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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 -
Molecules (Basel, Switzerland) Feb 2024The reaction of molybdenum complexes with a tris(pyrazolyl)borate ligand (EtN[TpMo(CO)] and EtN[Tp*Mo(CO)] (Tp = hydridotris(pyrazolyl)borate, Tp* =...
The reaction of molybdenum complexes with a tris(pyrazolyl)borate ligand (EtN[TpMo(CO)] and EtN[Tp*Mo(CO)] (Tp = hydridotris(pyrazolyl)borate, Tp* = hydridotris(3,5-dimethylpyrazolyl)borate)) and InBr at a 1:1 molar ratio afforded molybdenum-indane complexes (EtN[TpMo(CO)(InBr)] and EtN[Tp*Mo(CO)(InBr)] ). In addition, tungsten-indane complexes, EtN[TpW(CO)(InBr)] and EtN[Tp*W(CO)(InBr)] , were obtained by the reaction of corresponding tungsten complexes. Complex reacted with HO to form the hydrido complex Tp*W(CO)H, in which the W-In bond was cleaved. On the other hand, reacted with three equiv. of AgNO to form EtN[Tp*W(CO){In(ONO)}] , in which three substituents on the In were exchanged while retaining the W-In dative bond. Complexes - were fully characterized using NMR measurements and elemental analyses, and the structures of - and EtN[Tp*W(CO)] were determined via X-ray crystallography. These are the first examples of mononuclear molybdenum- and tungsten-indane complexes with Mo-In and W-In dative bonds.
PubMed: 38398509
DOI: 10.3390/molecules29040757 -
ACS Nano Jul 2023Extracellular vesicles (EVs) are continually released from cancer cells into biofluids, carrying actionable molecular fingerprints of the underlying disease with...
Extracellular vesicles (EVs) are continually released from cancer cells into biofluids, carrying actionable molecular fingerprints of the underlying disease with considerable diagnostic and therapeutic potential. The scarcity, heterogeneity and intrinsic complexity of tumor EVs present a major technological challenge in real-time monitoring of complex cancers such as glioblastoma (GBM). Surface-enhanced Raman spectroscopy (SERS) outputs a label-free spectroscopic fingerprint for EV molecular profiling. However, it has not been exploited to detect known biomarkers at the single EV level. We developed a multiplex fluidic device with embedded arrayed nanocavity microchips (MoSERS microchip) that achieves 97% confinement of single EVs in a minute amount of fluid (<10 μL) and enables molecular profiling of single EVs with SERS. The nanocavity arrays combine two featuring characteristics: (1) An embedded MoS monolayer that enables label-free isolation and nanoconfinement of single EVs due to physical interaction (Coulomb and van der Waals) between the MoS edge sites and the lipid bilayer; and (2) A layered plasmonic cavity that enables sufficient electromagnetic field enhancement inside the cavities to obtain a single EV level signal resolution for stratifying the molecular alterations. We used the GBM paradigm to demonstrate the diagnostic potential of the SERS single EV molecular profiling approach. The MoSERS multiplexing fluidic achieves parallel signal acquisition of glioma molecular variants (EGFRvIII oncogenic mutation and MGMT expression) in GBM cells. The detection limit of 1.23% was found for stratifying these key molecular variants in the wild-type population. When interfaced with a convolutional neural network (CNN), MoSERS improved diagnostic accuracy (87%) with which GBM mutations were detected in 12 patient blood samples, on par with clinical pathology tests. Thus, MoSERS demonstrates the potential for molecular stratification of cancer patients using circulating EVs.
Topics: Humans; Glioblastoma; Molybdenum; Brain Neoplasms; Glioma; Extracellular Vesicles; Spectrum Analysis, Raman
PubMed: 37366177
DOI: 10.1021/acsnano.2c09222 -
Spectrochimica Acta. Part A, Molecular... Oct 2023The rapid determination of ore grade can improve the efficiency of beneficiation. The existing molybdenum ore grade determination methods lag behind the beneficiation...
The rapid determination of ore grade can improve the efficiency of beneficiation. The existing molybdenum ore grade determination methods lag behind the beneficiation work. Therefore, this paper proposes a method based on a combination of Visible-infrared spectroscopy and machine learning to rapidly determine molybdenum ore grade. Firstly, 128 molybdenum ores were collected as spectral test samples to obtain spectral data. Then 13 latent variables were extracted from the 973 spectral features using partial least square. The Durbin-Watson test and the runs test were used to detect the partial residual plots and augmented partial residual plots of LV and LV to determine the non-linear relationship between spectral signal and molybdenum content. Extreme Learning Machine (ELM) was used instead of linear modeling methods to model the grade of molybdenum ores because of the non-linear behavior of the spectral data. In this paper, the Golden Jackal Optimization of adaptive T-distribution was used to optimize the parameters of the ELM to solve the problem of unreasonable parameters. Aiming at solving ill-posed problems by ELM, this paper decomposes the ELM output matrix by using the improved truncated singular value decomposition. Finally, this paper proposes an extreme learning machine method based on a modified truncated singular value decomposition and a Golden Jackal Optimization of adaptive T-distribution (MTSVD-TGJO-ELM). Compared with other classical machine learning algorithms, MTSVD-TGJO-ELM has the highest accuracy. This provides a new method for rapid detection of ore grade in the mining process and facilitates accurate beneficiation of molybdenum ores to improve ore recovery rate.
PubMed: 37156173
DOI: 10.1016/j.saa.2023.122789 -
Basic & Clinical Pharmacology &... Sep 2023Inhalation studies are the gold standard for assessing the toxicity of airborne materials. They require considerable time, special equipment, and large amounts of test...
Inhalation studies are the gold standard for assessing the toxicity of airborne materials. They require considerable time, special equipment, and large amounts of test material. Intratracheal instillation is considered a screening and hazard assessment tool as it is simple, quick, allows control of the applied dose, and requires less test material. The particle-induced pulmonary inflammation and acute phase response in mice caused by intratracheal instillation or inhalation of molybdenum disulphide or tungsten particles were compared. End points included neutrophil numbers in bronchoalveolar lavage fluid, Saa3 mRNA levels in lung tissue and Saa1 mRNA levels in liver tissue, and SAA3 plasma protein. Acute phase response was used as a biomarker for the risk of cardiovascular disease. Intratracheal instillation of molybdenum disulphide or tungsten particles did not produce pulmonary inflammation, while molybdenum disulphide particles induced pulmonary acute phase response with both exposure methods and systemic acute phase response after intratracheal instillation. Inhalation and intratracheal instillation showed similar dose-response relationships for pulmonary and systemic acute phase response when molybdenum disulphide was expressed as dosed surface area. Both exposure methods showed similar responses for molybdenum disulphide and tungsten, suggesting that intratracheal instillation can be used for screening particle-induced acute phase response and thereby particle-induced cardiovascular disease.
Topics: Animals; Mice; Tungsten; Acute-Phase Reaction; Cardiovascular Diseases; RNA, Messenger
PubMed: 37312155
DOI: 10.1111/bcpt.13915 -
Journal of Inorganic Biochemistry Aug 2023The electron paramagnetic resonance (EPR) investigation of mononuclear cis- and trans-(L1O)MoOCl complexes...
The electron paramagnetic resonance (EPR) investigation of mononuclear cis- and trans-(L1O)MoOCl complexes [L1OH = bis(3,5-dimethylpyrazolyl)-3-tert-butyl-2-hydroxy-5-methylphenyl)methane] reveals a significant difference in their spin Hamiltonian parameters which reflect different equatorial and axial ligand fields created by the heteroscorpionate donor atoms. Density functional theory (DFT) was used to calculate the values of principal components and relative orientations of the g and A tensors, and the molecular framework in four pairs of isomeric mononuclear oxo‑molybdenum(V) complexes (cis- and trans-(L1O)MoOCl, cis,cis- and cis,trans-(L-NS)MoOCl [L-NSH = N,N'-dimethyl-N,N'-bis(mercaptophenyl)ethylenediamine], cis,cis- and cis,trans-(L-NS)MoO(SCN), and cis- and trans-[(dt)MoO(OMe)] [dtH = 2,3-dimercapto-2-butene]). Scalar relativistic DFT calculations were conducted using three different exchange-correlation functionals. It was found that the use of hybrid exchange-correlation functional with 25% of the Hartree-Fock exchange leads to the best quantitative agreement between theory and experiment. A simplified ligand-field approach was used to analyze the influence of the ligand fields in all cis- and trans-isomers on energies and contributions of molybdenum d-orbital manifold to g and A tensors and relative orientations. Specifically, contributions that originated from the spin-orbit coupling of the d, d, and d orbitals into the ground state have been discussed. The new findings are discussed in the context of the experimental data of mononuclear molybdoenzyme, DMSO reductase.
Topics: Electron Spin Resonance Spectroscopy; Molybdenum; Density Functional Theory; Ligands
PubMed: 37149488
DOI: 10.1016/j.jinorgbio.2023.112228 -
Advanced Healthcare Materials Jan 2024The complex wound environment of diabetic wounds leads to poor treatment efficacy, and the inflammatory disorders and vascular injury are the primary causes of death in...
Controllable Adaptive Molybdate-Oligosaccharide Nanoparticles Regulate M2 Macrophage Mitochondrial Function and Promote Angiogenesis via PI3K/HIF-1α/VEGF Pathway to Accelerate Diabetic Wound Healing.
The complex wound environment of diabetic wounds leads to poor treatment efficacy, and the inflammatory disorders and vascular injury are the primary causes of death in such patients. Herein, a sprayable, controllable adaptive, pH-responsive nanosystem of molybdate and oligosaccharide (CMO) is specially developed as an immunomodulatory and angiogenesis-promotion material for diabetic wound healing. CMO exhibited pH-responsive release of Mo and oligosaccharide (COS), specifically in response to the alkalescent environment observed in diabetic wounds. CMO provide an anti-inflammatory environment by promoting M2 polarization through significantly stimulating macrophage mitochondrial function. Specifically, CMO with a certain concentration reduce reactive oxygen species (ROS) and tumor necrosis factor α (TNF-α) expression, and upregulated mitochondrial membrane potential (MMP), superoxide dismutase (SOD), and interleukin 10 (IL-10) expression in macrophages. Moreover, CMO facilitate angiogenesis via upregulating the PI3K/HIF-1α/VEGF pathway-a critical process for the formation of new blood vessels that supply nutrients and oxygen to the healing tissue. Remarkably, CMO promote cell viability and migration of endothelial cells, and enhance the expression of angiogenic genes. In vitro and in vivo studies suggest this simple but powerful nanosystem targeting mitochondrial function has the potential to become an effective treatment for diabetic wound healing.
Topics: Humans; Vascular Endothelial Growth Factor A; Phosphatidylinositol 3-Kinases; Endothelial Cells; Angiogenesis; Diabetes Mellitus; Wound Healing; Molybdenum
PubMed: 37922497
DOI: 10.1002/adhm.202302256 -
Protein Science : a Publication of the... Sep 2023Within the cell, the trace element molybdenum (Mo) is only biologically active when complexed either within the nitrogenase-specific FeMo cofactor or within the...
Within the cell, the trace element molybdenum (Mo) is only biologically active when complexed either within the nitrogenase-specific FeMo cofactor or within the molybdenum cofactor (Moco). Moco consists of an organic part, called molybdopterin (MPT) and an inorganic part, that is, the Mo-center. The enzyme which catalyzes the Mo-center formation is the molybdenum insertase (Mo-insertase). Mo-insertases consist of two functional domains called G- and E-domain. The G-domain catalyzes the formation of adenylated MPT (MPT-AMP), which is the substrate for the E-domain, that catalyzes the actual molybdate insertion reaction. Though the functions of E- and G-domain have been elucidated to great structural and mechanistic detail, their combined function is poorly characterized. In this work, we describe a structural model of the eukaryotic Mo-insertase Cnx1 complex that was generated based on cross-linking mass spectrometry combined with computational modeling. We revealed Cnx1 to form an asymmetric hexameric complex which allows the E- and G-domain active sites to align in a catalytic productive orientation toward each other.
Topics: Arabidopsis Proteins; Calnexin; Arabidopsis; Molybdenum; Coenzymes; Metalloproteins; Pteridines
PubMed: 37572332
DOI: 10.1002/pro.4753 -
ACS Applied Materials & Interfaces Sep 2023Developing highly active and robust oxygen catalysts is of great significance for the commercialization of Zn-air batteries (ZABs) with long-life stability. Herein,...
Developing highly active and robust oxygen catalysts is of great significance for the commercialization of Zn-air batteries (ZABs) with long-life stability. Herein, heterostructured catalysts comprising molybdenum carbide and metallic Co are prepared by a simple dicyandiamide-assisted pyrolysis strategy. Importantly, the crystalline phase of molybdenum carbide in the catalysts can be carefully regulated by adjusting the CoMo-imidazole precursor and dicyandiamide ratio. The electronic configuration of Co and Mo centers as well as the phase-dependent oxygen reduction reaction performance of these heterostructures (β-MoC/Co, β-MoC/η-MoC/Co, and η-MoC/Co) was disclosed. A highly active η-MoC/Co cathode enables ZABs with outstanding long-term stability over 850 h with a low voltage decaying rate of 0.06 mV·h and high peak power density of 162 mW·cm. This work provides a new idea for the rational design of efficient and stable cathode catalysts for ZABs.
PubMed: 37625012
DOI: 10.1021/acsami.3c06711 -
ACS Nano Aug 2023Soybean () is a crop of global significance and has low reliance on N fertilizers due to its biological nitrogen fixation (BNF) capacity, which harvests ambient N as a...
Soybean () is a crop of global significance and has low reliance on N fertilizers due to its biological nitrogen fixation (BNF) capacity, which harvests ambient N as a critical ecosystem service. BNF can be severely compromised by abiotic stresses. Enhancing BNF is increasingly important not only to alleviate global food insecurity but also to reduce the environmental impact of agriculture by decreasing chemical fertilizer inputs. However, this has proven challenging using current genetic modification or bacterial nodulation methods. Here, we demonstrate that a single application of a low dose (10 mg/kg) of molybdenum disulfide nanoparticles (MoS NPs) can enhance soybean BNF and grain yield by 30%, compared with conventional molybdate fertilizer. Unlike molybdate, MoS NPs can more sustainably release Mo, which then is effectively incorporated as a cofactor for the synthesis of nitrogenase and molybdenum-based enzymes that subsequently enhance BNF. Sulfur is also released sustainably and incorporated into biomolecule synthesis, particularly in thiol-containing antioxidants. The superior antioxidant enzyme activity of MoS NPs, together with the thiol compounds, protect the nodules from reactive oxygen species (ROS) damage, delay nodule aging, and maintain the BNF function for a longer term. The multifunctional nature of MoS NPs makes them a highly effective strategy to enhance plant tolerance to abiotic stresses. Given that the physicochemical properties of nanomaterials can be readily modulated, material performance (e.g., ROS capturing capacity) can be further enhanced by several synthesis strategies. This study thus demonstrates that nanotechnology can be an efficient and sustainable approach to enhancing BNF and crop yield under abiotic stress and combating global food insecurity.
Topics: Nitrogen Fixation; Glycine max; Molybdenum; Ecosystem; Reactive Oxygen Species; Fertilizers; Nitrogen
PubMed: 37498282
DOI: 10.1021/acsnano.3c02783