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Molecules (Basel, Switzerland) May 2023A story going back almost 40 years is presented in this manuscript. This is a different and more challenging way of reporting my research and I hope it will be useful to... (Review)
Review
A story going back almost 40 years is presented in this manuscript. This is a different and more challenging way of reporting my research and I hope it will be useful to and target a wide-ranging audience. When preparing the manuscript and collecting references on the subject of this paper-aldehyde oxidoreductase from -I felt like I was travelling back in time (and space), bringing together the people that have contributed most to this area of research. I sincerely hope that I can give my collaborators the credit they deserve. This study is not presented as a chronologic narrative but as a grouping of topics, the development of which occurred over many years.
Topics: Humans; Aldehyde Oxidoreductases; Desulfovibrio gigas; Desulfovibrio; Molybdenum; Aldehyde Dehydrogenase
PubMed: 37241969
DOI: 10.3390/molecules28104229 -
Protein Science : a Publication of the... Jan 2019An overview is provided of the molybdenum- and tungsten-containing enzymes that catalyze the interconversion of formate and CO , focusing on common structural and...
An overview is provided of the molybdenum- and tungsten-containing enzymes that catalyze the interconversion of formate and CO , focusing on common structural and mechanistic themes, as well as a consideration of the manner in which the mature Mo- or W-containing cofactor is inserted into apoprotein.
Topics: Aldehyde Oxidoreductases; Catalysis; Coenzymes; Formate Dehydrogenases; Molybdenum; Structure-Activity Relationship; Tungsten
PubMed: 30120799
DOI: 10.1002/pro.3498 -
Biosensors Aug 2023Cancer is a common illness with a high mortality. Compared with traditional technologies, biomarker detection, with its low cost and simple operation, has a higher... (Review)
Review
Cancer is a common illness with a high mortality. Compared with traditional technologies, biomarker detection, with its low cost and simple operation, has a higher sensitivity and faster speed in the early screening and prognosis of cancer. Therefore, extensive research has focused on the development of biosensors and the construction of sensing interfaces. Molybdenum disulfide (MoS) is a promising two-dimensional (2D) nanomaterial, whose unique adjustable bandgap shows excellent electronic and optical properties in the construction of biosensor interfaces. It not only has the advantages of a high catalytic activity and low manufacturing costs, but it can also further expand the application of hybrid structures through different functionalization, and it is widely used in various biosensors fields. Herein, we provide a detailed introduction to the structure and synthesis methods of MoS, and explore the unique properties and advantages/disadvantages exhibited by different structures. Specifically, we focus on the excellent properties and application performance of MoS and its composite structures, and discuss the widespread application of MoS in cancer biomarkers detection from both electrochemical and optical dimensions. Additionally, with the cross development of emerging technologies, we have also expanded the application of other emerging sensors based on MoS for early cancer diagnosis. Finally, we summarized the challenges and prospects of MoS in the synthesis, functionalization of composite groups, and applications, and provided some insights into the potential applications of these emerging nanomaterials in a wider range of fields.
Topics: Biomarkers, Tumor; Molybdenum; Catalysis; Electronics; Neoplasms
PubMed: 37754082
DOI: 10.3390/bios13090848 -
Toxicology Feb 2023Molybdenum disulphide (MoS) is a constituent of many products. To protect humans, it is important to know at what air concentrations it becomes toxic. For this, we...
Molybdenum disulphide (MoS) is a constituent of many products. To protect humans, it is important to know at what air concentrations it becomes toxic. For this, we tested MoS particles by nose-only inhalation in mice. Exposures were set to 13, 50 and 150 mg MoS/m (=8, 30 and 90 mg Mo/m), corresponding to Low, Mid and High exposure. The duration was 30 min/day, 5 days/week for 3 weeks. Molybdenum lung-deposition levels were estimated based on aerosol particle size distribution measurements, and empirically determined with inductively coupled plasma-mass spectrometry (ICP-MS). Toxicological endpoints were body weight gain, respiratory function, pulmonary inflammation, histopathology, and genotoxicity (comet assay). Acellular reactive oxygen species (ROS) production was also determined. The aerosolised MoS powder had a mean aerodynamic diameter of 800 nm, and a specific surface area of 8.96 m/g. Alveolar deposition of MoS in lung was estimated at 7, 27 and 79 µg/mouse and measured as 35, 101 and 171 µg/mouse for Low, Mid and High exposure, respectively. Body weight gain was lower than in controls at Mid and High exposure. The tidal volume was decreased with Low and Mid exposure on day 15. Increased genotoxicity was seen in bronchoalveolar lavage (BAL) fluid cells at Mid and High exposures. ROS production was substantially lower than for carbon black nanoparticles used as bench-mark, when normalised by mass. Yet if ROS of MoS was normalised by surface area, it was similar to that of carbon black, suggesting that a ROS contribution to the observed genotoxicity cannot be ruled out. In conclusion, effects on body weight gain and genotoxicity indicated that Low exposure (13 mg MoS/m, corresponding to 0.8 mg/m for an 8-hour working day) was a No Observed Adverse Effect Concentration (NOAEC,) while effects on respiratory function suggested this level as a Lowest Observed Adverse Effect Concentration (LOAEC).
Topics: Humans; Mice; Animals; Molybdenum; Reactive Oxygen Species; Soot; Respiratory Aerosols and Droplets; Lung; Bronchoalveolar Lavage Fluid; Weight Gain; Inhalation Exposure; Particle Size
PubMed: 36641057
DOI: 10.1016/j.tox.2023.153428 -
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 -
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 -
International Journal of Environmental... May 2020Nontuberculous mycobacteria (NTM) are environmental bacteria that may cause chronic lung disease. Environmental factors that favor NTM growth likely increase the risk of...
Nontuberculous mycobacteria (NTM) are environmental bacteria that may cause chronic lung disease. Environmental factors that favor NTM growth likely increase the risk of NTM exposure within specific environments. We aimed to identify water-quality constituents (Al, As, Cd, Ca, Cu, Fe, Pb, Mg, Mn, Mo, Ni, K, Se, Na, Zn, and pH) associated with NTM disease across Colorado watersheds. We conducted a geospatial, ecological study, associating data from patients with NTM disease treated at National Jewish Health and water-quality data from the Water Quality Portal. Water-quality constituents associated with disease risk were identified using generalized linear models with Poisson-distributed discrete responses. We observed a highly robust association between molybdenum (Mo) in the source water and disease risk. For every 1- unit increase in the log concentration of molybdenum in the source water, disease risk increased by 17.0%. We also observed a statistically significant association between calcium (Ca) in the source water and disease risk. The risk of NTM varied by watershed and was associated with watershed-specific water-quality constituents. These findings may inform mitigation strategies to decrease the overall risk of exposure.
Topics: Colorado; Humans; Molybdenum; Mycobacterium Infections, Nontuberculous; Nontuberculous Mycobacteria; Water Pollution; Water Quality
PubMed: 32485845
DOI: 10.3390/ijerph17113854 -
Nature Feb 2017The development of catalyst-controlled stereoselective olefin metathesis processes has been a pivotal recent advance in chemistry. The incorporation of appropriate...
The development of catalyst-controlled stereoselective olefin metathesis processes has been a pivotal recent advance in chemistry. The incorporation of appropriate ligands within complexes based on molybdenum, tungsten and ruthenium has led to reactivity and selectivity levels that were previously inaccessible. Here we show that molybdenum monoaryloxide chloride complexes furnish higher-energy (Z) isomers of trifluoromethyl-substituted alkenes through cross-metathesis reactions with the commercially available, inexpensive and typically inert Z-1,1,1,4,4,4-hexafluoro-2-butene. Furthermore, otherwise inefficient and non-stereoselective transformations with Z-1,2-dichloroethene and 1,2-dibromoethene can be effected with substantially improved efficiency and Z selectivity. The use of such molybdenum monoaryloxide chloride complexes enables the synthesis of representative biologically active molecules and trifluoromethyl analogues of medicinally relevant compounds. The origins of the activity and selectivity levels observed, which contradict previously proposed principles, are elucidated with the aid of density functional theory calculations.
Topics: Alkenes; Catalysis; Chlorides; Fluorocarbons; Ligands; Molybdenum
PubMed: 28114300
DOI: 10.1038/nature21043 -
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