Low Dose of Nickel and Benzo [a] Anthracene in Rat-Diet, Induce Apoptosis, Fibrosis, and Initiate Carcinogenesis in Liver via NF-Æ˜ß Pathway.

Environmental contaminants such as polycyclic aromatic hydrocarbon (PAH) and heavy metals are major contaminants of food such as fish thus serving as source of exposure to human. This study was designed to evaluate the carcinogenic risk and other risks associated with long-term consumption of environmentally relevant dose of nickel and benzo [a] anthracene in rats. Thirty-six (36) male rats weighing between 80 and 100 g were assigned into 6 groups of 6 animals each; normal, nickel-, and benzo [a] anthracene-exposed groups for 12 and 24 weeks, respectively. Micronucleus and comet analyses were done in the blood, liver, and bone marrow. Liver function, redox, and inflammatory markers (AST, ALT, GGT, SOD, GSH, MDA, protein carbonyl, protein thiol, total protein, IL-10, 1L-1ß, TNF-α, TGF-ß NF-Ƙß, and 8-oxodeoxyguansine) were analysed by standard methods. Immuno-histochemical quantification of Bax, Bcl2, and Erk 1/2 as well as mRNA expression of cyclin D1 was done in liver. From the results, weight gain was observed in varying degrees throughout the exposure period. The polychromatic erythrocytes/normochromatic erythrocytes ratio > 0.2 indicates no cytotoxic effects on the bone marrow. Percentage-MnPCE in blood significantly (p < 0.05) increased throughout exposure duration. Percentage tail DNA in blood was significantly (< 0.05) increased at weeks 20 and 24 in the exposed groups and in liver at weeks 12 (16.22 ± 0.47) and 24 (17.00 ± 0.36) of nickel-exposed rats. The aspartate amino transferase (AST):alanine amino transferase (ALT) ratio indicated fatty liver disease in the benzo [a] anthracene (0.90) and acute liver injury in the nickel (> 10 times greater than the upper limits of the reference group) exposed groups during the first 12 weeks. Observation from the histological and cytological data of the liver revealed the presence of inflammation, fibrosis, and high nuclear/cytoplasmic ratio, respectively, in the nickel and benzo [a] anthracene groups. Only benzo [a] anthracene induced liver oxidative stress with significant (p < 0.05) decrease in SOD (0.64 ± 0.02) activity and increase in protein carbonyl (7.60 ± 0.80 × 10-5) and MDA (57.10 ± 6.64) concentration after 24 weeks. Benzo [a] anthracene up-regulated the cyclin D1 expression and significantly (p < 0.05) increased the levels of the cytokines. Nickel and benzo [a] anthracene significantly (p < 0.05) increased the Bax (183.45 ± 6.50 and 199.76 ± 10.04) and Erk 1/2 (108.25 ± 6.41 and 136.74 ± 4.22) levels when compared with the control (37.43 ± 22.22 and 60.37 ± 17.86), respectively. Overall result showed that the toxic effects of nickel and benzo [a] anthracene might involve fibrosis, cirrhosis, apoptosis, and inflammation of the liver. As clearly demonstrated in this study, benzo [a] anthracene after the 24 weeks of exposure stimulates carcinogenic process by suppressing the liver antioxidant capacity, altering apoptotic, cell proliferation, and differentiation pathways.

Multifunctional (4-in-1) Therapeutic Applications of Nickel Thiocyanate Nanoparticles Impregnated Cotton Gauze as Antibacterial, Antibiofilm, Antioxidant and Wound Healing Agent.

The wounds, arises from accidents, burns, surgeries, diabetes, and trauma, can significantly impact well-being and present persistent clinical challenges. Ideal wound dressings should be flexible, stable, antibacterial, antioxidant and anti-inflammatory in nature, facilitating a scarless rapid wound healing. Initiatives were taken to create antibacterial cotton fabrics by incorporating agents like antibiotics and metallic nanoparticles. However, due to a lack of multifunctionality, these materials were not highly effective in causing scarless and rapid wound healing. In this article, nickel thiocyanate nanoparticle (NiSCN-NPs) impregnated cotton gauze wound dressing (NiSCN-CG) was developed. These nanoparticles were non-toxic to normal human cell lines till 1 mg/mL dose and did not cause skin irritation in the rat model. Further, NiSCN-NPs exhibited antimicrobial, antibiofilm and antioxidant activities confirmed using different in vitro experiments. In vivo wound healing studies in rat models using NiSCN-CG demonstrated rapid scarless wound healing. The nickel thiocyanate impregnated cotton gauze presents a novel approach in scarless wound healing, and as an antimicrobial agent, offering a promising solution for diverse wounds and infections in the future.

Electrodeposited carbon nanostructured nickel composite coatings: A review.

The utilization of high-strength materials that can retain their strength after successive use under high mineral moisture (maximum weight of 1098 kg) for aerospace, automotive, and electromagnetic devices is challenging. Generally, coatings of nickel (Ni) and its alloys are utilized in the aforementioned applications, but the continuous use of the system degrades its mechanical stability and structural integrity. For the automotive and aerospace uses, the material should have high mechanical strength, wear tolerance, corrosion resistance, and magnetism. The bare Ni coatings can be altered with enhanced mechanical, tribological and electrochemical performances by using various reinforcements in the coatings. The abundantly used reinforcing agents are mainly carbonaceous nanoallotropes (such as graphene, carbon nanotubes, and diamond) for the fabrication of composite coatings. The current review unfolds the introduction of nickel and the major cause of damage to bare nickel coatings. Moreover, the review sheds light on how to mitigate the damage of nickel coatings with an emphasis on giving a flavor of distinct carbonaceous nanoallotropes. The conjugated studies on mechanical, wear, corrosion, and magnetic behavior of electrodeposited Ni-carbonaceous composite coatings are embraced in the review. Therefore, the present review can be endorsed by the readers for the protection of aircraft, automotive, and electromagnetic appliances.

Micro-computed tomography analysis of shaping ability of nickel-titanium instruments activated by continuous rotation or adaptive motion.

This study assessed the ability of Twisted File Adaptive (TFA), TruNatomy (TRN) and VDW.Rotate (VR) instruments activated by continuous rotation (CR) and adaptive motion (AM) to shape curved root canals. Thirty mandibular molars with two separate mesial canals 20°-40° curved were collected and scanned using micro-computed tomography (µCT). The canals were then randomly assigned into six groups (n = 10): TRN, VR or TFA instruments activated by CR or AM. TRN groups 17.02, 20.04 and 26.04; VR groups 15.04, 20.05 and 25.06; TFA groups were shaped consecutively using 15K-file, 20.04 and 25.06. After they were shaped, the canals were scanned again. The volume of removed dentin, canal transportation and centring ratio were calculated µCT images. All data were analysed using the Kruskal-Wallis test or one-way analysis of variance (p < 0.05). With both kinematics, the TRN instrument removed the least amount of dentin, the VR-CR and the TFA-AM removed the most (p < 0.05). The transportation and centring ratios among all groups were similar (p > 0.05). The volume of dentin removed, the diameter or design features of the instruments and different kinematics did not affect the centring ratio and the amount of transportation and remained within safe limits. All three instruments activated by either kinematics were found to have similar effectiveness in shaping curved root canals.

Structure-Related Electronic and Magnetic Properties in Ultrathin Epitaxial NixFe3-xO4 Films on MgO(001).

Off-stoichiometric NixFe3-xO4 ultrathin films (x < 2.1) with varying Ni content x and thickness 16 (±2) nm were grown on MgO(001) by reactive molecular beam epitaxy. Synchrotron-based high-resolution X-ray diffraction measurements reveal vertical compressive strain for all films, resulting from a lateral pseudomorphic adaption of the film to the substrate lattice without any strain relaxation. Complete crystallinity with smooth interfaces and surfaces is obtained independent of the Ni content x. For x < 1 an expected successive conversion from Fe3O4 to NiFe2O4 is observed, whereas local transformation into NiO structures is observed for films with Ni content x > 1. However, angle-resolved hard X-ray photoelectron spectroscopy measurements indicate homogeneous cationic distributions without strictly separated phases independent of the Ni content, while X-ray absorption spectroscopy shows that also for x > 1, not all Fe2+ cations are substituted by Ni2+ cations. The ferrimagnetic behavior, as observed by superconducting quantum interference device magnetometry, is characterized by decreasing saturation magnetization due to the formation of antiferromagnetic NiO parts.

Mitochondrial Fission in Nickel Nanoparticle-Induced Reproductive Toxicity: An In Vitro GC-1 Cell Study.

Reproductive disorders and declining fertility rates are significant public health concerns affecting birth rates and future populations. Male infertility, often due to spermatogenesis defects, may be linked to environmental pollutants like nickel nanoparticles (Ni NPs). Ni NPs are extensively utilized across different industries. Nevertheless, their potential adverse effects cannot be overlooked. Previous studies have linked the reproductive toxicity induced by Ni NPs with disturbances in mitochondrial function. Mitochondrial division/fusion dynamics are crucial to their proper function, yet little is known about how Ni NPs perturb these dynamics and whether such perturbation contributes to the impairment of the male reproductive system. Herein, we demonstrated that the exposure of Ni NPs to the mouse-derived spermatogonia cell line (GC-1 cells) triggered DRP1-mediated mitochondrial division and the enhanced impairment of mitochondria, consequently promoting mitochondria-dependent cell apoptosis. Notably, both the mitochondrial division inhibitor (Mdivi-1) and lentiviral-transfected cells with low expression of Dnm1l-DK in these cells could mitigate the toxic effects induced by Ni NPs, pointing to the potential role of mitochondrial dynamics in Ni NP-induced reproductive toxicity. Collectively, our work contributes to the understanding of the mechanisms by which Ni NPs can impact male reproductive function and identifies mitochondrial division as a potential target for intervention.

Unveiling Metal Tolerance Mechanisms in Leersia hexandra Swartz under Cr/Ni Co-Pollution by Studying Endophytes and Plant Metabolites.

Heavy metal pollution poses significant environmental challenges, and understanding how plants and endophytic bacteria interact to mitigate these challenges is of utmost importance. In this study, we investigated the roles of endophytic bacteria, particularly Chryseobacterium and Comamonas, in Leersia hexandra Swartz (L. hexandra) in response to chromium and nickel co-pollution. Our results demonstrated the remarkable tolerance of Chryseobacterium and Comamonas to heavy metals, and their potential to become dominant species in the presence of co-pollution. We observed a close relationship between these endophytic bacteria and the significant differences in metabolites, particularly carbohydrates, flavonoids, and amino acids in L. hexandra. These findings shed light on the potential of endophytic bacteria to promote the production of aspartic acid and other metabolites in plants as a response to abiotic stressors. Furthermore, our study presents a new direction for plant and bioremediation strategies in heavy metal pollution and enhances our understanding of L. hexandra's mechanisms for heavy metal tolerance.

Nickel-catalyzed Intramolecular Hydrosilylation of Alkynes: Embracing Conventional and Electrochemical Routes.

Nickel-catalyzed intramolecular hydrosilylation can be efficiently achieved with high regio- and stereoselectivities through two distinct methodologies. The first approach utilizes a conventional method, involving the reduction of nickel salt (NiBr2-2,2'-bipyridine) using manganese metal. The second method employs a one-step electrochemical reaction, utilizing the sacrificial anode process and NiBr2bipy catalysis. Both methods yield silylated heterocycles in good to high yields through a syn-exo-dig cyclization process. Control experiments and molecular electrochemistry (cyclic voltammetry) provided further insights into the reaction mechanism.

High-Performance Thermoelectric Fibers from Metal-Backboned Polymers for Body-Temperature Wearable Power Devices.

Metal-backboned polymers (MBPs), with a unique backbone consisting of bonded metal atoms, are promising for optic, electric, magnetic, and thermoelectric fields. However, the application of MBP remains relatively understudied. Here, we develop a shear-induced orientation method to construct a flexible nickel-backboned polymer/carbon nanotube (NBP/CNT) thermoelectric composite fiber. It demonstrated a power factor of 719.48 µW ⋅m-1 K-2, which is ca. 3.5 times as high as the bare CNT fiber. Remarkably, with the regulation of carrier mobility and carrier concentration of NBP, the composite fiber further showed simultaneous increases in electrical conductivity and Seebeck coefficient in comparison to the bare CNT fiber. The NBP/CNT fiber can be integrated into fabrics to harvest thermal energy of human body to generate an output voltage of 3.09 mV at a temperature difference of 8 K. This research opens a new avenue for the development of MBPs in power supply.

Melatonin is a Neuroprotective and Antioxidant Agent against Neurotoxicity Induced by an Intrahippocampal Injection of Nickel in Rats.

The investigation into the hippocampal function and its response to heavy metal exposure is crucial for understanding the mechanisms underlying neurotoxicity, this can potentially inform strategies for mitigating the adverse effects associated with heavy metal exposure. Melatonin is an essential neuromodulator known for its efficacy as an antioxidant. In this study, we aimed to determine whether melatonin could protect against Nickel (Ni) neurotoxicity. To achieve this, we performed an intracerebral injection of Ni (300 µM NiCl2) into the right hippocampus of male Wistar rats, followed by melatonin treatment. Based on neurobehavioral and neurobiochemical assessments, our results demonstrate that melatonin efficiently enhances Ni-induced behavioral dysfunction and cognitive impairment. Specifically, melatonin treatment positively influences anxious behavior, significantly reduces immobility time in the forced swim test (FST), and improves learning and spatial memory abilities. Moreover, neurobiochemical assays revealed that melatonin treatment modulates the Ni-induced alterations in oxidative stress balance by increasing antioxidant enzyme activities, such as superoxide dismutase (SOD) and catalase (CAT). Additionally, we observed that melatonin significantly attenuated the increased levels of lipid peroxidation (LPO) and nitric oxide (NO). In conclusion, the data from this study suggests that melatonin attenuates oxidative stress, which is the primary mechanism responsible for Ni-induced neurotoxicity. Considering that the hippocampus is the main structure involved in the pathology associated with heavy metal intoxication, such as Ni, these findings underscore the potential therapeutic efficacy of melatonin in mitigating heavy metal-induced brain damage.

Trends in work-related respiratory diseases attributed to nickel, chromium and cobalt in the UK: descriptive findings from The Health and Occupation Research (THOR) network 1996-2019.

BACKGROUND: Occupational exposure to metals can be associated with respiratory diseases which can adversely affect the individual's health, finances and employment. Despite this, little is known about the incidence of these respiratory conditions over prolonged periods of time. AIMS: This study aimed to investigate the trends in the incidence of work-related respiratory diseases attributed to nickel, chromium and cobalt in the UK. METHODS: Cases of occupational respiratory diseases caused by nickel, chromium or cobalt reported to Surveillance of Work-related and Occupational Respiratory Disease (SWORD), the UK-based surveillance scheme between 1996 and 2019 (inclusive), were extracted and grouped into six 4-year time periods. Cases were characterised by causative metal exposure, occupational and industrial sector. Incidence rates diseases (adjusted for physician participation and response rate) were calculated using ONS employment data. RESULTS: Of cases reported to SWORD during the study period, 1% (173 actual cases) of respiratory problems were attributed to nickel, chromium or cobalt. Diagnoses of asthma compromised the largest proportion of diagnoses (74.4%), followed by lung cancer (8.9%) and pneumoconiosis (6.7%). Cases had a mean age of 47 years (SD 13); 93% were men. The annual incidence fell from 1.6 per million employed in the first 4-year period, to 0.2 in the most recent period. CONCLUSIONS: Over 24 years, a decline in the incidence of metal-related occupational respiratory diseases was observed in the UK. This could be attributed to improvements in working conditions which resulted in reduced metal exposure but could also be due to closure of industries that might have generated case returns.

Study on mechanism underlying the acceleration of pitting corrosion of B30 copper-nickel alloy by sulfate-reducing bacteria in seawater.

In this paper, the relationship between the pitting corrosion formation of B30 copper-nickel (CuNi) alloy and the metabolism of sulfate-reducing bacteria (SRB) was investigated. Combined with the influence of temperature during the actual operation of the cooling systems, the evolution law of the alloy passivation film was analyzed, and the mechanism of SRB promoting the accelerated development of B30 CuNi alloy pitting corrosion was revealed. The results show that SRB significantly promoted the pitting formation and development of B30 CuNi alloy. The maximum pitting depth was 3.9 µm in the sterile system and 15.3 µm with SRB, which was 3.9 times higher than that of sterile system. The loose porous Cu2S film formed by SRB metabolites and copper matrix was easily penetrated by corrosive anions, which promoted copper dissolution and led to pit nucleation. The sulfide adsorbed on the surface prevented or delayed the passivation of B30 CuNi alloy by blocking the adsorption site of O atom, and the corrosion nuclei continued to grow. The non-uniformity caused by the film peeling accelerated the longitudinal development of pitting corrosion, and the expansion and coalescence of adjacent pits caused the transverse development of pitting corrosion. Temperature had a certain influence on the SRB and the formation of B30 CuNi alloy passivation film. The passivation film was formed rapidly at 50 °C with poor quality and the passivation property of Cu2O film was weakened. With the increase of temperature, the pitting potential of sterile system negative shifted from 0.447 to 0.360 V (vs. SCE), while SRB system from 0.340 to 0.198 V (vs. SCE), and the pitting resistance decreased. The passivation film with defects and the Cu2S reduced the barrier efficiency of the film and accelerated the pitting corrosion of B30 CuNi alloy.

A Single Terminal [NiII-OH] Catalyst for Direct Julia-Type Olefination and α-Alkylation Involving Sulfones and Alcohols.

A terminal [NiII-OH] complex 1, supported by triflamide-functionalized NHC ligands, showed divergent reactivity for the reaction of sulfone with alcohol, contingent on base concentration, temperature, and time. Julia-type olefination of alcohols with sulfones was achieved using one equiv. of base, whereas lowering base loading to 0.5 equiv. afforded α-alkylated sulfones. Besides excellent substrate scope and selectivity, biologically active stilbene derivatives DMU-212, pinosylvin, resveratrol, and piceatannol were synthesized in high yield under Julia-type olefination conditions. An extensive array of controlled experiments and DFT calculations provide valuable insight on the reaction pathway.

In-situ growth of Mn-Ni3S2 on nickel foam for catalytic ozonation of p-nitrophenol.

In this study, a new catalyst for catalytic ozonation was obtained by in-situ growth of Mn-Ni3S2 nanosheets on the surface of nickel foam (NF). The full degradation of p-nitrophenol (PNP) was accomplished under optimal conditions in 40 min. The effects of material dosage, ozone dosage, pH and the presence of inorganic anions on the degradation efficiency of PNP were investigated. ESR analysis showed that singlet oxygen (1O2) and superoxide radical (O2•-) are the main contributors of PNP degradation. This study offers a new combination of supported catalysts with high efficiency and easy recovery, which provides a new idea for wastewater treatment.

Ecological impacts and potential hazards of nickel on soil microbes, plants, and human health.

Nickel (Ni) contamination poses a serious environmental concern, particularly in developing countries: where, anthropogenic activities significantly contributes to Ni accumulations in soils and waters. The contamination of agricultural soils with Ni, increases risks of its entry to terrestrial ecosystems and food production systems posing a threat to both food security and safety. We examined the existing published articles regarding the origin, source, accumulation, and transport of Ni in soil environments. Particularly, we reviewed the bioavailability and toxic effects of Ni to soil invertebrates and microbes, as well as its impact on soil-plant interactions including seed germination, nutrient uptake, photosynthesis, oxidative stress, antioxidant enzyme activity, and biomass production. Moreover, it underscores the potential health hazards associated with consuming crops cultivated in Ni-contaminated soils and elucidates the pathways through which Ni enters the food chain. The published literature suggests that chronic Ni exposure may have long-term implications for the food supply chain and the health of the public. Therefore, an aggressive effort is required for interdisciplinary collaboration for assessing and mitigating the ecological and health risks associated with Ni contamination. It also argues that these measures are necessary in light of the increasing level of Ni pollution in soil ecosystems and the potential impacts on public health and the environment.

Ruthenium Single Atomic Sites Surrounding the Support Pit with Exceptional Photocatalytic Activity.

Single-metal atomic sites and vacancies can accelerate the transfer of photogenerated electrons and enhance photocatalytic performance in photocatalysis. In this study, a series of nickel hydroxide nanoboards (Ni(OH)x NBs) with different loadings of single-atomic Ru sites (w-SA-Ru/Ni(OH)x) were synthesized via a photoreduction strategy. In such catalysts, single-atomic Ru sites are anchored to the vacancies surrounding the pits. Notably, the SA-Ru/Ni(OH)x with 0.60 wt % Ru loading (0.60-SA-Ru/Ni(OH)x) exhibits the highest catalytic performance (27.6 mmol g-1 h-1) during the photocatalytic reduction of CO2 (CO2RR). Either superfluous (0.64 wt %, 18.9 mmol g-1 h-1; 3.35 wt %, 9.4 mmol-1 h-1) or scarce (0.06 wt %, 15.8 mmol g-1 h-1; 0.29 wt %, 21.95 mmol g-1 h-1; 0.58 wt %, 23.4 mmol g-1 h-1) of Ru sites have negative effect on its catalytic properties. Density functional theory (DFT) calculations combined with experimental results revealed that CO2 can be adsorbed in the pits; single-atomic Ru sites can help with the conversion of as-adsorbed CO2 and lower the energy of *COOH formation accelerating the reaction; the excessive single-atomic Ru sites occupy vacancies that retard the completion of CO2RR.

Rational Design of Nanosheet Array-Like Layered-Double-Hydroxide-Derived NiCo2O4 In Situ Grown on Reduced-Graphene-Oxide-Coated Nickel Foam for High-Performance Solid-State Supercapacitors.

The investigation of high-performance supercapacitors is essential for accelerating the development of energy storage devices. In this work, a 3D hierarchical nanosheet array-like nickel cobaltite/reduced graphene oxide/nickel foam composite (NiCo2O4/rGO/NF) was assembled via an aqueous coprecipitation-hydrothermal strategy assisted by citric acid. Benefiting from a NiCo layered-double-hydroxide precursor with an atomic-level lattice confinement effect of metal ions and effective hybridization with rGO, the NiCo2O4/rGO/NF composite is featured as thin NiCo2O4 nanosheets (∼113.6 nm × 11.2 nm) composed of NiCo2O4 nanoparticles (∼10.9 nm) vertically staggered on the surface of a rGO-modified NF skeleton, leading to high surface area, abundant mesoporous structure, and active site exposure. The as-obtained NiCo2O4/rGO/NF was directly used as a binder-free integrated electrode for supercapacitors, achieving an excellent specific capacitance of 2863.4 F g-1 (1503.3 C g-1) at 1 A g-1, a superior rate performance of 2335.2 F g-1 at 20 A g-1, and a stability retention of 91.7% after 5000 cycles. More impressively, a solid-state asymmetric supercapacitor assembled by the present NiCo2O4/rGO/NF integrated electrode as the positive electrode and commercial activated carbon as the negative electrode achieved a high energy density of 69.2 Wh kg-1 at a power density of 800 W kg-1, and the energy density at a peak power density of 20004 W kg-1 still remained at 48.9 Wh kg-1, also showing a good cycling stability of 87.2% retention over 10000 cycles. The present facile synthesis strategy of the as-obtained NiCo2O4/rGO/NF nanosheet array composite can be used for the design and construction of many other transition-metal oxide/graphene/NF composite materials with excellent structural stability and performance in energy storage and other related areas.

DFT and TDDFT exploration on electronic transitions and bonding aspect of DPA and PTDC ligated transition metal complexes.

CONTEXT: In this study, we have investigated the structure, reactivity, bonding, and electronic transitions of DPA and PDTC along with their Ni-Zn complexes using DFT/TD-DFT methods. The energy gap between the frontier orbitals was computed to understand the reactivity pattern of the ligands and metal complexes. From the energies of FMO's, the global reactivity descriptors such as electron affinity, ionization potential, hardness (η), softness (S), chemical potential (µ), electronegativity (χ), and electrophilicity index (ω) have been calculated. The complexes show a strong NLO properties due to easily polarization as indicated by the narrow HOMO-LUMO gap. The polarizability and hyperpolarizabilities of the complexes indicate that they are good candidates for NLO materials. Molecular electrostatic potential (MEP) maps identified electrophilic and nucleophilic sites on the surfaces of the complexes. TDDFT and NBO analyses provided insights into electronic transitions, bonding, and stabilizing interactions within the studied complexes. DPA and PDTC exhibited larger HOMO-LUMO gaps and more negative electrostatic potentials compared to their metal complexes suggesting the higher reactivity. Ligands (DPA and PDTC) had absorption spectra in the range of 250 nm to 285 nm while their complexes spanned 250 nm to 870 nm. These bands offer valuable information on electronic transitions, charge transfer and optical behavior. This work enhances our understanding of the electronic structure and optical properties of these complexes. METHODS: Gaussian16 program was used for the optimization of all the compounds. B3LYP functional in combination with basis sets, such as LanL2DZ for Zn, Ni and Cu while 6-311G** for other atoms like C, H, O, N, and S was used. Natural bond orbital (NBO) analysis is carried out to find out how the filled orbital of one sub-system interacts with the empty orbital of another sub-system. The ORCA software is used for computing spectral features along with the zeroth order regular approximation method (ZORA) to observe its relativistic effects. TD-DFT study is carried out to calculate the excitation energy by using B3LYP functional.

Subclinical immune responses to nickel in sensitized individuals-a dose-response study.

BACKGROUND: Nickel is the leading cause of contact allergy in Europe, with 14.5% of the adult population being sensitized. Despite regulations limiting nickel release from consumer items, the incidence and prevalence of nickel allergy remain high. OBJECTIVE: To investigate the clinical and subclinical immune response to low-dose nickel exposure on nickel pre-exposed skin to assess the adequacy of current regulatory limits. METHOD: Nickel-allergic and healthy controls were patch tested with nickel twice with a 3-4 weeks interval. The first exposure used the diagnostic concentration of 2000 µg/cm2 nickel sulphate, and the same skin areas were then re-exposed to 0.2, 0.5, 12.8 and 370 µg/cm2 nickel sulphate. After 48 h, the patch reactions were examined for clinical signs of eczema, and skin biopsies were collected. The transcriptomic immune profile was analysed with Nanostring nCounter and quantitative polymerase chain reaction. RESULTS: Two nickel-allergic participants (15%) had clinical reactions to the regulatory limiting doses for nickel (0.2/0.5 µg/cm2) following re-exposure. There was immune activation in all skin areas following re-exposure to nickel, predominantly mediated by up-regulation of cytokines and chemokines. In all nickel re-exposed skin areas, 81 genes were up-regulated independent from the clinical response. In skin areas exposed to 0.2 µg/cm2, 101 immune-related genes were differentially expressed, even when no clinical response was observed. Healthy controls showed up-regulation of three genes in response to nickel re-exposures without any clinical reactions. CONCLUSION: Immune activation can be induced in skin with local memory to nickel upon challenge with nickel doses within the regulatory limits. Our findings suggest that the regulatory limits in the European nickel regulation may not provide sufficient protection for consumers against low-dose exposures.

Toward High-Performance Hydrogenation at Room Temperature Through Tailoring Nickel Catalysts Stable in Aqueous Solution.

The development of highly active, reusable catalysts for aqueous-phase reactions is challenging. Herein, metallic nickel is encapsulated in a nitrogen-doped carbon-silica composite (SiO2@Ni@NC) as a catalyst for the selective hydrogenation of vanillin in aqueous media. The constructed catalyst achieved 99.8% vanillin conversion and 100% 4-hydroxymethyl-2-methoxyphenol selectivity at room temperature. Based on combined scanning transmission electron microscopy, X-ray photoelectron spectroscopy, and Raman analyses, the satisfactory catalytic performance is attributed to the composite structure consisting of an active metal, carbon, and silica. The hydrophilic silica core promoted dispersion of the catalyst in aqueous media. Moreover, the external hydrophobic NC layer has multiple functions, including preventing oxidation or leaching of the internal metal, acting as a reducing agent to reduce the internal metal, regulating the active-site microenvironment by enriching the concentrations of H2 and organic reactants, and modifying the electronic structure of the active metal via metal-support interactions. Density functional theory calculations indicated that NC facilitates vanillin adsorption and hydrogen dissociation to promote aqueous-phase hydrogenation. This study provides an efficient strategy for constructing encapsulated Ni-based amphiphilic catalysts to upgrade biomass-derived compounds.