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1.
Proc Natl Acad Sci U S A ; 121(14): e2319288121, 2024 Apr 02.
Artículo en Inglés | MEDLINE | ID: mdl-38527206

RESUMEN

Design tactics and mechanistic studies both remain as fundamental challenges during the exploitations of earth-abundant molecular electrocatalysts for CO2 reduction, especially for the rarely studied Cr-based ones. Herein, a quaterpyridyl CrIII catalyst is found to be highly active for CO2 electroreduction to CO with 99.8% Faradaic efficiency in DMF/phenol medium. A nearly one order of magnitude higher turnover frequency (86.6 s-1) over the documented Cr-based catalysts (<10 s-1) can be achieved at an applied overpotential of only 190 mV which is generally 300 mV lower than these precedents. Such a high performance at this low driving force originates from the metal-ligand cooperativity that stabilizes the low-valent intermediates and serves as an efficient electron reservoir. Moreover, a synergy of electrochemistry, spectroelectrochemistry, electron paramagnetic resonance, and quantum chemical calculations allows to characterize the key CrII, CrI, Cr0, and CO-bound Cr0 intermediates as well as to verify the catalytic mechanism.

2.
Proc Natl Acad Sci U S A ; 119(22): e2120716119, 2022 05 31.
Artículo en Inglés | MEDLINE | ID: mdl-35605120

RESUMEN

SignificanceFor oxide catalysts, it is important to elucidate and further control their atomic structures. In this work, well-defined CrO2 bilayer islands and Cr2O7 dinuclear clusters have been grown on Au(111) and unambiguously identified by scanning tunneling microscopy and theoretical calculations. Upon cycled redox treatments, the two kinds of oxide nanostructures can be reversibly transformed. It is interesting to note that both Cr oxides do not exist in bulk but need to be stabilized by the metal surface and the specific environment. Our results suggest that both redox atmosphere and interface confinement effects can be used to construct an oxide nanostructure with the specific chemical state and structure.

3.
Nano Lett ; 24(25): 7601-7608, 2024 Jun 26.
Artículo en Inglés | MEDLINE | ID: mdl-38870328

RESUMEN

Metallic ferromagnetic transition metal dichalcogenides have emerged as important building blocks for scalable magnetic and memory applications. Downscaling such systems to the ultrathin limit is critical to integrate them into technology. Here, we achieved layer-by-layer control over the transition metal dichalcogenide Cr1.6Te2 by using pulsed laser deposition, and we uncovered the minimum critical thickness above which room-temperature magnetic order is maintained. The electronic and magnetic structures are explored experimentally and theoretically, and it is shown that the films exhibit strong in-plane magnetic anisotropy as a consequence of large spin-orbit effects. Our study elucidates both magnetic and electronic properties of Cr1.6Te2 and corroborates the importance of intercalation to tune the magnetic properties of nanoscale materials' architectures.

4.
BMC Plant Biol ; 24(1): 115, 2024 Feb 16.
Artículo en Inglés | MEDLINE | ID: mdl-38365582

RESUMEN

Chromium (Cr) stress significantly hinders crop production by disrupting nutrient uptake, impairing plant growth, and contaminating soil, posing a substantial threat to agricultural sustainability. The use of deashed biochar (DAB) and strigolactone can be an effective solution to mitigate this issue. Deashed biochar enhances crop production by improving soil structure, water retention, and nutrient availability while mitigating the bioavailability of toxic substances. Strigolactone boosts plant growth by stimulating root growth, branching, shoot formation, and overall plant physiology. Nevertheless, the scientific rationale behind their collective use as an amendment to counter Cr stress remains to be substantiated. Therefore, in this study, a blend of DAB and strigolactone was employed as additives in radish cultivation, both in the absence of Cr stress and under the influence of 200Cr stress. Four treatments, i.e., 0, 20µM Strigolactone, DAB, and 20µM Strigolactone + DAB, were applied in four replications following a completely randomized design. Results demonstrate that 20µM Strigolactone + DAB produced significant improvement in radish shoot length (27.29%), root length (45.60%), plant fresh weight (33.25%), and plant dry weight (78.91%), compared to the control under Cr stress. Significant enrichment in radish chlorophyll a (20.41%), chlorophyll b (58.53%), and total chlorophyll (31.54%) over the control under Cr stress, prove the efficacy of 20µM Strigolactone + DAB treatment. In conclusion, 20µM Strigolactone + DAB is the recommended amendment for mitigating Cr stress in radish. Farmers should consider using Strigolactone + DAB amendments to combat Cr stress and enhance radish growth, contributing to a more resilient agricultural ecosystem.


Asunto(s)
Compuestos Heterocíclicos con 3 Anillos , Lactonas , Raphanus , Contaminantes del Suelo , Cromo , Clorofila A , Ecosistema , Carbón Orgánico , Suelo/química
5.
IUBMB Life ; 2024 Jul 25.
Artículo en Inglés | MEDLINE | ID: mdl-39051846

RESUMEN

Heavy metals, a major source of pollution in the environment, pose a substantial threat due to their non-biodegradability and ability to accumulate in living organisms, causing health problems. Recently, researchers have been searching for cost-effective and safe ways to remove heavy metals from polluted waterways using agricultural waste substitutes. The present study focused on the low-cost treatments for the reduction of chromium Cr+6 metal from the effluent, wherein it has been found that chemically and bacterially treated agro-waste had increased heavy metal ion adsorption capabilities. A sequential optimization of the process parameters was attempted using Plackett-Burman design (PBD) and central composite design of response surface methodology (CCD-RSM) for the maximum reduction of the chromium metal from the effluent. A total of eight parameters were screened out using a 12-run PBD experiment. Out of the eight parameters, time, HCl, NaOH, and bacterial treatments were found to be significantly affecting the maximum reduction of Cr+6 from the effluent. To investigate the interactions' effects of the chosen parameters, they were evaluated using CCD-RSM. Maximum 74% Cr+6 reduction was achieved under the optimum treatment to rice husk of HCl 4.52 N, NaOH 3.53 N, bacterial suspension 7.41%, and with an interaction time 14.32 min using 30 run CCD-RSM experiment. A scanning electron microscope was used to confirm the effects of selected variables on the agro-waste for the Cr+6 reductions, as well as a Fourier transform infrared spectrometer.

6.
New Phytol ; 241(2): 676-686, 2024 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-37974482

RESUMEN

Marine phytoplankton can interchange trace metals in various biochemical functions, particularly under metal-limiting conditions. Here, we investigate the stimulating and toxicity effect of chromium (Cr) on a marine Chlorophyceae Osetreococcus tauri under Fe-replete and Fe-deficient conditions. We determined the growth, photosynthesis, and proteome expressions of Osetreococcus tauri cultured under different Cr and Fe concentrations. In Fe-replete conditions, the presence of Cr(VI) stimulated significantly the growth rate and the maximum yield of photochemistry of photosystem II (Fv /Fm ) of the phytoplankton, while the functional absorption cross-section of photosystem II (σPSII ) did not change. Minor additions of Cr(VI) partially rescued phytoplankton growth under Fe-limited conditions. Proteomic analysis of this alga grown in Fe-replete normal and Fe-replete with Cr addition media (10 µM Cr) showed that the presence of Cr significantly decreased the expression of phosphate-transporting proteins and photosynthetic proteins, while increasing the expression of proteins related to carbon assimilation. Cr can stimulate the growth and photosynthesis of O. tauri, but the effects are dependent on both the Cr(VI) concentration and the availability of Fe. The proteomic results further suggest that Cr(VI) addition might significantly increase starch production and carbon fixation.


Asunto(s)
Complejo de Proteína del Fotosistema II , Proteómica , Complejo de Proteína del Fotosistema II/metabolismo , Cromo/toxicidad , Cromo/metabolismo , Fotosíntesis , Fitoplancton/metabolismo , Proteoma/metabolismo
7.
Toxicol Appl Pharmacol ; 485: 116889, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-38479592

RESUMEN

Hexavalent chromium [Cr(VI)] is considered a major environmental health concern and lung carcinogen. However, the exact mechanism by which Cr(VI) causes lung cancer in humans remains unclear. Since several reports have demonstrated a role for inflammation in Cr(VI) toxicity, the present study aimed to apply transcriptomics to examine the global mRNA expression in human lung fibroblasts after acute (24 h) or prolonged (72 and 120 h) exposure to 0.1, 0.2 and 0.3 µg/cm2 zinc chromate, with a particular emphasis on inflammatory pathways. The results showed Cr(VI) affected the expression of multiple genes and these effects varied according to Cr(VI) concentration and exposure time. Bioinformatic analysis of RNA-Seq data based on the Gene ontology (GO), Kyoto Encyclopedia of Genes and Genomes (KEGG) and MetaCore databases revealed multiple inflammatory pathways were affected by Cr(VI) treatment. qRT-PCR data corroborated RNA-Seq findings. This study showed for the first time that Cr(VI) regulates key inflammatory pathways in human lung fibroblasts, providing novel insights into the mechanisms by which Cr(VI) causes lung cancer.


Asunto(s)
Cromo , Fibroblastos , Pulmón , Transcriptoma , Humanos , Cromo/toxicidad , Fibroblastos/efectos de los fármacos , Fibroblastos/metabolismo , Fibroblastos/patología , Pulmón/efectos de los fármacos , Pulmón/metabolismo , Pulmón/patología , Transcriptoma/efectos de los fármacos , Perfilación de la Expresión Génica/métodos , Neoplasias Pulmonares/genética , Neoplasias Pulmonares/inducido químicamente , Neoplasias Pulmonares/patología , Neoplasias Pulmonares/metabolismo , Inflamación/inducido químicamente , Inflamación/genética , Inflamación/metabolismo , Cromatos/toxicidad , Compuestos de Zinc/farmacología , Compuestos de Zinc/toxicidad , Línea Celular , Carcinogénesis/efectos de los fármacos , Carcinogénesis/inducido químicamente , Carcinogénesis/genética , Transducción de Señal/efectos de los fármacos
8.
Toxicol Appl Pharmacol ; 489: 117007, 2024 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-38901695

RESUMEN

We are facing a rapidly growing geriatric population (65+) that will live for multiple decades and are challenged with environmental pollution far exceeding that of previous generations. Consequently, we currently have a poor understanding of how environmental pollution will impact geriatric health distinctly from younger populations. Few toxicology studies have considered age differences with geriatric individuals. Critically, all top ten most prevalent age-related diseases are linked to metal exposures. Hexavalent chromium [Cr(VI)] is a metal of major environmental health concern that can induce aging phenotypes and neurotoxicity. However, there are many knowledge gaps for Cr(VI) neurotoxicity, including how Cr(VI) impacts behavior. To address this, we exposed male rats across three ages (3-, 7-, and 18-months old) to Cr(VI) in drinking water (0, 0.05, 0.1 mg/L) for 90 days. These levels reflect the maximum contaminant levels determined by the World Health Organization (WHO) and the U.S. Environmental Protection Agency (US EPA). Here, we report how these Cr(VI) drinking water levels impacted rat behaviors using a battery of behavior tests, including grip strength, open field assay, elevated plus maze, Y-maze, and 3-chamber assay. We observed adult rats were the most affected age group and memory assays (spatial and social) exhibited the most significant effects. Critically, the significant effects were surprising as rats should be particularly resistant to these Cr(VI) drinking water levels due to the adjustments applied in risk assessment from rodent studies to human safety, and because rats endogenously synthesize vitamin C in their livers (vitamin C is a primary reducer of Cr[VI] to Cr[III]). Our results emphasize the need to broaden the scope of toxicology research to consider multiple life stages and suggest the current regulations for Cr(VI) in drinking water need to be revisited.


Asunto(s)
Envejecimiento , Conducta Animal , Cromo , Animales , Cromo/toxicidad , Masculino , Conducta Animal/efectos de los fármacos , Ratas , Síndromes de Neurotoxicidad/etiología , Aprendizaje por Laberinto/efectos de los fármacos , Factores de Edad , Agua Potable , Contaminantes Químicos del Agua/toxicidad
9.
Chemistry ; 30(7): e202302970, 2024 Feb 01.
Artículo en Inglés | MEDLINE | ID: mdl-38032060

RESUMEN

Starting from C6 H4 (PCl2 )2 and the TMS-substituted ylide (TMS)2 C=PR3 (TMS=trimethylsilyl, R=p-tolyl), the phosphonium-substituted diphosphaindenylide PPI was prepared in two steps. CASSCF calculations as well as the reactivity toward diphenyl acetylene suggest a notable biradical character in PPI. Reaction with [Cr(CO)3 (MeCN)3 ] affords the complex [Cr(CO)3 (η5 -PPI)] (5). This complex was employed to explore the ligand properties of PPI, which demonstrates considerable potential through the combination of strong metal-ligand interactions and the possibility of a pronounced indenyl effect.

10.
Chemistry ; 30(5): e202301099, 2024 Jan 22.
Artículo en Inglés | MEDLINE | ID: mdl-37903737

RESUMEN

In the tetraazamacrocyclic ligand N,N'-dimethyl-2,11-diaza-[3.3](2,6)pyridinophane (L-N4 Me2 ), the two pyridine units are separated from each other by sp3 -hybridized triatomic bridges. Such electronically isolated pyridine moieties are considerably less prone to reductions than di- or triimines. A detailed structural, magnetic, and spectroscopic investigation of the complexes [Cr(L-N4 Me2 )(OAc)2 ] and [Cr(L-N4 Me2 )(OAc)2 ](PF6 ), in combination with theoretical calculations, reveals that the reduced complex must be described as a chromium(III) ion coordinated to the anionic radical ligand (L-N4 Me2 )⋅- rather than a low-spin chromium(II) ion bound to closed-shell ligands. Thus, it is, to the best of our knowledge, only the second example of a stable and structurally characterized metal complex containing a reduced isolated pyridine unit. The stability is attributed to the delocalization of the unpaired electron across the two pyridine units, mediated by their interaction to the metal ion.

11.
Chemistry ; 30(9): e202303765, 2024 Feb 12.
Artículo en Inglés | MEDLINE | ID: mdl-38088491

RESUMEN

A neutral silylyne complex with a Cr≡Si triple bond was prepared by dehydrogenation of a chromium silylene complex with Cr-H and Si-H bonds, and was isolated as monomeric crystals, unlike dimeric forms of its tungsten and molybdenum congeners. The strong Cr(δ-)-Si(δ+) bond polarity was revealed by the reaction with MeOH and DFT calculations. The chromium silylyne complex reacted with H2 under LED (365 nm) irradiation to reproduce the precursor silylene complex with a (H)Cr=Si(H) moiety, as a result of 1,2-H-H addition across the Cr≡Si triple bond. Similarly, the chromium silylyne complex reacted with benzene under irradiation to afford an 1,2-addition product with a (H)Cr=Si(Ph) moiety, via benzene C-H bond activation accompanied by Si-C bond forming.

12.
Chemistry ; 30(31): e202400856, 2024 Jun 03.
Artículo en Inglés | MEDLINE | ID: mdl-38523568

RESUMEN

There has been much progress on mononuclear chromium(III) complexes featuring luminescence and photoredox activity, but dinuclear chromium(III) complexes have remained underexplored in these contexts until now. We identified a tridentate chelate ligand able to accommodate both meridional and facial coordination of chromium(III), to either access a mono- or a dinuclear chromium(III) complex depending on reaction conditions. This chelate ligand causes tetragonally distorted primary coordination spheres around chromium(III) in both complexes, entailing comparatively short excited-state lifetimes in the range of 400 to 800 ns in solution at room temperature and making photoluminescence essentially oxygen insensitive. The two chromium(III) ions in the dimer experience ferromagnetic exchange interactions that result in a high spin (S=3) ground state with a coupling constant of +9.3 cm-1. Photoinduced energy transfer from the luminescent ferromagnetically coupled dimer to an anthracene derivative results in sensitized triplet-triplet annihilation upconversion. Based on these proof-of-principle studies, dinuclear chromium(III) complexes seem attractive for the development of fundamentally new types of photophysics and photochemistry enabled by magnetic exchange interactions.

13.
Chemistry ; 30(10): e202303059, 2024 Feb 16.
Artículo en Inglés | MEDLINE | ID: mdl-37847124

RESUMEN

The fluorobasic character of the strong oxidative fluorinator, XeF6 , and the oxidative resistance of the [XeF5 ]+ and [Xe2 F11 ]+ cations have been exploited for the syntheses of several novel Cr(VI) dianion salts. The reactions of XeF6 and CrO2 F2 in anhydrous HF and by direct fusion of the reactants in melts have yielded the first dinuclear Cr(VI) oxyfluoro-dianion salts, [XeF5 ]2 [Cr2 O4 F6 ], [XeF5 ]2 [Cr2 O4 F6 ] ⋅ 4HF, [XeF5 ]2 [Cr2 O4 F6 ] ⋅ 2XeOF4 , and mononuclear Cr(VI) oxyfluoro-dianion salt, [XeF5 ][Xe2 F11 ][CrO2 F4 ]. The salts were structurally characterized by low-temperature (LT) single-crystal X-ray diffraction (SCXRD) and LT Raman spectroscopy. The [CrO2 F4 ]2- and [Cr2 O4 F6 ]2- dianions have distorted octahedral cis-dioxo Cr(VI) coordination spheres in which two F-atoms are trans to one another and two F-atoms are trans to O-atoms, where the [Cr2 O4 F6 ]2- dianion is the fluorine-bridged dimer of the [CrO2 F3 ]- anion. Quantum-chemical calculations were used to obtain the energy-minimized, gas-phase geometries, and the calculated vibrational spectra of the gas-phase dianions and their ion-pairs, which were used to aid in the vibrational frequency assignments of the crystalline salts. NBO and MEPS analyses and SCXRD show these salts are comprised of intimate ion-pairs in which their cations and anions interact through primarily electrostatic Xe- - -F σ-hole bonds.

14.
Arch Biochem Biophys ; 752: 109872, 2024 02.
Artículo en Inglés | MEDLINE | ID: mdl-38141908

RESUMEN

Trivalent chromium (Cr(III)) is sometimes taken as a long-term supplement, but its effectiveness is unclear. Recently, Cr(III) reportedly modulates peroxisome proliferator-activated receptor gamma (PPARγ) expression. Our previous study reported that increased PPARγ after 24 h Cr(III) treatment promoted erythropoietin (EPO) production in HepG2 cells. In the current study, we analyzed 4-week Cr(III) treatment effects on PPARγ and EPO production in HepG2 cells. Long-term Cr(III) treatment resulted in significantly elevated mRNA expression levels of PPARγ and EPO compared to controls. Additionally, treatment with a PPARγ inhibitor suppressed EPO mRNA expression. Increased EPO mRNA expression due to stimulation with hypoxia or cobalt was unaffected by long-term Cr(III) treatment. Administration of lipopolysaccharide and pyocyanin which causes oxidative stress, promoted EPO production, but this effect was attenuated in cells treated with Cr(III). Long-term Cr(III) treatment increased hypoxia inducible factor (HIF)-1α and 2α mRNA expression and protein levels. Increased PPARγ, induced by long-term Cr(III) treatment, suppressed sirtuin1 (SIRT1) mRNA expression and increased EPO mRNA expression, suggesting that increased PPARγ attenuated the suppressive effect of SIRT1 on HIF. These results suggest that the sustained increase in PPARγ during long-term Cr(III) treatment maintains increased EPO production through a mechanism different from that observed under hypoxia.


Asunto(s)
Eritropoyetina , PPAR gamma , Humanos , Células Hep G2 , Sirtuina 1 , Hipoxia , ARN Mensajero/genética , ARN Mensajero/metabolismo , Subunidad alfa del Factor 1 Inducible por Hipoxia/genética
15.
Transgenic Res ; 2024 Jul 24.
Artículo en Inglés | MEDLINE | ID: mdl-39044015

RESUMEN

An essential aromatic plant, Pelargonium graveolens, does not grow well in areas where chromium contamination is a problem. Because of oxidative stress and the collapse of the photosynthetic system, crops frequently sustain severe damage. The production of excess ethylene, known as stress ethylene, which is detrimental to plant growth, the formation of roots, and early senescence, is also increased by heavy metal exposure. The effectiveness of the 1-aminocyclopropane-1-carboxylic acid (ACC) deaminase gene in transgenic Pelargonium graveolens under the control of CaMV 35S promoter was investigated to lessen the stress ethylene during chromium stress. Chromium was administered as potassium dichromate (K2Cr2O7) at four distinct concentrations (100 µM, 200 µM, 300 µM, and 500 µM) to transgenic and wild-type P. graveolens and stress-induced physiological changes were monitored. Transgenic P. graveolens demonstrated greater tolerance to chromium stress than wild-type P. graveolens, as evidenced by higher leaf-relative water content, chlorophyll content, CO2 absorption, transpiration rate, stomatal conductance, proline buildup, and antioxidant activity. The L1, L5, and L7, ACC deaminase-expressing transgenic lines also show a drop in ACC content during chromium stress, which subsequently lowered ethylene synthesis. Therefore, the reported transgenic P. graveolens lines having the ACC deaminase gene could be useful resources for growing in chromium-prone regions.

16.
Neurochem Res ; 49(3): 660-669, 2024 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-38010603

RESUMEN

Hexavalent chromium (Cr (VI)), one of the most detrimental pollutants, has been ubiquitously present in the environment and causes serious toxicity to humans, such as hepatotoxicity, nephrotoxicity, pulmonary toxicity, and cardiotoxicity. However, Cr (VI)-induced neurotoxicity in primary neuron level has not been well explored yet. Herein, potassium dichromate (K2Cr2O7) was employed to examine the neurotoxicity of Cr (VI) in rat primary hippocampal neurons. MTT test was used to examine the neural viability. Mitochondrial dysfunction was assessed by the JC-1 probe and Mito-Tracker probe. DCFH-DA and Mito-SOX Red were utilized to evaluate the oxidative status. Bcl-2 family and MAPKs expression were investigated using Western blotting. The results demonstrated that Cr (VI) treatment dose- and time-dependently inhibited neural viability. Mechanism investigation found that Cr (VI) treatment causes mitochondrial dysfunction by affecting Bcl-2 family expression. Moreover, Cr (VI) treatment also induces intracellular reactive oxygen species (ROS) generation, DNA damage, and MAPKs activation in neurons. However, inhibition of ROS by glutathione (GSH) effectually balanced Bcl-2 family expression, attenuated DNA damage and the MAPKs activation, and eventually improved neural viability neurons. Collectively, these above results above suggest that Cr (VI) causes significant neurotoxicity by triggering mitochondrial dysfunction, ROS-mediated oxidative damage and MAKPs activation.


Asunto(s)
Enfermedades Mitocondriales , Estrés Oxidativo , Humanos , Ratas , Animales , Especies Reactivas de Oxígeno/metabolismo , Cromo/toxicidad , Glutatión/metabolismo , Proteínas Proto-Oncogénicas c-bcl-2/metabolismo
17.
Int Microbiol ; 2024 Jun 25.
Artículo en Inglés | MEDLINE | ID: mdl-38916652

RESUMEN

Plants exposed to heavy metals (HMs) stress negatively affect their development and production capacity. Chromium (Cr), Cadmium (Cd), and Lead (Pb) are the most common hazardous trace metals in agriculture. The physiological, biochemical, and molecular characteristics of crops are being affected. Phytoremediation is a method to alleviate heavy metals from the contaminated soil. The study aims to evaluate the phytoremediation ability of Vigna radiata L. (mung bean) in the absence and the presence of multi-metal tolerant and plant growth promoting Pseudomonas geniculata strain TIU16A3 isolated from soil of tannery industrial estate, Kolkata, West Bengal, India. The strain was further assessed with increasing concentrations of Cr, Cd, and Pb (10, 20, 40, and 80 µg/mL) when the mung bean plant was a test crop. The strain significantly increased plant growth, chlorophyll content, increased level of antioxidant enzymes such as superoxide dismutase, peroxidase, and catalase, and decreased oxidative stress indicators like H2O2 and electrolyte leakage in the presence of Cr, Cd, and Pb as compared to plants grown in the absence of Pseudomonas geniculata strain. Shoot length responsive gene (Aux/IAA) in the presence of heavy metal alone and Pseudomonas geniculata treated Cd and Cr showed higher relative expression of (Aux/IAA) compared to Pb. Due to these intrinsic abilities, Pseudomonas geniculata strain TIU16A3 can be a plant growth promoter and thus can help in the remediation of heavy metal (Cr, Cd, and Pb) contaminated soil.

18.
Environ Sci Technol ; 58(27): 12225-12236, 2024 Jul 09.
Artículo en Inglés | MEDLINE | ID: mdl-38885124

RESUMEN

Nanoscale zerovalent iron synthesized using borohydride (B-NZVI) has been widely applied in environmental remediation in recent decades. However, the contribution of boron in enhancing the inherent reactivity of B-NZVI and its effectiveness in removing hexavalent chromium [Cr(VI)] have not been well recognized and quantified. To the best of our knowledge, herein, a core-shell structure of B-NZVI featuring an Fe-B alloy shell beneath the iron oxide shell is demonstrated for the first time. Alloyed boron can reduce H+, contributing to more than 35.6% of H2 generation during acid digestion of B-NZVIs. In addition, alloyed B provides electrons for Fe3+ reduction during Cr(VI) removal, preventing in situ passivation of the reactive particle surface. Meanwhile, the amorphous oxide shell of B-NZVI exhibits an increased defect density, promoting the release of Fe2+ outside the shell to reduce Cr(VI), forming layer-structured precipitates and intense Fe-O bonds. Consequently, the surface-area-normalized capacity and surface reaction rate of B-NZVI are 6.5 and 6.9 times higher than those of crystalline NZVI, respectively. This study reveals the importance of alloyed B in Cr(VI) removal using B-NZVI and presents a comprehensive approach for investigating electron pathways and mechanisms involved in B-NZVIs for contaminant removal.


Asunto(s)
Borohidruros , Boro , Hierro , Hierro/química , Borohidruros/química , Boro/química , Cromo/química , Electrones , Aleaciones/química
19.
Environ Sci Technol ; 58(17): 7279-7290, 2024 Apr 30.
Artículo en Inglés | MEDLINE | ID: mdl-38629869

RESUMEN

Exposure to hexavalent chromium damages genetic materials like DNA and chromosomes, further elevating cancer risk, yet research rarely focuses on related immunological mechanisms, which play an important role in the occurrence and development of cancer. We investigated the association between blood chromium (Cr) levels and genetic damage biomarkers as well as the immune regulatory mechanism involved, such as costimulatory molecules, in 120 workers exposed to chromates. Higher blood Cr levels were linearly correlated with higher genetic damage, reflected by urinary 8-hydroxy-2'-deoxyguanosine (8-OHdG) and blood micronucleus frequency (MNF). Exploratory factor analysis revealed that both positive and negative immune regulation patterns were positively associated with blood Cr. Specifically, higher levels of programmed cell death protein 1 (PD-1; mediated proportion: 4.12%), programmed cell death ligand 1 (PD-L1; 5.22%), lymphocyte activation gene 3 (LAG-3; 2.11%), and their constitutive positive immune regulation pattern (5.86%) indirectly positively influenced the relationship between blood Cr and urinary 8-OHdG. NOD-like receptor family pyrin domain containing 3 (NLRP3) positively affected the association between blood Cr levels and inflammatory immunity. This study, using machine learning, investigated immune regulation and its potential role in chromate-induced genetic damage, providing insights into complex relationships and emphasizing the need for further research.


Asunto(s)
Cromatos , Aprendizaje Automático , Humanos , Estudios Transversales , Contaminantes Ambientales , Masculino , Daño del ADN , Adulto , Femenino , Persona de Mediana Edad , Biomarcadores
20.
J Fluoresc ; 2024 Feb 17.
Artículo en Inglés | MEDLINE | ID: mdl-38367156

RESUMEN

Fluorescent carbon dots (Trp-CDs) were prepared using tryptophan as precursor and were characterized on the basis of elemental analysis, powder-XRD, IR, Raman spectroscopy, 13C-NMR, UV-Vis, fluorescence and TEM. Trp-CDs exhibit poor fluorescence in 100% water but showed strong Aggregation Induced Emission (AIE) in ethanol and higher alcohols. The anion sensing study of Trp-CD revealed that it selectively detects CN- and Cr2O7-2 and from fluorescence quenching titration study, quenching constant, LOD and range of detection were evaluated. The emission life-time of Trp-CD before and after addition of CN- and Cr2O7-2 were measured, the decay curve before addition of anion was best fitted with a bi-exponential function with life-time of τ1 2.79 ns (10.74%) and τ2 18.93 ns (89.26%). The mechanistic study revealed that for CN-, the fluorescence quenching is due to its interaction with protons attached to surface functional groups and for Cr2O7-2, it is due to inner filter effect (IFE). Sensing strips were prepared by coating Trp-CDs onto various solid surfaces including agarose films and were used for detection of CN- and Cr2O7-. Trp-CD was found to be nontoxic and biocompatible and used as staining agent for Artemia and Bacteria (Bacillus Subtilis, Pseudomonas) and detection of CN- and Cr2O7-.

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