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Journal of the American Chemical Society Nov 2023The oxygen-tolerant and molybdenum-dependent formate dehydrogenase FdsDABG from is capable of catalyzing both formate oxidation to CO and the reverse reaction (CO...
The oxygen-tolerant and molybdenum-dependent formate dehydrogenase FdsDABG from is capable of catalyzing both formate oxidation to CO and the reverse reaction (CO reduction to formate) at neutral pH, which are both reactions of great importance to energy production and carbon capture. FdsDABG is replete with redox cofactors comprising seven Fe/S clusters, flavin mononucleotide, and a molybdenum ion coordinated by two pyranopterin dithiolene ligands. The redox potentials of these centers are described herein and assigned to specific cofactors using combinations of potential-dependent continuous wave and pulse EPR spectroscopy and UV/visible spectroelectrochemistry on both the FdsDABG holoenzyme and the FdsBG subcomplex. These data represent the first redox characterization of a complex metal dependent formate dehydrogenase and provide an understanding of the highly efficient catalytic formate oxidation and CO reduction activity that are associated with the enzyme.
Topics: Molybdenum; Formate Dehydrogenases; Cupriavidus necator; Carbon Dioxide; Oxidation-Reduction; Formates
PubMed: 37967365
DOI: 10.1021/jacs.3c10199 -
Environmental Geochemistry and Health Jul 2024Shaanxi Province is located in the most important molybdenum ore district in the world, but a lot of molybdenum tailings have been released, polluting the environment...
Shaanxi Province is located in the most important molybdenum ore district in the world, but a lot of molybdenum tailings have been released, polluting the environment and wasting resources seriously. Taking eleven tailing samples collected at the main molybdenum tailings ponds in Shaanxi Province as the research object, the physical, chemical, and mineralogical characteristics were studied through scanning electron microscope, X-ray fluorescence, X-ray diffraction, inductively coupled plasma mass spectrometer, and others. The ecological risk and utilization potential of molybdenum tailings were investigated through leaching test, geo-accumulation index, potential ecological risk assessment, and other methods. The results demonstrated that the main chemical and mineralogical composition of various molybdenum tailings in Shaanxi Province is similar, and the predominant mineral composition is muscovite, quartz, microcline, and calcite. The potential ecological risk of heavy metals in six molybdenum tailings is high, while Pb and Cd are the main pollution risk elements. Molybdenum tailings contain considerable amounts of critical minerals with huge potential economic value, and molybdenum tailings with high environmental hazards could be converted into a possible source for critical minerals by recovering the critical minerals and repurposing the secondary tailings as an additive or cement substitute. This study provides an innovative idea for the pollution treatment of molybdenum tailings and indicates the prospect of molybdenum tailings as a secondary source for critical minerals.
Topics: Molybdenum; China; Environmental Monitoring; Risk Assessment; Mining; Spectrometry, X-Ray Emission; Metals, Heavy; X-Ray Diffraction; Microscopy, Electron, Scanning; Soil Pollutants
PubMed: 38954233
DOI: 10.1007/s10653-024-02049-5 -
Chemistry, An Asian Journal Jun 2023Molybdenum carbide is one of non-precious metal materials and it is a promising electrocatalyst for hydrogen production. Synthesis and improvement of molybdenum...
Molybdenum carbide is one of non-precious metal materials and it is a promising electrocatalyst for hydrogen production. Synthesis and improvement of molybdenum carbide's catalytic performance is of great significance. Herein, carbon-based Mo C with hybrid phase of MoO was fabricated by matching the composition of Mo and C derived from pomelo peel and optimizing raw carbon amount and prolysis temperature. The resulting MoO /Mo C@C is composed of loose microspheres with mesoporous microstructure and is self-assembled from nanoparticles. The results show that MoO /Mo C@C2 material exhibits excellent HER performance and only a low overpotentials of 143 mV is needed to drive the current density of 10 mA cm in alkaline solution, and Tafel slopes are only 63.4 mV dec , respectively. Notably, it has potential application at low overpotentials to drive large current density and this strategy also provides a universal route to prepare non-noble metal catalyst with hybrid phase of oxide/carbide.
Topics: Molybdenum; Carbon; Oxides; Hydrogen
PubMed: 37150746
DOI: 10.1002/asia.202300292 -
Inorganic Chemistry Sep 2022The complex [TEA][Tp*Mo(O)(SBMOPP)] () [TEA = tetraethylammonium, Tp* = tris(3,5-dimethylpyrazolyl)hydroborate, and BMOPP = 6-(3-butynyl-2-methyl-2-ol)-2-pivaloyl...
The complex [TEA][Tp*Mo(O)(SBMOPP)] () [TEA = tetraethylammonium, Tp* = tris(3,5-dimethylpyrazolyl)hydroborate, and BMOPP = 6-(3-butynyl-2-methyl-2-ol)-2-pivaloyl pterin] is a structural analogue of the molybdenum cofactor common to all pyranopterin molybdenum enzymes because it possesses a pyranopterin-ene-1,2-dithiolate ligand (SBMOPP) that exists primarily in the ring-closed pyrano structure as a resonance hybrid of ene-dithiolate and thione-thiolate forms. Compound , the protonated [Tp*Mo(O)(SBMOPP-H)] () and one-electron-oxidized [Tp*Mo(O)(SBMOPP)] [] species have been studied using a combination of electrochemistry, electronic absorption, and electron paramagnetic resonance (EPR) spectroscopy. Additional insight into the nature of these molecules has been derived from electronic structure computations. Differences in dithiolene C-S bond lengths correlate with relative contributions from both ene-dithiolate and thione-thiolate resonance structures. Upon protonation of to form , large spectroscopic changes are observed with transitions assigned as Mo(xy) → pyranopterin metal-to-ligand charge transfer and dithiolene → pyranopterin intraligand charge transfer, respectively, and this underscores a dramatic change in electronic structure between and . The changes in electronic structure that occur upon protonation of are also reflected in a large >300 mV increase in the Mo(V/IV) redox potential for , resulting from the greater thione-thiolate resonance contribution and decreased charge donation that stabilize the Mo(IV) state in with respect to one-electron oxidation. EPR spin Hamiltonian parameters for one-electron-oxidized and uncyclized [Tp*Mo(O)(SBDMPP)] [] [BDMPP = 6-(3-butynyl-2,2-dimethyl)-2-pivaloyl pterin] are very similar to each other and to those of [Tp*MoO(bdt)] (bdt = 1,2-ene-dithiolate). This indicates that the dithiolate form of the ligand dominates at the Mo(V) level, consistent with the demand for greater S → Mo charge donation and a corresponding increase in Mo-S covalency as the oxidation state of the metal is increased. Protonation of represents a simple reaction that models how the transfer of a proton from neighboring acidic amino acid residues to the Mo cofactor at a nitrogen atom within the pyranopterin dithiolene (PDT) ligand in pyranopterin molybdenum enzymes can impact the electronic structure of the Mo-PDT unit. This work also illustrates how pyran ring-chain tautomerization drives changes in resonance contributions to the dithiolene chelate and may adjust the reduction potential of the Mo ion.
Topics: Electron Spin Resonance Spectroscopy; Ligands; Molybdenum; Pterins; Thiones
PubMed: 36000991
DOI: 10.1021/acs.inorgchem.2c01234 -
Journal of Materials Chemistry. B Jun 2024With the advancement in the field of biomedical research, there is a growing demand for biodegradable electronic devices. Biodegradable supercapacitors (SCs) have...
With the advancement in the field of biomedical research, there is a growing demand for biodegradable electronic devices. Biodegradable supercapacitors (SCs) have emerged as an ideal solution for mitigating the risks associated with secondary surgeries, reducing patient discomfort, and promoting environmental sustainability. In this study, MoN@Mo-foil was prepared as an active material for biodegradable supercapacitors through high-temperature and nitridation processes. The composite electrode exhibited superior electrochemical performance in both aqueous and solid-state electrolytes. In the case of the solid-state electrolyte, the MoN@Mo-foil composite electrode-based device demonstrated excellent cycling stability and electrochemical performance. Additionally, the composite electrode exhibited rapid and complete biodegradability in a 3% HO solution. Through detailed experimental analysis and performance testing, we verified the potential application of the MoN@Mo-foil composite electrode in biodegradable supercapacitors. This work provides a new choice of degradable material for developing biomedical electronic devices.
Topics: Electrodes; Electric Capacitance; Humans; Molybdenum; Electrochemical Techniques; Biocompatible Materials; Particle Size; Surface Properties
PubMed: 38771646
DOI: 10.1039/d4tb00649f -
Molecules (Basel, Switzerland) Oct 2023In prokaryotes, the role of Mo/W enzymes in physiology and bioenergetics is widely recognized. It is worth noting that the most diverse family of Mo/W enzymes is... (Review)
Review
In prokaryotes, the role of Mo/W enzymes in physiology and bioenergetics is widely recognized. It is worth noting that the most diverse family of Mo/W enzymes is exclusive to prokaryotes, with the probable existence of several of them from the earliest forms of life on Earth. The structural organization of these enzymes, which often include additional redox centers, is as diverse as ever, as is their cellular localization. The most notable observation is the involvement of dedicated chaperones assisting with the assembly and acquisition of the metal centers, including Mo/W-bisPGD, one of the largest organic cofactors in nature. This review seeks to provide a new understanding and a unified model of Mo/W enzyme maturation.
Topics: Metalloproteins; Prokaryotic Cells; Oxidation-Reduction; Energy Metabolism; Molecular Chaperones; Molybdenum
PubMed: 37894674
DOI: 10.3390/molecules28207195 -
Contrast Media & Molecular Imaging 2022The study investigates the diagnostic efficacy of ultrasound combined with the molybdenum target mode in breast cancer staging and the relationship between blood flow...
Differential Efficacy of B-Ultrasound Combined with Molybdenum Target Detection Mode for Breast Cancer Staging and Correlation of Blood Flow Parameters with IGF-1 and IGF-2 Expression Level and Prognosis.
The study investigates the diagnostic efficacy of ultrasound combined with the molybdenum target mode in breast cancer staging and the relationship between blood flow parameters and the expression of insulin-like growth factor 1 (IGF-1) and factor 2 (IGF-2) and prognosis. A total of 96 patients admitted to hospital from January 2020 to January 2021 are included in the breast cancer group, and 58 patients admitted to our hospital during the same period are included in the control group, who are diagnosed with benign breast lesions. All patients receive clinicopathological diagnosis, ultrasound detection, and X-ray molybdenum detection. Ultrasound detection, molybdenum target detection, ultrasound combined with the molybdenum target detection mode, and clinicopathological diagnosis results are compared. B-ultrasound combined with the molybdenum target detection mode has high efficiency in diagnosing breast cancer and differentiating pathological stages. Besides, blood flow parameters of patients are closely related to IGF-1 and IGF-2, and IGF-1 and IGF-2 expressions are closely related to the prognosis of patients. Subsequent diagnosis of the disease degree of breast cancer patients can be carried out by ultrasound combined with the molybdenum target detection mode. In addition, the expression of IGF-1 and IGF-2 in patients can be monitored to improve the clinical diagnosis and treatment plan to improve the prognosis of patients, which has a high clinical application value and is worth promoting.
Topics: Breast Neoplasms; Female; Humans; Insulin-Like Growth Factor I; Insulin-Like Growth Factor II; Molybdenum; Neoplasm Staging; Prognosis
PubMed: 35845730
DOI: 10.1155/2022/9198626 -
Nature Nanotechnology Jun 2021Many nanoscale biomaterials fail to reach the clinical trial stage due to a poor understanding of the fundamental principles of their in vivo behaviour. Here we describe...
Many nanoscale biomaterials fail to reach the clinical trial stage due to a poor understanding of the fundamental principles of their in vivo behaviour. Here we describe the transport, transformation and bioavailability of MoS nanomaterials through a combination of in vivo experiments and molecular dynamics simulations. We show that after intravenous injection molybdenum is significantly enriched in liver sinusoid and splenic red pulp. This biodistribution is mediated by protein coronas that spontaneously form in the blood, principally with apolipoprotein E. The biotransformation of MoS leads to incorporation of molybdenum into molybdenum enzymes, which increases their specific activities in the liver, affecting its metabolism. Our findings reveal that nanomaterials undergo a protein corona-bridged transport-transformation-bioavailability chain in vivo, and suggest that nanomaterials consisting of essential trace elements may be converted into active biological molecules that organisms can exploit. Our results also indicate that the long-term biotransformation of nanomaterials may have an impact on liver metabolism.
Topics: Administration, Intravenous; Animals; Apolipoproteins E; Biological Availability; Biotransformation; Blood Proteins; Disulfides; Female; Liver; Macrophages; Mice, Inbred BALB C; Mice, Transgenic; Molecular Dynamics Simulation; Molybdenum; Nanostructures; Protein Corona; Serum Albumin, Human; Spleen; Tissue Distribution; Mice
PubMed: 33603238
DOI: 10.1038/s41565-021-00856-w -
ACS Applied Bio Materials Nov 2022Nowadays, the over use of antibiotics has led to the production of biofilms, which cause antimicrobial treatment to fail and thus are a severe threat to public health...
Nowadays, the over use of antibiotics has led to the production of biofilms, which cause antimicrobial treatment to fail and thus are a severe threat to public health globally. Therefore, exploiting antibiofilm agents is highly urgent. In the present study, we report an assembly that is rationally constructed by biogenic amine spermine (Spm) and molybdenum (Mo)-containing polyoxometalate clusters (Mo), which present efficient antibiofilm and bactericidal effects. On the one hand, the assembly of Mo/Spm produces large aggregates, which favors 808 nm absorption and exhibits an improved photothermal transition (PTT) under near-infrared (NIR) irradiation. On the other hand, the assembly with Spm enhanced Mo uptake to both the biofilm and bacteria, which improved both biofilm elimination and antibacterial effects. Therefore, in addition to providing an efficient antibacterial agent of Mo/Spm assembly, the present study also offers guidance on the future design of hybrid antibacterial assemblies with efficient effects.
Topics: Molybdenum; Spermine; Anti-Bacterial Agents; Biofilms
PubMed: 36264761
DOI: 10.1021/acsabm.2c00692 -
Small (Weinheim An Der Bergstrasse,... May 2022Human health can be affected by materials indirectly through exposure to the environment or directly through close contact and uptake. With the ever-growing use of 2D...
Human health can be affected by materials indirectly through exposure to the environment or directly through close contact and uptake. With the ever-growing use of 2D materials in many applications such as electronics, medical therapeutics, molecular sensing, and energy storage, it has become more pertinent to investigate their impact on the immune system. Dendritic cells (DCs) are highly important, considering their role as the main link between the innate and the adaptive immune system. By using primary human DCs, it is shown that hexagonal boron nitride (hBN), graphene oxide (GO) and molybdenum disulphide have minimal effects on viability. In particular, it is evidenced that hBN and GO increase DC maturation, while GO leads to the release of reactive oxygen species and pro-inflammatory cytokines. hBN and MoS increase T cell proliferation with and without the presence of DCs. hBN in particular does not show any sign of downstream T cell polarization. The study allows ranking of the three materials in terms of inherent toxicity, providing the following trend: GO > hBN ≈ MoS , with GO the most cytotoxic.
Topics: Dendritic Cells; Humans; Molybdenum
PubMed: 35451183
DOI: 10.1002/smll.202107652