 100 accessions of Musa spp. from the Amazon region of Ecuador, applying 73 qualitative and quantitative descriptors in addition to the ecogeographic characterization. The multivariate analyses identified four large groups: The first is composed of the Musa AAB Simmonds ecotype “Hartón Plantain” and the “Cuerno Clone”. The second group is composed of the Musa acuminata Colla ecotype “Orito”. The third group is composed of the Musa acuminata ecotype “Malay plantain or red plantain”; and the fourth group is composed of the Musa × paradisiaca L. AAB ecotype “Barraganete” and banana or banana materials and the Musa AAB Simmonds ecotype “Plátano Dominico”. The qualitative descriptors with the highest discriminant value were the shape of the ♂ floret bud, the appearance of the rachis, and the pigmentation of the compound tepal, and the quantitative discriminant characters were the height of the pseudostem, the length of the leaf blade, the width of the leaf blade, and the weight of the raceme. The analysis with CAPFITOGEN of these 100 accessions through the ecogeographic characterization map identified 23 categories, highlighting category 20 with a coverage of 40.35%, which mainly includes the provinces of Orellana, Sucumbíos, part of Napo, Pastaza, and Morona Santiago. This category occurs within an annual temperature range between 21.6 °C and 27 °C, an apparent density of 1.25 to 1.44 g cm⁻³, and a cation exchange capacity (CEC) of 4 to 29 Cmol kg⁻¹. The morphological characterization of 100 Musa accessions revealed significant phenotypic variability, with four distinct morphological groups identified through cluster analysis. Key differences were observed in traits such as bunch weight, fruit length, and vegetative vigor. This variability highlights the potential of certain accessions for use in genetic improvement programs. The findings contribute valuable information for the efficient conservation, selection, and utilization of the Musa germplasm in Ecuadorian agroecosystems. The results demonstrate the existence of an important genetic variability in the INIAP Musa Germplasm Bank in the Ecuadorian Amazon region. Full article

Background/Objective: Salinity is a growing problem affecting a large portion of global agricultural land, particularly in areas where water resources are scarce. The objective of this study was to provide physiological and molecular information on salt-tolerant citrus rootstocks to mitigate the detrimental effects of salinity on citriculture. Methods: Ten accessions belonging to eight Citrus species and four to Poncirus trifoliata Raf. were tested for salinity tolerance (0 and 15 mM NaCl for 1 year) in terms of vegetative and Cl⁻ tissue distribution traits. In addition, most accessions were evaluated for leaf Na⁺ and other cations. Results: All salt tolerant accessions tended to restrict the leaf Cl⁻ content, although in a lower degree than the Cleopatra mandarin. However, differences in their ability to restrict leaf [Na⁺] were evident, contributing to a classification of trifoliate and sour orange accessions that matched their genotypic grouping based on allele sharing at a marker targeting candidate gene coding for the NPF5.9 transporter within LCL-6 quantitative trait locus. Conclusions: Our markers targeting LCl-6 candidate genes coding for NPF5.9, PIP2.1, and CHX20 (citrus GmSALT3 ortholog) could be efficient tools for managing the detected salt tolerance diversity in terms of both Cl⁻ and Na⁺ homeostasis in rootstock breeding programs derived from these species, in addition to Citrus reshni. Full article

Recently, graphene oxide (GO) has been largely investigated as a potential adsorbent towards dyes. However, the major obstacle to its full employment is linked to its natural powder consistence, which greatly complexifies the operations of recovery and reuse. With the aim to overcome this issue, the present work reports on the design of GO-modified carbon nanotubes buckypapers (BPs), in which the main component, GO, is entirely entrapped in the BP grid generated by CNTs for the double purpose of (a) increasing adsorption performance of GO-BPs and (b) ensure a fast process of regeneration and reuse. Adsorption experiments were performed towards several dyes: Acid Blue 29 (AB29), Crystal Violet (CV), Eosyn Y (EY), Malachite Green (MG), and Rhodamine B (RB) (C_i = 50 ppm, pH = 6). Results demonstrated that adsorption is strictly dependent on the charge occurring both on GO-BP and dye surfaces, observing great adsorption capacities towards MG (493.44 mg g⁻¹), RB (467.35 mg g⁻¹), and CV (374.53 mg g⁻¹), due to the best coupling of dye cationic form with negative GO-BP surface. Adsorption isotherms revealed that dyes capture onto GO-BPs is thermodynamically favored (ΔG < 0), becoming more negative at 313 K. Kinetic studies evidenced that the process can be described through a pseudo-first-order model, with MG, RB, and CV exhibiting the highest values of k₁. In view of these results, the following trend in GO-BP adsorption performance has been derived: MG ≈ RB > CV > AB29 > EY. Full article

Spent coffee grounds (SCG) are produced in large quantities during coffee brewing, contributing to environmental concerns. Additionally, cationic dyes from textile, paper, and leather wastewater pose a major pollution issue. This study explores SCG as an adsorbent for methylene blue (MB) dye. A novel comparison of SCG cleaning methods with warm water, accelerated solvent extraction (ASE), supercritical fluid extraction (SFE), and ultrasound-induced cavitation (US) is presented. In addition, the chemical modifications of SCG using acetylation, acid (HNO₃), and base (KOH) treatment that have not been reported before are presented. ATR-FTIR confirmed the inclusion of functional groups, for example, the nitro group in SCG treated with HNO₃, and an increase in carboxylic groups in the samples treated with KOH and HNO₃. SEM analysis revealed a consistent porous texture across samples, with SCG-SFE, SCG-US, and SCG-HNO₃ showing smaller pores, and SCG-ASE displaying elongated cavities. Adsorption isotherm tests followed the Freundlich and Langmuir models, indicating favorable adsorption. The Langmuir maximum adsorption capacity (q_max) varied among cleaning methods from 65.69 mg/g (warm water) to 93.32 mg/g (SFE). In contrast, in base- and acid-treated SCG, a three- to four-fold increase in adsorption capacity was observed, with q_max values of 171.60 mg/g and 270.64 mg/g, respectively. These findings demonstrate that SCG washed with warm water and chemically treated achieves adsorption capacities comparable to other biosorbents reported in the literature. Therefore, SCG represents a promising, low-cost, and sustainable material for removing cationic dyes from wastewater, contributing to waste valorization and environmental protection. Full article