High Mn2 Research Articles

From Ultrafast Photoinduced Small Polarons to Cooperative and Macroscopic Charge-Transfer Phase Transition.

We study by femtosecond infrared spectroscopy the ultrafast and persistent photoinduced phase transition of the Rb0.94Mn0.94Co0.06[Fe(CN)6]0.98 ⋅ 0.2H2O material, induced at room temperature by a single laser shot. This system exhibits a charge-transfer based phase transition with a 75 K wide thermal hysteresis, centred at room temperature, from the low temperature Mn3+-N-C-Fe2+ tetragonal phase to the high temperature Mn2+-N-C-Fe3+ cubic phase. At room temperature, the photoinduced phase transition is persistent. However, the out-of-equilibrium dynamics leading to this phase is multi-scale. Femtosecond infrared spectroscopy, particularly sensitive to local reorganizations through the evolution of the frequency of the N-C vibration modes with the different characteristic electronic states, reveals that at low laser fluence and on short time scale, the photoexcitation of the Mn3+-N-C-Fe2+ phase creates small charge-transfer polarons [Mn2+-N-C-Fe3+]* within ≃250 fs. The local trapping of photoinduced intermetallic charge-transfer is characterized by the appearance of a polaronic infrared band, due to the surrounding Mn2+-N-C-Fe2+ species. Above a threshold fluence, when a critical fraction of small CT-polarons is reached, the macroscopic phase transition to the persistent Mn2+-N-C-Fe3+ cubic phase occurs within ≃ 100 ps. This non-linear photo-response results from elastic cooperativity, intrinsic to a switchable lattice and reminiscent of a feedback mechanism.

From Ultrafast Photoinduced Small Polarons to Cooperative and Macroscopic Charge‐Transfer Phase Transition

AbstractWe study by femtosecond infrared spectroscopy the ultrafast and persistent photoinduced phase transition of the Rb0.94Mn0.94Co0.06[Fe(CN)6]0.98 ⋅ 0.2H2O material, induced at room temperature by a single laser shot. This system exhibits a charge‐transfer based phase transition with a 75 K wide thermal hysteresis, centred at room temperature, from the low temperature Mn3+−N−C−Fe2+ tetragonal phase to the high temperature Mn2+−N−C−Fe3+ cubic phase. At room temperature, the photoinduced phase transition is persistent. However, the out‐of‐equilibrium dynamics leading to this phase is multi‐scale. Femtosecond infrared spectroscopy, particularly sensitive to local reorganizations through the evolution of the frequency of the N−C vibration modes with the different characteristic electronic states, reveals that at low laser fluence and on short time scale, the photoexcitation of the Mn3+−N−C−Fe2+ phase creates small charge‐transfer polarons [Mn2+−N−C−Fe3+]* within ≃250 fs. The local trapping of photoinduced intermetallic charge‐transfer is characterized by the appearance of a polaronic infrared band, due to the surrounding Mn2+−N−C−Fe2+ species. Above a threshold fluence, when a critical fraction of small CT‐polarons is reached, the macroscopic phase transition to the persistent Mn2+−N−C−Fe3+ cubic phase occurs within ≃ 100 ps. This non‐linear photo‐response results from elastic cooperativity, intrinsic to a switchable lattice and reminiscent of a feedback mechanism.

Remote Magneto–Thermal Modulation of Reactive Oxygen Species Balance Enhances Tissue Regeneration In Vivo

AbstractOne of the hallmarks of tissue repair is the production of reactive oxygen species (ROS), which modulate processes such as cell proliferation. Although several attempts have been made to manipulate ROS levels to increase tissue repair, the lack of techniques able to remotely manipulate the redox homeostasis with spatio–temporal fashion has hindered its progress. Herein, a new approach for tuning the ROS levels using magnetic nanoparticles (MNPs) that act as nanoheaters when exposed to an alternating magnetic field is presented. Two manganese–iron oxide (MnxFe3−xO4) MNPs (with a low and a high Mn2+ content) are designed and probed for the possibility of modulating the ROS balance by magneto–thermal stimulation in the invertebrate model organism Hydra vulgaris, able to fully regenerate. By evaluating the expression of selected genes involved in the maintenance of ROS homeostasis and proliferation pathways, a biphasic modulation of the ROS levels played by the MNPs is found. While MNPs with a lower Mn2+ content are able to positively modulate the regeneration potential under magnetostimulation, MNPs with a higher Mn2+ content cause a different redox imbalance, negatively affecting the regeneration dynamic. This innovative approach reveals a novel way of manipulating redox homeostasis that can advance in the field of tissue engineering.

Mn-Ag bimetals supported on plate-like ZSM-5 as efficient and stable catalysts for the catalytic combustion of toluene: Synergistic effects and catalytic mechanisms

Ag-modified MnO2 loaded on plate-like ZSM-5 (PZ5) with different Ag/Mn ratios were synthesized by an in-situ growth method and used as catalysts for toluene combustion, as a probe molecule of volatile organic compounds (VOCs). The results showed that Ag doping greatly enhanced the toluene combustion activity (Mn50Agy/PZ5). Among them, Mn50Ag0.04/PZ5 showed the highest catalytic activity for toluene combustion with 90 % conversion of toluene at 234 °C (T90), and the reaction rate calculated per unit mass of Mn was 1.22×10−7 at 220 °C, which was 2.7 times higher than that of MnO2. In addition, Mn50Ag0.04/PZ5 exhibited excellent long-term stability and water resistance. Various characterizations indicated that the excellent performance of Mn50Ag0.04/PZ5 was attributed to its higher Mn2++Mn3+/Mn4+ ratios, higher reducibility, and more active surface adsorbed oxygen species. Finally, in-situ DRIFTS studies confirmed that Ag doping did not alter the catalytic combustion pathway of toluene over the Mn50Ag0.04/PZ5 catalyst but could accelerate the rate of conversion of toluene to the final products because the transfer of electrons from Ag+ to lattice oxygen persuaded the weaken of the Mn-O bond, and then made it easier for bulk lattice oxygen to migrate towards the Ag-MnO2 interface or catalysts’ surface, thus showing the better catalytic performance for toluene combustion.

Quantum sensing of microRNAs with nitrogen-vacancy centers in diamond

Label-free detection of nucleic acids such as microRNAs holds great potential for early diagnostics of various types of cancers. Measuring intrinsic biomolecular charge using methods based on field effect has been a promising way to accomplish label-free detection. However, the charges of biomolecules are screened by counter ions in solutions over a short distance (Debye length), thereby limiting the sensitivity of these methods. Here, we measure the intrinsic magnetic noise of paramagnetic counter ions, such as Mn2+, interacting with microRNAs using nitrogen-vacancy (NV) centers in diamond. All-atom molecular dynamics simulations show that microRNA interacts with the diamond surface resulting in excess accumulation of Mn ions and stronger magnetic noise. We confirm this prediction by observing an increase in spin relaxation contrast of the NV centers, indicating higher Mn2+ local concentration. This opens new possibilities for next-generation quantum sensing of charged biomolecules, overcoming limitations due to the Debye screening.

Effect of the type of ion-exchange resin on Mn<sup>2+</sup> adsorption in the presence of competing cations

Present in soils, ground and surface waters, manganese is among the most common metals in Earth crust. It is also an essential trace element to the functioning of several enzymes in the human body. However, exposure to high manganese concentrations can also be harmful to humans with psychiatric and motor effects and therefore, manganese concentrations in drinking water and also industrial effluents are regulated. In the current work, the adsorption of Ca<sup>2+</sup>, Mg<sup>2+</sup> and Mn<sup>2+</sup> on three different ion-exchange resins: (i) aminophosphonic acid - chelating (Purolite S950), (ii) polyacrylic weak acid cation (Purolite C104E) and (iii) polystyrene strong acid cation (Purolite C100) was investigated. The results revealed that Purolite S950 had the highest Mn2+ uptake (37.9 mg/mL-resin or 0.69 mmol/mL-resin) as compared to Ca<sup>2+</sup> (3.2 mg/mL-resin or 0.08 mmol/mL-resin) and Mg<sup>2+</sup> (~0 mg/mL-resin) and was selected for further kinetics and equilibrium studies. The results indicated Purolite S950 as particularly suited to be applied in the treatment of neutral mine waters with high Mg/Mn ratios. Additionally, Purolite S950 showed a small affinity for Ca<sup>2+</sup> and therefore an efficient Mn<sup>2+</sup> removal will depend on the Ca/Mn ratio of the mine water under treatment. According to the kinetic analysis, manganese sorption on Purolite S950 was described by the pseudo-second order model (r<sup>2</sup> > 0.98) with an activation energy of 10.40 kJ/mol and thus pore-difussion was the rate controlling step of the process. In terms of equilibrium studies, manganese sorption on Purolite S950 followed the Langmuir model with maximum loadings of up to 41.5 mg/mL-resin. The thermodynamic modelling indicated an exothermic process (-85.0 kJ/mol, as standard enthalpy) with a standard entropy of -274 J/mol.K, which was ascribed to the release of two adsorbed H<sup>+</sup> ions for each Mn<sup>2+</sup> ion taken up from solution

Synthesis and luminescence properties of a novel narrow band green-emitting Na2MgAl10O17:Mn2+ phosphor for backlight display

An activator’s selective occupation of a host is of great significance for designing high-quality white light-emitting diodes (w-LEDs) phosphors, while achieving a full-spectrum single-phase white light emission phosphor is challenging. For developing high-performance and green-emitting phosphors with narrow bands used for backlight display, a series of Na2Mg1-xAl10O17:xMn2+ (NMAO:xMn2+) phosphors with high Mn2+ concentration were synthesized. The NMAO:0.65Mn2+ green phosphor exhibits an ultra-narrow band green emission with full width at half maximum (FWHM) about 27 nm and peak position at 513 nm when excited by the blue light with wavelength of 450 nm. The NMAO:0.65Mn2+ not only has a super narrow band which is narrower than β-SiAlON:Eu2+ (FWHM ∼ 55 nm) but also shows an exceptional thermal stability performance (77% peak intensity @423 K). A w-LED device was assembled with NMAO:0.65Mn2+, a blue GaInN chip and K2SiF6:Mn4+ phosphors, which represents a wide color-gamut of 112% National Television System Committee (NTSC) standard under the current of 50 mA. These results demonstrate the NMAO:0.65Mn2+ has potential superiority in application of backlight display.

Platinum Nanoparticles-Enhanced Ferritin-Mn2+ Interaction for Magnetic Resonance Contrast Enhancement and Efficient Tumor Photothermal Therapy.

Nanoplatforms with high Mn2+ coordination can display efficient T1 magnetic resonance imaging (MRI) contrast enhancement. Herein, an earth gravity-like method for enhanced interaction between Ferritin (Fn) and Mn2+ by the growth of platinum nanoparticles (PNs) in Fn's cage structure via a biomineralization method is first proposed. Fn has good biocompatibility and can provide a suitable growth site for PNs. PNs with negative charge have certain attraction to Mn2+ with positive charge, improving Fn's loading capacity of Mn2+ by attraction force; and thus, achieving efficient MRI contrast enhancement. In addition, PNs can be applied for efficient photothermal therapy (PTT) under near infrared ray (NIR) irradiation. Systemic delivery of this nanoplatform shows obvious MRI contrast enhancement and tumor progression inhibition after NIR irradiation, as well as no obvious side effects. Therefore, this nanoplatform has the potential to contribute to nanotheranostic for clinical transformation.

Enhancing manganese removal through pre-deposition of powdered activated carbon-manganese oxide (PAC-MnOx) film on gravity-driven ceramic membrane: The impact of biofilm integrity and fluid dynamics

Manganese is widely distributed in the natural environment, and its presence in drinking water poses a risk to human health. In this study, an integrated pre-deposited powdered activated carbon (PAC) and manganese oxide (MnOx) bio-functional layer of inorganic origin was coupled with gravity-driven ceramic membrane (GDCM) reactor. The study aims to investigate the effects of the membrane pore size and functional layer integrity on the Mn2+ removal and flux. The results reveal that the average Mn2+ removal efficiency of the large pore size membranes (300 kDa and 0.45 μm) was lower (75 % – 78 %) compared to those with smaller pores (15 kDa and 50 kDa) (87 % – 88 %) during long-term operation. Such differences are attributed to a period of manganese leakage before the PAC-MnOx matured in large-pore membrane units and a longer residence time in small-pore membranes. The functional layer leaded to reversible fouling, which was more prominent in membranes with larger pores (contributing to 93 % of total resistance) than those with smaller ones (ranging from 51.7 % to 61.9 %). Although the damaged functional layer resulted in occasional high Mn2+ concentrations in the effluent, it did not significantly impact long-term flux development. Optical coherence tomography (OCT), in conjunction with COMSOL analysis, non-destructively evaluate biofilm formation process and indicate a homogeneous flow field and mass transfer in the “dual layers” (active film layer and ceramic membrane layer) of the GDCM. The presence of manganese-oxidizing bacteria (Hyphomicrobium, Reyranella, and Pseudomonas) in the GDCM reactor was verified using confocal laser scanning microscopy (CLSM) and high-throughput sequencing. Additional material characterization revealed that a portion of the PAC-MnOx exhibited characteristics of birnessite, with autocatalytic oxidation of Mn2+, and that Mn (III) and Mn (IV) were the primary species in MnOx, which exhibited excellent catalytic oxidation and adsorption capabilities for Mn (II), respectively. Overall, the developed PAC-MnOx GDCM system shows great promise in efficiently removing manganese and producing water of desired quality, thereby holding potential in applications across several sectors of advanced water treatment processes.

Tuning Ag+ and Mn2+ doping in ZnS:Ag,Mn embedded polymers for flexible white light emitting films

Flexible Light Emitting Diodes are versatile lighting solutions that offer bendable and adaptable illumination possibilities. A soft, flexible white luminescent film (1 mm) shows promise for foldable electroluminescent devices and applications. This film was fabricated using ZnS:Ag and Mn. Under different excitation wavelengths, the phosphors emit blue light due to Ag+ luminescence centers and red light from the d-d transition of Mn2+. The blue emission is greatly suppressed at high Mn2+ doping levels, requiring reduced Ag+ doping in co-doped ZnS:Ag,Mn compared to solo-doped ZnS:Ag samples. By adjusting Ag+ and Mn2+ concentrations, the ZnS:Ag(1%),Mn(0.2%) phosphors show a proper intensity ratio of blue and red emissions, making them a promising candidate for future white light applications.

Thermochemical oxidation of methane by manganese oxides in hydrothermal sediments

Microbial anaerobic oxidation of methane coupled to the reduction of Mn(IV)-oxides, typically MnO2, derived from continental weathering and riverine transport has been proposed as a globally important sink of methane. However, the potential role of hydrothermal Mn(IV) oxide-rich sediments as a methane sink, and the mechanisms of underpinning methane oxidation at high-temperature hydrothermal fields remain poorly understood. Here, we report the occurrence of almost pure rhodochrosite with extremely negative δ13CPDB values (as low as –76.4‰) in direct association with hausmannite formed through hydrothermal activity in the Late Triassic Heqing Mn deposit in Southern China. Based on detailed petrography and geochemistry, this rhodochrosite is interpreted as the result of the thermochemical oxidation of methane by hausmannite during early diagenesis. Given high hydrothermal Mn2+ and CH4 release coupled to low sulfate concentration observed in the Archean oceans, we propose that hydrothermal Mn(IV) oxides may have been effective methane sinks in Earth’s ancient oceans.

Reaction selectivity-regulation via interfacial reconstruction for preventing hazardous slime generation: Driving mechanism of Pb-based anode with oxygen vacancy-rich MnO2

Limited selectivity in coexisted anodic reactions on lead-based anodes leads to severe lead-dissolution, anodic slime-generation and high energy-consumption. Herein, anodic reaction selectivity was regulated by phase-controlled MnO2 (MnO2-PC) on lead-based anodes which was prepared under a lower voltage and a higher Mn2+ concentration. Compared with α-MnO2 formed under normal conditions, composite phase of γ-MnO2 and ε-MnO2 was obtained from MnO2-PC with specific crystal planes exposure and rich oxygen vacancy defects enabling higher oxygen evolution reaction selectivity (OER, overpotential reduced by ∼99 mV). Meanwhile, reaction of lead corrosion and manganese oxidation, as the main reasons for generation of hazardous lead-containing slime, were synergistically suppressed by 86.8% and 91.7%, respectively. Density functional theory (DFT) calculations further clarified that the change in coordinative environment of Mn and O brought lower energy barrier of rate-determining step of OER and stronger electron delocalization ability of MnO2, beneficial for promoting the catalysis of OER. MnO2-PC also displayed excellent inhibition effects on the generation and accumulation of Mn3+, an important precursor of MnO2 slime, and changed the selectivity in the oxidative path of Mn2+. The long-term electrolysis tests proved the stable performance of Pb–Ag/MnO2-PC. This study provides an efficient, low-cost, high economic benefits and environmental-friendly strategy for designing target functional materials towards reaction selectivity regulation via phase-control and microstructure reconstruction.

A mutant R70V/E166A of short manganese peroxidase showing Mn2+-independent dye decolorization.

Il-MnP1, a short-type manganese peroxidase from Irpex lacteus F17, can oxidize some substrates in the absence of Mn2+, but the catalysis was much lower than in the presence of Mn2+. Here, we report a mutant R70V/E166A of Il-MnP1 with some unique properties, which possessed clearly higher catalysis for the decolorization of anthraquinone and azo dyes in the absence of Mn2+ than that of Il-MnP1. Importantly, the optimum pH of R70V/E166A for decolorization of anthraquinone dyes (Reactive Blue 19, RB19) was 6.5, and the mutant achieved high decolorization activities in the range of pH 4.0-7.0, whereas Il-MnP1 only showed decolorization for RB19 at pH 3.5-4.0. In addition, the optimum H2O2 concentration of R70V/E166A for RB19 decolorization was eight times that of Il-MnP1 and the H2O2 stability has improved 1.4 times compared with Il-MnP1. Furthermore, Mn2+ competitively inhibited the oxidation of RB19 by R70V/E166A, explaining the higher catalytic activity of the mutant R70V/E166A in the absence of Mn2+. Molecular docking results suggested that RB19 binds to the distal side of the heme plane in mutant R70V/E166A, which extended from the heme δ-side to the heme γ-side, and close to the mutated residues of R70V and E166A, whereas RB19 could not access the heme pocket of Il-MnP1 due to the steric hindrance of the side-chain group of Arg 70. Thus, this study constructed a useful mutant R70V/E166A and analyzed its higher Mn2+-independent activity, which is very important for better understanding the Mn2+-independent catalytic mechanism for short manganese peroxidases. KEY POINTS: • The mutant R70V/E166A of atypical MnP1 of I. lacteus F17 shows unique catalytic properties. • At pH 6.5, the R70V/E166A had a strong ability to decolorize anthraquinone dyes in the absence of Mn2+. • The binding sites of Reactive Blue 19 in mutant R70V/E166A were elucidated.

Highly Efficient Narrow‐Band Green Emission in LaZn1‐xMnxAl11O19 Magnetoplumbite Phosphors toward White LED Application and Optical Thermometer

AbstractMn2+‐doped phosphors with narrow‐band green emission are promising for white light‐emitting diodes (WLEDs) to achieve high color rendering index and efficacy. Here, a series of narrow‐band green‐emitting LaZn1−xMnxAl11O19 (0.01 ≤ x ≤ 0.30) magnetoplumbite phosphors (λem = 515 nm) with full width at half maximum (FWHM) of ≈26 nm are designed based on highly symmetrical crystallographic structure. These green phosphors exhibit good photoluminescence quantum yield (PLQY) and small thermal quenching (TQ) performance (86%@423 K) under 450 nm blue light excitation. By further heavy doping Mn2+ into LaZnAl11O19, a broadband red emission peaking at ≈672–697 nm appears upon blue light excitation due to the Mn2+–Mn2+ super‐exchange interactions. A dual‐wavelength emission in LaZn1−xMnxAl11O19 (0.5 ≤ x ≤ 1.0) phosphors provides thermal‐sensitive emission for ratiometric temperature sensing with good relative sensitivity. Benefitting from the Eu2+ → Mn2+ energy transfer, the green emission from Mn2+ is increased by 26 times, and the internal QY of La0.97Zn1−xMnxAl11O19:0.03Eu2+ reaches as high as 88% upon 350 nm light excitation. The efficient blue‐to‐green phosphors are obtained and used as candidates for violet‐excited WLEDs. This study has a guiding role in the development of Mn2+‐doped phosphors in mineral structure with photoluminescence control based on high symmetry and Mn2+–Mn2+ dimers.

Geomatics-Based Modeling and Hydrochemical Analysis for Groundwater Quality Mapping in the Egyptian Western Desert: A Case Study of El-Dakhla Oasis

Groundwater is the single source of water in El-Dakhla Oasis, western desert, Egypt. The main objective of this study is an assessment of groundwater in the area for agriculture and drinking compared to Egyptian and World Health Organization criteria. Most the contamination of water in the study area comes from human and agricultural activities. Thirty soil profiles were studied in the area and we assessed soil quality. Seventy-four samples were taken from the area’s groundwater wells to assess the chemical characteristics of the groundwater. Moreover, the contamination of groundwater by farming and anthropogenic activities was assessed using a land use/land cover (LULC) map. Nine standard water criteria were determined to assess groundwater quality for agriculture. Furthermore, the resulting risk to human health and agricultural crops has been addressed. Therefore, the drinking quality of groundwater samples is graded as low as the hydrochemical study showed high TH, EC, TDS, Ca2+, Mg2+, Mn2+, and Fe2+ contents of 40.5%, 2.7%, 1.4%, 3.8%, 1.6%, 86.5%, and 100%, respectively. Human health is risked by drinking this water, which negatively affects hair, skin, and eyes, with greatest exposure to enteric pathogens. Using these criteria, the majority of groundwater samples cause harmful effects on soil types and are toxic to sensitive crops (vegetable crops). In conclusion, the output of this research is a map showing groundwater suitable for consumption and agriculture in El-Dakhla Oasis based on all indices using the Geographic Information Systems (GIS) model. Additionally, there was evidence of a linear relationship between soil quality and irrigation water quality (R2 = 0.90). This emphasis on tracking changes in soil/water quality was brought on by agricultural practices and environmental variables.

Cloning and characterization of the major AP endonuclease from Staphylococcus aureus

Apurinic/apyrimidinic (AP) endonucleases are key enzymes involved in the repair of abasic sites and DNA strand breaks. Complete genome analysis of Staphylococcus aureus identified a single AP endonuclease, SaNfo, which is a member of the endonuclease IV family exemplified by Escherichia coli Nfo. At present, it remains unknown whether SaNfo possesses DNA repair activities similar to its counterparts from E. coli and other bacteria. Here, we report that the purified SaNfo protein contains efficient AP endonuclease and nucleotide incision repair (NIR) activities. Optimal reaction conditions for SaNfo-catalysed AP endonuclease activity are high ionic strength and Mn2+ concentration, pH in range 7.5–9.0 and the temperature optimum of 37–45 °C. Cell-free extracts of S. aureus exhibited efficient AP site cleavage and NIR activities. Heterologous expression of SaNfo strongly reduces the sensitivity of AP endonuclease-deficient E. coli xth nfo strain to methylmethanesulfonate and H2O2. Site-directed mutagenesis showed that the Glu258 residue is critical for the SaNfo enzyme function. The AP endonuclease but not the NIR activity of SaNfo were stimulated by the β-clamp (SaDnaN dimer), suggesting that it might participate in the organization of BER in S. aureus. Overall, our data confirm that the activity, substrate specificity and in vivo functionality of S. aureus Nfo are consistent with this protein being the major AP endonuclease for the repair of DNA damage generated by endogenous and host-imposed factors.

Fabrication of CsPb1−x Mn x Br3−2x Cl2x (x = 0–0.5) quantum dots for near UV photodetector application

Abstract In this study, CsPb1–x Mn x Br3–2x Cl2x (x = 0–0.5) nanoparticles were synthesized directly in toluene solvents at high temperature. This approach results in small-size nanoparticles, which can be used in photoelectric components without adding a filtration process to eliminate high-temperature solvents such as octadecene. The high content Mn2+-incorporated CsPb(Cl/Br)3 host is observed by strongly wideband emission at 592 nm of manganese d-states spin and orbital forbidden transition. After infiltration into mesoporous TiO2, the Mn2+ ion receives energy from the CsPb(Cl/Br)3 host (irradiated 405 nm light-emitting diode source) and effectively transfers to the TiO2 scaffold layer. As a result, a metal/semiconductor/metal planar structure photodetector with m-TiO2/CsPb1–x Mn x Br3–2x Cl2x (x = 0–0.5) composite showed several figures of merit compared to bare m-TiO2 and m-TiO2/CsPbBr3 such as on/off ratio of 104 times, responsivity of 1.67 A·W−1, and detectivity of 4.42 × 109 Jones. The key factors contributing to the growth of the on/off ratio include the decreasing dark current and enhancing exciton energy and transportation due to the infiltration of CsPb1–x Mn x Br3–2x Cl2x (x = 0–0.5) perovskite quantum dots into mesopores of the m-TiO2 scaffold layer.

Metal tolerance protein family members are involved in Mn homeostasis through internal compartmentation and exocytosis in Brassica napus

Mineral elements, including manganese (Mn), are indispensable for plant growth and development. However, plants cultivated on acidic soils are vulnerable to Mn2+ toxicity due to a prevalently phytotoxic level of Mn2+. Metal tolerance proteins (MTPs) were demonstrated to be essential for metal homeostasis and tolerance in different plant species. In this study, we present the functional characteristics of BnMTP8 and BnMTP9 from Brassica napus. The expression level of BnMTP8 was most prominent in rapeseed roots and was only markedly up-regulated in shoots by excess Mn2+. In contrast, BnMTP9 was most abundant in shoots. Expression of BnMTP8 and BnMTP9 in Saccharomyces cerevisiae compensated the Mn2+-hypersensitivity of Δpmr1 by increasing metal sequestration and efflux, respectively. In addition, heteroexpression of BnMTP8 restored Mn2+ tolerance of Arabidopsis mtp8 mutants and increased Mn2+ accumulation in tissues and leaf vacuoles. Expression of BnMTP9 in Arabidopsis mtp11 mutants restored their growth and reduced Mn2+ concentrations in mesophyll protoplasts and tissues upon elevated levels of Mn2+. Transient expression of GFP-fusion constructs in protoplasts showed that BnMTP8 and BnMTP9 localize to pre-vacuolar compartments and the trans-Golgi network, respectively. However, high extracellular Mn2+ in Arabidopsis root cells triggered BnMTP8-GFP relocation to the tonoplast and BnMTP9-GFP relocation to the plasma membrane, suggesting that these two proteins are involved in vacuolar Mn2+ sequestration and cytosolic Mn2+ export, respectively. Taken together, these findings indicate that BnMTP8 and BnMTP9 load Mn2+ into vesicles for subsequent delivery to the vacuole or secretion into extracellular spaces, respectively, thereby cooperating to maintain Mn2+ homeostasis in the roots and shoots of rapeseed.

Non-enzymatic formation of isoprene and 2-methyl-3-buten-2-ol (2-MBO) by manganese

It has been suggested that isoprene synthesis by isoprene synthase (IspS) proceeds via a substrate-assisted mechanism. The authors observed a non-enzymatic isoprene formation by Mn2+, which represents the basis of IspS enzyme reaction. Because IspS and many other terpene synthases require Mn2+ metal ions as cofactor, this study characterized the formation reaction for the first time. Metal ions including Mn2+ non-enzymatically produced both isoprene and 2-methyl-3-buten-2-ol (2-MBO) from dimethylallyl pyrophosphate (DMADP). Isoprene formation was most enhanced by Fe2+ and, to a lesser extent, by Mn2+ or Cu2+. Ni2+, Co2+, Mg2+, and Ba2+ exhibited a low activity to generate both isoprene and 2-MBO. The proportion of isoprene and 2-MBO varied with the Mn2+ concentration: isoprene predominated over 2-MBO at a higher Mn2+ concentration. Similarly, isoprene formation by Mn2+ increased exponentially as temperature increased with predominance of isoprene over 2-MBO at higher temperature. Both isoprene and 2-MBO formation was enhanced by acidic and neutral pH compared to alkaline conditions. Molecular dynamic simulation of DMADP suggested that the formation reaction is initiated by deprotonation of hydrogen on allyl terminal carbon by phosphate oxygen and generates carbocation and allyl anion intermediates. This is followed by quenching to produce isoprene or by hydroxyl addition to form 2-MBO. Thus, this study provided an insight into reaction mechanism of isoprene and 2-MBO biosynthesis and highlighted some parts of isoprene emission from terrestrial plants, which could be formed by non-enzymatic mechanism.

Near-unity photoluminescence quantum yield Mn-doped two-dimensional halide perovskite platelets via hydrobromic acid-assisted synthesis

Although two-dimensional lead halide based perovskite has been developed for nearly five years, the room temperature preparation for achieving high efficiency Mn2+ emission in the lead halide perovskites is still facing huge challenges. Herein, we studied photoluminescent properties of highly emitting Mn2+ ions doped PEA2PbBr4 perovskite platelets synthesized at room temperature by a facile hydrobromic acid-assisted (HBr-assisted) solid-liquid mixing strategy. The Mn-doped platelets with different Mn doping levels were synthesized by controlling Mn/Pb molar feed ratio and HBr addition volume. The photoluminescence (PL) quantum yield (QY) of orange-color (605 nm) of Mn-doped platelets reached 98%. Their optical properties were studied by steady-state and time-resolved PL spectroscopy. The temperature-dependent PL spectra revealed that the improvement mechanism of Mn luminescence and thermal stability was related to the reduction of the nonradiative defect/trap states through the HBr-induced surface passivation and enhancement of the exciton-to-Mn2+ energy transfer. This work provides a facile HBr solution-assisted method for preparing high-quality 2D Mn-doped perovskite platelets with stable and efficient luminescence.