Folate Receptor Targeting Mn(II) Complex Encapsulated Porous Silica Nanoparticle as an MRI Contrast Agent for Early-State Detection of Cancer.

Cancer is recognized as one of the major causes of mortality, however, early-stage detection can increase the survival chance greatly. It is recognized that folate receptors are gradually overexpressed in the cellular membrane with the progress of cancer from stage 1 to stage 4. Utilizing the fact, herein, developed a porous silica nanoparticle system C1@SiO2-FA-NP; A) impregnated with thermodynamically stable Mn(II) complex (1) molecules within the core of the nanoparticle, and B) surface functionalized with folate units. It exhibited a high longitudinal relaxivity value r1 = 21.45 mM-1s-1 that substantially increased to r1 = 40.97 mM-1s-1 in the presence of 0.67 mM concentration of BSA under the physiological condition. The in vitro fluorescent images after surface conjugation of C1@SiO2-FA-NP with FITC (fluorescein isothiocyanate) buttressed the inclusion of the nanoparticle exclusively within the cancerous HeLa cells than that of healthy HEK293 cells. The importance of the surface-bound folate unit in the nanoparticle is further established by comparing the fluorescent images of HeLa cells in the absence of the group. Finally, the applicability of C1@SiO2-FA-NP as the T1-weighted MRI contrast agent for early-stage cancer diagnosis is established within C57BL/6 mice after infecting the mice with HeLa cells.

Well-Defined Mn(II)-complex Catalyzed Switchable De(hydrogenative) Csp3 -H Functionalization of Methyl Heteroarenes: A Sustainable Approach for Diversification of Heterocyclic Motifs.

Catalytic activities of Mn(I) complexes derived from expensive MnBr(CO)5 salt have been explored in various dehydrogenative transformations. However, the reactivity and selectivity of inexpensive high spin Mn(II) complexes are uncommon. Herein, we have synthesized four new Mn(II) complexes and explored switchable alkenylation and alkylation of methyl heteroarenes employing a single Mn(II)catalyst. The developed protocol selectively furnishes a series of functionalized E-heteroarenes and C-alkylated heteroarenes with good to excellent yields. Various medicinally and synthetically useful compounds are successfully synthesized using our developed protocol. Various controls and kinetics experiments were executed to shed light on the mechaism,which reveals that α-C-H bond breaking of alcohol is the slowest step.

Highly Efficient Detection of Pd2+ in Aqueous Medium by an Elusive Mn(II) Coordination Polymer.

Herein, we report the synthesis of a Mn(II)-based coordination polymer (CP); and its structure, phase consistency and thermal stability have been established by single-crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD) and thermalgravimetric analysis (TGA) respectively. This is the first example of paramgnetic Mn(II)-based CP that acts as pH-dependent emitting material [λem=525 nm (pH=2.0-4.0) and 450 nm (pH=5.0-12.0)]. Its emission is quenched by Pd2+ in aqueous medium in presence of other thirteen cations with reasonably low pH-dependent limits of detection (LODs) [21.178 ppb (pH=3), 15.005 ppb (pH=7.0) and 59.940 ppb (pH=10.0)] as described by well-established mechanism. Therefore, urgency of such stable sensor remains high in regard to the environmental pollution.

Highly Efficient Degradation of Emerging Contaminants with Sodium Bicarbonate-Enhanced Mn(II)/Peracetic Acid Process: Formation and Contribution of Mn(V).

Organic ligands have been extensively used to enhance the catalytic performance of manganese ion (Mn(II)) for peracetic acid (PAA). In this study, sodium bicarbonate (NaHCO3), an economical and eco-friendly inorganic ligand, was introduced to enhance the degradation of emerging contaminants (ECs) in the Mn(II)/PAA process. NaHCO3 could significantly improve the oxidizing ability of the Mn(II)/PAA process over the initial pH range of 3.0-11.0. Mn(V) was identified as the primary reactive species for degrading naproxen in the NaHCO3/Mn(II)/PAA process. HCO3- could complex with Mn(II) to generate Mn(II)-HCO3-, which has a lower redox potential to enhance the catalytic activity of Mn(II). Mn(II)-HCO3- reacted with PAA to produce Mn(III)-HCO3- and CH3C(O)O•. Mn(V)-HCO3- was generated via two-electron transfer between Mn(III)-HCO3- and PAA. Although organic radicals were detected in the NaHCO3/Mn(II)/PAA process, naproxen was mainly degraded by Mn(V)-HCO3- via one-electron transfer along with the formation of MnO2. Notably, the coexisting hydrogen peroxide was vital in the reduction of MnO2 to Mn(II/III), thereby enhancing the continuous generation of Mn(V)-HCO3-. NaHCO3/Mn(II)/PAA process exhibited exceptional oxidation performance in actual water samples. This study proposed a strategy utilizing an eco-friendly inorganic ligand to address the inherent drawbacks of organic ligand-enhanced Mn(II)/PAA processes and highlighted its potential applications in the removal of ECs.

Single Droplet Tweezer Revealing the Reaction Mechanism of Mn(II)-Catalyzed SO2 Oxidation.

Sulfate aerosol is one of the major components of secondary fine particulate matter in urban haze that has crucial impacts on the social economy and public health. Among the atmospheric sulfate sources, Mn(II)-catalyzed SO2 oxidation on aerosol surfaces has been regarded as a dominating one. In this work, we measured the reaction kinetics of Mn(II)-catalyzed SO2 oxidation in single droplets using an aerosol optical tweezer. We show that the SO2 oxidation occurs at the Mn(II)-active sites on the aerosol surface, per a piecewise kinetic formulation, one that is characterized by a threshold surface Mn(II) concentration and gaseous SO2 concentration. When the surface Mn(II) concentration is lower than the threshold value, the reaction rate is first order with respect to both Mn(II) and SO2, agreeing with our traditional knowledge. But when surface Mn(II) concentration is above the threshold, the reaction rate becomes independent of Mn(II) concentration, and the reaction order with respect to SO2 becomes greater than unity. The measured reaction rate can serve as a tool to estimate sulfate formation based on field observation, and our established parametrization corrects these calculations. This framework for reaction kinetics and parametrization holds promising potential for generalization to various heterogeneous reaction pathways.

Effects of biochar on the manganese enrichment and oxidation by a microalga Scenedesmus quadricauda in the aquatic environment.

Microalgae play a significant impact in the biogeochemical cycle of Mn(II) in the aquatic ecosystem. Meanwhile, the inflow of biochar into the water bodies is bound to impact the aquatic organisms. However, the influence of biochar on the manganese transformation in algae-rich water has not drawn much attention. Thus, we studied the effects of rice straw biochar on manganese enrichment and oxidation by a common type of algae in freshwater (Scenedesmus quadricauda). The results showed that Mn(II) was absorbed intracellularly and adsorbed extracellularly by active algal cells. A significant portion of enriched Mn(II) was oxidized to amorphous precipitates MnO2, MnOOH, and Mn2O3. Moreover, the extracellular bound Mn(II) content in the coexistent system of algae and biochar increased compared with the pure Scenedesmus quadricauda system. Nevertheless, the intracellular Mn content was continually lowered as the biochar dose rose from an initial 0.2 to 2.0 g·L-1, suggesting that Mn assimilation of the cell was suppressed. It was calculated that the total enrichment ability of Scenedesmus quadricauda in the algae-biochar coexistent system was 0.31- 15.32 mg Mn/g biomass, more than that in the pure algae system. More importantly, with biochar in the algae system, the amount of generated MnOx increased, and more Mn(II) was oxidized into highly-charged Mn(IV). This was probably because the biochar could relieve the stress of massive Mn(II) on algae and support the MnOx precipitates. In brief, moderate biochar promoted the Mn(II) accumulation by algal cells and its oxidation activity. This study offers deeper insight into the bioconversion of Mn(II) by algae and the potential impact of biochar application to the aquatic system.

Highly Efficient Utilization of Ferrate(VI) Oxidation Capacity Initiated by Mn(II) for Contaminant Oxidation: Role of Manganese Species.

Manganese ion [Mn(II)] is a background constituent existing in natural waters. Herein, it was found that only 59% of bisphenol A (BPA), 47% of bisphenol F (BPF), 65% of acetaminophen (AAP), and 49% of 4-tert-butylphenol (4-tBP) were oxidized by 20 µM of Fe(VI), while 97% of BPA, 95% of BPF, 96% of AAP, and 94% of 4-tBP could be oxidized by the Fe(VI)/Mn(II) system [20 µM Fe(VI)/20 µM Mn(II)] at pH 7.0. Further investigations showed that bisphenol S (BPS) was highly reactive with reactive iron species (RFeS) but was sluggish with reactive manganese species (RMnS). By using BPS and methyl phenyl sulfoxide (PMSO) as the probe compounds, it was found that reactive iron species contributed primarily for BPA oxidation at low Mn(II)/Fe(VI) molar ratios (below 0.1), while reactive manganese species [Mn(VII)/Mn(III)] contributed increasingly for BPA oxidation with the elevation of the Mn(II)/Fe(VI) molar ratio (from 0.1 to 3.0). In the interaction of Mn(II) and Fe(VI), the transfer of oxidation capacity from Fe(VI) to Mn(III), including the formation of Mn(VII) and the inhibition of Fe(VI) self-decay, improved the amount of electron equivalents per Fe(VI) for BPA oxidation. UV-vis spectra and dominant transformation product analysis further revealed the evolution of iron and manganese species at different Mn(II)/Fe(VI) molar ratios.

New Cu(II), Mn(II) and Mn(III) Schiff base complexes cause noncovalent interactions: X-ray crystallography survey, Hirshfeld surface analysis and molecular simulation investigation against SARS-CoV-2.

In this study, polynuclear Cu(II) complex (1), Mn(II) and Mn(III) complex (2) have been prepared with a Schiff base ligand derived from 2-Hydroxy-3-methoxybenzaldehyde with 2-amino-2-methyl-1-propanol. The compounds were characterized by elemental analysis, FT-IR, and UV-Vis spectroscopy. The molecular and crystal structures of (1-2) were determined by the single-crystal x-ray diffraction technique. It turned out that Cu(II) complex (1) forms an S4 -symmetrical tetrameric cage structure, with square-planar coordinated Cu and bridging O atoms at the vertexes of the approximate cube. In the crystal structure of 1, there are large channels along the c-axis, between the tetramers; the solvent- DMSO molecules, occupies these channels. In turn, the complex (2) creates a centrosymmetric trimeric structure, with three octahedrally coordinated Mn ions bridged by O atoms from ligand molecules and acetate ions. The electrochemical behavior studies of the complexes in DMSO displayed the electronic effects of the groups on the redox potential. The redox behavior of Schiff base (1) and (2) complexes included quasi -reversible and irreversible voltammograms, respectively. Intermolecular interactions in the solid states were studied by Hirshfeld surface analysis. These studies provide a comprehensive description of these inter-contact exchanges using an attractive graphical representation using Hirshfeld surfaces and fingerprint plots, along with enrichment ratios. Furthermore, assessment of the inhibitory effect against coronavirus (main protease SARS-CoV-2) was performed by a molecular docking study for both complexes (1 and 2). Both complexes showed a good affinity for CoV-2 for PDB protein ID: 6M03 and 6Y2F.

NMR-Relaxometric Investigation of Mn(II)-Doped Polyoxometalates in Aqueous Solutions.

Solution behavior of K;5[(Mn(H2O))PW11O39]·7H2O (1), Na3.66(NH4)4.74H3.1[(MnII(H2O))2.75(WO(H2O))0.25(α-B-SbW9O33)2]·27H2O (2), and Na4.6H3.4[(MnII(H2O)3)2(WO2)2(ß-B-TeW9O33)2]·19H2O (3) was studied with NMR-relaxometry and HPLC-ICP-AES (High Performance Liquid Chromatography coupled with Inductively Coupled Plasma Atomic Emission Spectroscopy). According to the data, the [(Mn(H2O))PW11O39]5- Keggin-type anion is the most stable in water among the tested complexes, even in the presence of ethylenediaminetetraacetic acid (EDTA) or diethylenetriaminepentaacetic acid (DTPA). Aqueous solutions of 2 and 3 anions are less stable and contain other species resulting from dissociation of Mn2+. Quantum chemical calculations show the change in Mn2+ electronic state between [Mn(H2O)6]2+ and [(Mn(H2O))PW11O39]5-.

The Effects of Mono- and Bivalent Linear Alkyl Interlayer Spacers on the Photobehavior of Mn(II)-Based Perovskites.

Mn(II)-based perovskite materials are being intensively explored for lighting applications; understanding the role of ligands regarding their photobehavior is fundamental for their development. Herein, we report on two Mn (II) bromide perovskites using monovalent (perovskite 1, P1) and bivalent (perovskite 2, P2) alkyl interlayer spacers. The perovskites were characterized with powder X-ray diffraction (PXRD), electron spin paramagnetic resonance (EPR), steady-state, and time-resolved emission spectroscopy. The EPR experiments suggest octahedral coordination in P1 and tetrahedral coordination for P2, while the PXRD results demonstrate the presence of a hydrated phase in P2 when exposed to ambient conditions. P1 exhibits an orange-red emission, while P2 shows a green photoluminescence, as a result of the different types of coordination of Mn(II) ions. Furthermore, the P2 photoluminescence quantum yield (26%) is significantly higher than that of P1 (3.6 %), which we explain in terms of different electron-phonon couplings and Mn-Mn interactions. The encapsulation of both perovskites into a PMMA film largely increases their stability against moisture, being more than 1000 h for P2. Upon increasing the temperature, the emission intensity of both perovskites decreases without a significant shift in the emission spectrum, which is explained in terms of an increase in the electron-phonon interactions. The photoluminescence decays fit two components in the microsecond regime-the shortest lifetime for hydrated phases and the longest one for non-hydrated phases. Our findings provide insights into the effects of linear mono- and bivalent organic interlayer spacer cations on the photophysics of these kinds of Mn (II)-based perovskites. The results will help in better designs of Mn(II)-perovskites, to increase their lighting performance.

Small Molecule Pytren-4QMn Metal Complex Slows down Huntington's Disease Progression in Male zQ175 Transgenic Mice.

Huntington's disease (HD) is an inherited neurodegenerative disorder considered a rare disease with a prevalence of 5.7 per 100,000 people. It is caused by an autosomal dominant mutation consisting of expansions of trinucleotide repeats that translate into poly-glutamine enlarged mutant huntingtin proteins (mHTT), which are particularly deleterious in brain tissues. Since there is no cure for this progressive fatal disease, searches for new therapeutic approaches are much needed. The small molecule pytren-4QMn (4QMn), a highly water-soluble mimic of the enzyme superoxide dismutase, has shown in vivo beneficial anti-inflammatory activity in mice and was able to remove mHTT deposits in a C. elegans model of HD. In this study, we assessed 4QMn therapeutic potential in zQ175 neo-deleted knock-in mice, a model of HD that closely mimics the heterozygosity, genetic injury, and progressive nature of the human disease. We provide evidence that 4QMn has good acute and chronic tolerability, and can cross the blood-brain barrier, and in male, but not female, zQ175 mice moderately ameliorate HD-altered gene expression, mHtt aggregation, and HD disease phenotype. Our data highlight the importance of considering sex-specific differences when testing new therapies using animal models and postulate 4QMn as a potential novel type of small water-soluble metal complex that could be worth further investigating for its therapeutic potential in HD, as well as in other polyglutamine diseases.

Modification of Multiwalled Carbon Nanotubes and Their Mechanism of Demanganization.

Multiwalled carbon nanotubes (MWCNTs) were modified by oxidation and acidification with concentrated HNO3 and H2SO4, and the modified multiwalled carbon nanotubes (M-MWCNTs) and raw MWCNTs were characterized by several analytical techniques. Then the demanganization effects of MWCNTs and M-MWCNTs were well investigated and elucidated. The experimental data demonstrated that the adsorption efficiency of Mn(II) could be greatly promoted by M-MWCNTs from about 20% to 75%, and the optimal adsorption time was 6 h and the optimal pH was 6. The results of the kinetic model studies showed that Mn(II) removal by M-MWCNTs followed the pseudo-second-order model. Isothermal studies were conducted and the results demonstrated that the experimental data fitted well with the three models. The reliability of the experimental results was well verified by PSO-BP simulation, and the present conclusion could be used as a condition for further simulation. The research results provide a potential technology for promoting the removal of manganese from wastewater; at the same time, the application of various mathematical models also provides more scientific ideas for the research of the mechanism of adsorption of heavy metals by nanomaterials.

More negative charges on roots enhanced manganese(II) uptake in leguminous and non-leguminous poaceae crops.

BACKGROUND: Manganese (Mn) is an essential micronutrient for plants, whereas excess Mn(II) in soils leads to its toxicity to crops. Mn(II) is adsorbed onto plant roots from soil solution and then absorbed by plants. Root charge characteristics should affect Mn(II) toxicity to crops and Mn(II) uptake by the roots of the crops. However, the differences in the effects of root surface charge on the uptake of Mn(II) among various crop species are not well understood. RESULTS: The roots of nine legumes and six non-legume poaceae were obtained by hydroponics and the streaming potential method and spectroscopic analysis were used to measure the zeta potentials and functional groups on the roots, respectively. The results indicate that the exchangeable Mn(II) adsorbed by plant roots was significantly positively correlated with the Mn(II) accumulated in plant shoots. Legume roots carried more negative charges and functional groups than non-legume poaceae roots, which was responsible for the larger amounts of exchangeable Mn(II) on legume roots in 2 h and the Mn(II) accumulated in their shoots in 48 h. Coexisting cations, such as Ca2+ and Mg2+ , were most effective in decreasing Mn(II) taken up by roots and accumulated in shoots than K+ and Na+ . This was because Ca2+ and Mg2+ could compete with Mn(II) for active sites on plant roots more strongly compared to K+ and Na+ . CONCLUSION: The root surface charge and functional groups are two important factors influencing Mn(II) uptake by roots and accumulation in plant shoots. © 2023 Society of Chemical Industry.

Induced transformation of antimony trioxide by Mn(II) oxidation and their co-transformed mechanism.

Antimony (Sb) is a toxic and carcinogenic element that often enters soil in the form of antimony trioxide (Sb2O3) and coexists with manganese (Mn) in weakly alkaline conditions. Mn oxides such as birnessite have been found to promote the oxidative dissolution of Sb2O3, but few researches concerned the co-transformations of Sb2O3 and Mn(II) in environment. This study investigated the mutual effect of abiotic oxidation of Mn(II) and the coupled oxidative dissolution of Sb2O3. The influencing factors, such as Mn(II) concentrations, pH and oxygen were also discussed. Furthermore, their co-transformed mechanism was also explored based on the analysis of Mn(II) oxidation products with or without Sb2O3 using XRD, SEM and XPS. The results showed that the oxidative dissolution of Sb2O3 was enhanced under higher pH and higher Mn(II) loadings. With a lower Mn(II) concentration such as 0.01 mmol/L Mn(II) at pH 9.0, the improved dissolution of Sb2O3 was attributed to the generation of dissolved intermediate Mn(III) species with strong oxidation capacity. However, under higher Mn(II) concentrations, both amorphous Mn(III) oxides and intermediate Mn(III) species were responsible for promoting the oxidative dissolution of Sb2O3. Most released Sb (∼72%) was immobilized by Mn oxides and Sb(V) was dominant in the adsorbed and dissolved total Sb. Meanwhile, the presence of Sb2O3 not only inhibited the removal of Mn(II) by reducing Mn(III) to Mn(II) but also affected the final products of Mn oxides. For example, amorphous Mn oxides were formed instead of crystalline Mn(III) oxides, such as MnOOH. Furthermore, rhodochrosite (MnCO3) was formed with the high Mn(II)/Sb2O3 ratio, but without being observed in the low Mn(II)/Sb2O3 ratio. The results of study could help provide more understanding about the fate of Sb in the environment and the redox transformation of Mn.

Environmental Mn(II) enhances the activity of dissimilatory arsenate-respiring prokaryotes from arsenic-contaminated soils.

Many investigations suggest that dissimilatory arsenate-respiring prokaryotes (DARPs) play a key role in stimulating reductive mobilization of As from solid phase into groundwater, but it is not clear how environmental Mn(II) affects the DARPs-mediated reductive mobilization of arsenic. To resolve this issue, we collected soil samples from a realgar tailings-affected area. We found that there were diverse arsenate-respiratory reductase (arr) genes in the soils. The microbial communities had high arsenate-respiring activity, and were able to efficiently stimulate the reductive mobilization of As. Compared to the microcosms without Mn(II), addition of 10 mmol/L Mn(II) to the microcosms led to 23.99%-251.79% increases in the microbial mobilization of As, and led to 133.3%-239.2% increases in the abundances of arr genes. We further isolated a new cultivable DARP, Bacillus sp. F11, from the arsenic-contaminated soils. It completely reduced 1 mmol/L As(V) in 5 days under the optimal reaction conditions. We further found that it was able to efficiently catalyze the reductive mobilization and release of As from the solid phase; the addition of 2 mmol/L Mn(II) led to 98.49%-248.78% increases in the F11 cells-mediated reductive mobilization of As, and 70.6%-104.4% increases in the arr gene abundances. These data suggest that environmental Mn(II) markedly increased the DARPs-mediated reductive mobilization of As in arsenic-contaminated soils. This work provided a new insight into the close association between the biogeochemical cycles of arsenic and manganese.

Simultaneous oxidation of Mn(II) and As(III) on cupric oxide (CuO) promotes As(III) removal at circumneutral pH.

Oxidation of Mn(II) or As(III) by molecular oxygen is slow at pH < 9, while they can be catalytically oxidized in the presence of oxide minerals and then removed from contaminated water. However, the reaction mechanisms on simultaneous oxidation of Mn(II) and As(III) on oxide mineral surface and their accompanied removal efficiency remain unclear. This study compared Mn(II) oxidation on four common metal oxides (γ-Al2O3, CuO, α-Fe2O3 and ZnO) and investigated the simultaneous oxidation and removal of Mn(II) and As(III) through batch experiments and spectroscopic analyses. Among the tested oxides, CuO and α-Fe2O3 possess greater catalytic activity toward Mn(II) oxidation. Oxidation and removal kinetics of Mn(II) and As(III) on CuO indicate that O2 is the terminal electron acceptor for Mn(II) and As(III) oxidation on CuO, and Mn(II) acts as an electron shuttle to promote As(III) oxidation and removal. The main oxidized product of Mn(II) on CuO is high-valent MnOx species. This newly formed Mn(III) or Mn(IV) phases promote As(III) oxidation on CuO at circumneutral pH 8 and is reduced to Mn(II), which may be then released into solution. This study provides new insights into metal oxide-catalyzed oxidation of pollutants Mn(II) and As(III) and suggests that CuO should be considered as an efficient material to remediate Mn(II) and As(III) contamination.

Investigation of electrocatalytic activity of a new mononuclear Mn(II) complex for water oxidation in alkaline media.

Water splitting is a promising way to alleviate the energy crisis. In nature, water oxidation is done by a tetranuclear manganese cluster in photosystem II. Therefore, the study of water oxidation by Mn complexes is attractive in water splitting systems. In this report, a new mononuclear Mn(II) complex, MnL2 (HL = (E)-3-hydroxy-N'-(pyridin-2-ylmethylene)-2-naphthohydrazide) was prepared and characterized by spectroscopic techniques and single-crystal X-ray diffraction. Crystallographic analysis indicated that the geometry around the Mn(II) ion is distorted octahedral. The MnN4O2 coordination moiety is achieved by bounding of oxygen and two nitrogen donor atoms of two hydrazone ligands. The synthesized complex was also investigated for electrochemical water oxidation using electrochemical techniques, scanning electron microscopy, energy dispersive spectrometry, and PXRD analysis. Linear sweep voltammetry experiment showed that the modified carbon paste electrode by the complex displays high activity for water oxidation reaction with an overpotential of 565 mV at a current density of 10 mA cm-2 and Tafel slope of 105 mV dec-1 in an alkaline solution. It was found that the complex structure finally changes during the reaction and converts to Mn oxide nanoparticles which act as active catalytic species and oxidize the water.

Water oxidation reaction in the presence of a dinuclear Mn(II)-semicarbohydrazone coordination compound.

Water splitting, producing of oxygen, and hydrogen molecules, is an essential reaction for clean energy resources and is one of the challenging reactions for artificial photosynthesis. The Mn4Ca cluster in photosystem II (PS-II) is responsible for water oxidation in natural photosynthesis. Due to this, water oxidation reaction by Mn coordination compounds is vital for mimicking the active core of the oxygen-evolving complex in PS-II. Here, a new dinuclear Mn(II)-semicarbohydrazone coordination compound, [Mn(HL)(µ-N3)Cl]2 (1), was synthesized and characterized by various methods. The structure of compound 1 was determined by single crystal X-ray analysis, which revealed the Mn(II) ions have distorted octahedral geometry as (MnN4OCl). This geometry is created by coordinating of oxygen and two nitrogen donor atoms from semicarbohydrazone ligand, two nitrogen atoms from azide bridges, and chloride anion. Compound 1 was used as a catalyst for electrochemical water oxidation, and the surface of the electrode after the reaction was investigated by scanning electron microscopy, energy dispersive spectrometry, and powder X-ray diffraction analyses. Linear sweep voltammetry (LSV) experiments revealed that the electrode containing 1 shows high activity for chemical water oxidation with an electrochemical overpotential as low as 377 mV. Although our findings showed that the carbon paste electrode in the presence of 1 is an efficient electrode for water oxidation, it could not withstand water oxidation catalysis under bulk electrolysis and finally converted to Mn oxide nanoparticles which were active for water oxidation along with compound 1.

A soil-borne Mn(II)-oxidizing bacterium of Providencia sp. exploits a strategy of superoxide production coupled to hydrogen peroxide consumption to generate Mn oxides.

Bacterial non-enzymatic Mn(II) oxidation involving reactive oxygen species (ROS) (i.e., indirect oxidation), initially discovered from a marine alpha-proteobacterium, is believed to be of importance in controlling biogeochemical cycles. For soil-borne bacteria, however, evidence of indirect Mn(II) oxidation remains unclear. In this study, the indirect Mn(II) oxidation was evidenced in a soil-borne bacterium, Providencia sp. LLDRA6. First, with and without 50 mM of Mn(II) exposure for LLDRA6, 300 differentially expressed genes were found to be linked to Mn(II) exposure via transcriptome sequencing. Among them, an operon, responsible for phenylacetic acid catabolism, was sharply upregulated in transcription, drawing us a special attention, since its transcriptional upregulation has recently shown to be important for withstanding ROS. Next, a fluorometric probe, 2',7'-Dichlorofluorescin diacetate (DCFDA), was used to qualitatively detect ROS from cells, showing a distinct increase in fluorescence intensities of ROS during Mn(II) exposure. Furthermore, concentrations of superoxide and hydrogen peroxide from cells were detected, respectively, with and without Mn(II) exposure, exhibiting that when Mn(II) oxidation occurred, superoxide concentration significantly increased but hydrogen peroxide concentration significantly decreased. Particularly, superoxide produced by LLDRA6 was proven to be the oxidant for Mn(II) in the formation of Mn oxides. Finally, we predicted links between phenylacetic acid metabolism pathway and ROS during Mn(II) exposure, proposing that the excessive ROS, generated in response to Mn(II) exposure, transcriptionally activate phenylacetic acid catabolism presumably by increasing concentrations of highly reactive oxepins.

Providencia manganoxydans sp. nov., a Mn(II)-oxidizing bacterium isolated from heavy metal contaminated soils in Hunan Province, China.

A facultatively anaerobic, Gram-negative, rod-shaped bacterial strain designated as LLDRA6T, was isolated from heavy metal contaminated soils collected near a ceased smelting factory at Zhuzhou, Hunan Province, China. Strain LLDRA6T has the ability to oxidize Mn(II) and generate biogenic manganese oxides. The strain can grow in a wide range of temperature from 10-42°C and pH from 5 to 10. Comparative analysis of its complete 16S rRNA gene sequence suggests that strain LLDRA6T is highly similar to species within the genus Providencia. The complete genome of LLDRA6T is 4 342 370 bp with 40.18 mol% of G+C content and contains no plasmids. In comparison to the genomes of type strains in Providencia, LLDRA6T shows average nucleotide identity values between 76.60 and 80.89 %, and digital DNA-DNA hybridization values in a range of 21.2-24.6 %. Both multilocus sequence analysis and genomic phylogenetics indicate a new taxonomic status for LLDRA6T in Providencia. Chemotaxonomic analyses for LLDRA6T show that the predominant cellular fatty acids are C16 : 0, C14 : 0 and cyclo-C17 : 0, accounting for 32.7, 16.1 and 10.3 % of total fatty acids, respectively. The polar lipids consist of phosphatidylglycerol, diphosphatidylglycerol, phosphatidylethanolamine, four unidentified aminolipids, one unidentified phospholipid and three unidentified lipids. Within the cell wall, ribose and meso-diaminopimelic acid are the characteristic constituents for saccharides and amino acids, respectively. Respiratory quinones on cell membranes are composed of menaquinone (MK) and ubiquinone (coenzyme Q), including MK-8 (100.0 %), Q-7 (13.7 %) and Q-8 (86.3 %). Moreover, the positive results from d-lyxose and d-mannitol fermentation tests indicate that LLDRA6T is totally different from all the type strains within the genus Providencia. In summary, strain LLDRA6T represents a novel species in the genus Providencia, for which the name Providencia manganoxydans sp. nov. (type strain LLDRA6T=CCTCC AB 2021154T=KCTC 92091T) is proposed.