Search

Zinc germanium diphosphide (ZnGeP2) is a ternary semiconductor best known for its nonlinear optical properties. A primary application is optical parametric oscillators operating in the mid-infrared region. Controlled donor doping provides a method to minimize the acceptor-related absorption bands that limit the output power of these devices. In the present study, a ZnGeP2 crystal is doped with selenium during growth. Selenium substitutes for phosphorus and serves as a deep donor. Significant concentrations of native defects (zinc vacancies, germanium-on-zinc antisites, and phosphorous vacancies) are also present in the crystal. Electron paramagnetic resonance (EPR) is used to establish the atomic-level model for the neutral charge state of the selenium donor. The S = 1/2 signal from the neutral donors is produced at 6 K by illuminating with 633 nm light (electrons excited from doubly ionized Zn vacancies convert Se P + donors to Se P 0 donors). A g matrix, with principal values of 2.088, 2.203, and 1.904, is extracted from the angular dependence of the EPR spectrum. The principal-axis direction associated with the 1.904 principal value is close to a Se–Ge bond. This indicates an asymmetric distribution of unpaired spin density around the selenium ion and thus predicts the deep donor behavior. [ABSTRACT FROM AUTHOR]

Photosystem I (PSI) serves as a model system for studying fundamental processes such as electron transfer (ET) and energy conversion, which are not only central to photosynthesis but also have broader implications for bioenergy production and biomimetic device design. In this study, we employed electron paramagnetic resonance (EPR) spectroscopy to investigate key light-induced charge separation steps in PSI isolated from several green algal and cyanobacterial species. Following photoexcitation, rapid sequential ET occurs through either of two quasi-symmetric branches of donor/acceptor cofactors embedded within the protein core, termed the A and B branches. Using high-frequency (130 GHz) time-resolved EPR (TR-EPR) and deuteration techniques to enhance spectral resolution, we observed that at low temperatures prokaryotic PSI exhibits reversible ET in the A branch and irreversible ET in the B branch, while PSI from eukaryotic counterparts displays either reversible ET in both branches or exclusively in the B branch. Furthermore, we observed a notable correlation between low-temperature charge separation to the terminal [4Fe-4S] clusters of PSI, termed FA and FB, as reflected in the measured FA/FB ratio. These findings enhance our understanding of the mechanistic diversity of PSI's ET across different species and underscore the importance of experimental design in resolving these differences. Though further research is necessary to elucidate the underlying mechanisms and the evolutionary significance of these variations in PSI charge separation, this study sets the stage for future investigations into the complex interplay between protein structure, ET pathways, and the environmental adaptations of photosynthetic organisms.

The biological reduction of N2 to ammonia requires the ATP-dependent, sequential delivery of electrons from the Fe protein to the MoFe protein of nitrogenase. It has been demonstrated that CdS nanocrystals can replace the Fe protein to deliver photoexcited electrons to the MoFe protein. Herein, light-activated electron delivery within the CdS:MoFe protein complex was achieved in the frozen state, revealing that all the electron paramagnetic resonance (EPR) active E-state intermediates in the catalytic cycle can be trapped and characterized by EPR spectroscopy. Prior to illumination, the CdS:MoFe protein complex EPR spectrum was composed of a S = 3/2 rhombic signal (g = 4.33, 3.63, and 2.01) consistent with the FeMo-cofactor in the resting state, E0. Illumination for sequential 1-h periods at 233 K under 1 atm of N2 led to a cumulative attenuation of E0 by 75%. This coincided with the appearance of S = 3/2 and S = 1/2 signals assigned to two-electron (E2) and four-electron (E4) reduced states of the FeMo-cofactor, together with additional S = 1/2 signals consistent with the formation of E6 and E8 states. Simulations of EPR spectra allowed quantification of the different E-state populations, along with mapping of these populations onto the Lowe–Thorneley kinetic scheme. The outcome of this work demonstrates that the photochemical delivery of electrons to the MoFe protein can be used to populate all of the EPR active E-state intermediates of the nitrogenase MoFe protein cycle. [ABSTRACT FROM AUTHOR]

The effect of high temperature annealing under O2 and N2 atmospheres on the electrical properties and defect formation on Sn doped n-type β-Ga2O3 bulk samples was investigated by electron paramagnetic resonance (EPR) spectroscopy. EPR, being a volume sensitive technique, probes the entire sample volume. Our results show an electrical compensation being correlated with the formation of a negatively charged Ga vacancy defect VGa2−. This VGa center is different from the one observed after particle irradiation. The associated shift of the Fermi level reveals the presence of Fe3+, Cu2+, and Cr3+, which are residuals related to the growth conditions. The 1100 °C N2 annealed sample is fully compensated, and the neutral donor resonance is no longer observed. Our results directly confirm the thermal instability of Ga and Sn in n-type conducting samples. No oxygen vacancy related centers were detected. We discuss the various Ga vacancy centers reported previously. [ABSTRACT FROM AUTHOR]

Advancements in electronics and digitization have led to concerns about electromagnetic interference (EMI), necessitating effective EMI shielding measures. This study investigates the electromagnetic wave absorption properties of La n+1 Ni n O 3n+1 (n = 1, 2, 3) Ruddlesden-popper (RP) phases. While a single phase, La 2 NiO 4 , was obtained for n = 1, mixed phases of La 3 N 2 O 7-δ /La 4 Ni 3 O 10-δ were observed for n = 2 and 3. Electron paramagnetic resonance spectroscopy revealed superparamagnetic behavior for La 2 NiO 4 and multi-resonance peaks for La 3 Ni 2 O 7-δ , suggesting increased surface defects. La 3 Ni 2 O 7-δ exhibited enhanced absorption properties, with a minimum reflection loss of −19.4 dB and a broader (less than −10 dB) bandwidth covering 4.2 GHz (X-band) at a thickness of 1.4 mm, attributed to optimal conductivity, magnetic resonance, eddy current losses, and synergistic dielectric loss. The sample with n = 2 demonstrates potential for EMI absorption and electrostatic discharge (ESD) applications. [ABSTRACT FROM AUTHOR]

In order to study the effect of impurity iron in different valence states on the coloration mechanism of quartz, colorless synthetic quartz fabricated via ion implantation and its natural counterpart citrine with iron were compared after heating under different atmospheres. Ultraviolet-visible spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, electron paramagnetic resonance spectroscopy, and Fourier transform infrared spectroscopy were used to analyze the absorption property, valence states of iron, and type of O of both natural citrine and ion-implanted quartz. Experimental results showed the yellow color in quartz was mainly related to the charge transfer between Fe3+ and Fe2+, oxygen vacancies and the lattice oxygen, whereas the pink color in quartz was related to oxygen vacancies at a high temperature of 1200 °C. [ABSTRACT FROM AUTHOR]

Modulating the photogenerated electrons of CeO2 to activate O2 and efficiently photocatalytic degra- dation of chlorophenols is a highly desired goal. Herein, we have successfully fabricated an FePc/CeO2 heterojunction through H-bond induced assembly. The photocatalytic degradation of 2,4-DCP by the amount-optimized FePc/CeO2 nanocomposite was improved by 3 times compared with that by pure CeO2. By means of electron paramagnetic resonance (EPR) and single wavelength photocurrent spec- troscopy, it is confirmed that the excellent photocatalytic performance is mainly attributed to the for- mation of the Z-scheme heterojunction, which promotes charge separation and transfer, and the intro- duction of FePc broadens the visible light absorption range of the heterojunction. Moreover, O2 tempera- ture-programmed-desorbed curves and electrochemical O2 reduction measurement results demonstrate that the single Fe-N4(II) site in FePc is more conducive to promoting O2 activation than that of other metal phthalocyanines. Based on in situ FT-IR and liquid chromatography-tandem mass spectrometry (LC-MS/MS), a possible reaction pathway of 2,4-DCP degradation was proposed. This study provides a novel strategy for preparing CeO2 based Z-scheme heterojunctions with abundant monoatomic sites for pollutant degradation. [ABSTRACT FROM AUTHOR]

Polyradical cages are of great interest because they show very fascinating physical and chemical properties, but many challenges remain, especially for their synthesis and characterization. Herein, we present the synthesis of a polyradical cation cage 14⋅+ through post‐synthetic oxidation of a redox‐active phenothiazine‐based Pd2L4‐type coordination cage 1. It′s worth noting that 1 exhibits excellent reversible electrochemical and chemical redox activity due to the introduction of a bulky 3,5‐di‐tert‐butyl‐4‐methoxyphenyl substituent. The generation of 14⋅+ through reversible electrochemical oxidation is investigated by in situ UV/Vis‐NIR and EPR spectroelectrochemistry. Meanwhile, chemical oxidation of 1 can also produce 14⋅+ which can be reversibly reduced back to the original cage 1, and the process is monitored by EPR and NMR spectroscopies. Eventually, we succeed in the isolation and single crystal X‐ray diffraction analysis of 14⋅+, whose electronic structure and conformation are distinct to original 1. The magnetic susceptibility measurements indicate the predominantly antiferromagnetic interactions between the four phenothiazine radical cations in 14⋅+. We believe that our study including the facile synthesis methodology and in situ spectroelectrochemistry will shed some light on the synthesis and characterization of novel polyradical systems, opening more perspectives for developing functional supramolecular cages. [ABSTRACT FROM AUTHOR]

Cladosporium cladosporioides are the pigmented soil fungi containing melanin. The aim of this work was to determine the influence of amphotericin B on free radicals in the natural melanin isolated from pigmented fungi Cladosporium cladosporioides and to compare it with the effect in synthetic DOPA-melanin. Electron paramagnetic resonance (EPR) spectra were measured at X-band (9.3 GHz) with microwave power in the range of 2.2–70 mW. Amplitudes, integral intensities, linewidths of the EPR spectra, and g factors, were analyzed. The concentrations of free radicals in the tested melanin samples were determined. Microwave saturation of EPR lines indicates the presence of pheomelanin in addition to eumelanin in Cladosporium cladosporioides. o-Semiquinone free radicals in concentrations ~1020 [spin/g] exist in the tested melanin samples and in their complexes with amphotericin B. Changes in concentrations of free radicals in the examined synthetic and natural melanin point out their participation in the formation of amphotericin B binding to melanin. A different influence of amphotericin B on free radical concentration in Cladosporium cladosporioides melanin and in DOPA-melanin may be caused by the occurrence of pheomelanin in addition to eumelanin in Cladosporium cladosporioides. The advanced spectral analysis in the wide range of microwave powers made it possible to compare changes in the free radical systems of different melanin polymers. This study is important for knowledge about the role of free radicals in the interactions of melanin with drugs. [ABSTRACT FROM AUTHOR]

The Murun massif (Aldan shield, Russia) is particularly intriguing due to its group of alkali Ca-(K)-(Na) silicates, which includes many new and rare species. Additionally, it is also of interest for its beryllium mineralization. One of the unique beryllium Ca-(K)-(Na) silicates, odintsovite K2Na4Ca3Ti2Be4Si12O38, was investigated in this study. The aim of this study is to provide new insights into the crystal chemistry and spectroscopic properties of odintsovite. DFT modelling was used to interpret the experimental IR and Raman spectra. Determining the crystal-chemical formula of odintsovite is challenging due to the presence of atoms in different structural positions with varying valence states. The distribution of cations was determined by combining electron probe microanalysis with the results of crystal structure refinement. Luminescence of Eu3+ was observed in odintsovite upon excitation at around 532 nm. Analysis of the luminescence band splitting is related to the 4f–4f transitions in Eu3+ ions. Additionally, upon excitation at around 370 nm, luminescence with a peak at around 410 nm, associated with 5d–4f transitions in Ce3+ ions, was observed. [ABSTRACT FROM AUTHOR]

In this study, we report a novel synthesis technique for polysaccharides and conducting polymer composites. A series of polysaccharide/polyaniline composites were prepared via double-step polymerization by a sol–gel method developed herein. The chemical structure and the electronic properties of the composites were analyzed through Fourier transform infrared, ultraviolet–visible, and electron spin resonance spectroscopies. Composites with long effective conjugation lengths were obtained because the gelatinized polysaccharide acted as a template and host for the composite. [ABSTRACT FROM AUTHOR]

Peracetic acid (PAA) has attracted increasing attention in wastewater decontamination for yielding reactive oxygen species (ROS). In this study, mackinawite (FeS) was synthesized and applied as the heterogeneous catalyst for PAA activation. Using sulfamethoxazole (SMX) as the target pollutant, the influences of FeS dosage, PAA dosage and initial pH values on SMX degradation by the FeS/PAA process were investigated. Under optimal conditions, SMX could be completely removed within 5 min with the apparent first-order rate constant (kobs) of 7.71 × 10−4 s−1. Electron spin resonance spectroscopy (ESR) analysis and radical scavenging experiments were modulated to detect the active species. During the activation process of PAA, various active components were evidenced to be hydroxyl radicals (HO•), singlet oxygen (1O2), superoxide radicals (O2•−) and organic radicals (R-O•, e.g., CH3C(O)O• and CH3C(O)OO•), whereas HO• and R-O• were demonstrated as the dominant active species responsible for SMX abatement. Both dissolved Fe(II) ions and active sites on the surface of FeS were proven to be activators for PAA, and SMX abatement was highly promoted as a result. Furthermore, the acidic pH displayed superior efficiency in SMX decomposition compared with alkaline and neutral conditions. Five degradation pathways of SMX were put forward and the toxicity of byproducts was further evaluated. Overall, this study provided an efficient and environmentally friendly PAA activation approach using FeS, which might broaden its applicability in the remediation of micropollutants. [ABSTRACT FROM AUTHOR]

In this work, we demonstrate the first pulsed electron paramagnetic resonance (EPR) experiments performed under magic angle spinning (MAS) at high magnetic field. Unlike nuclear magnetic resonance (NMR) and dynamic nuclear polarization (DNP), commonly performed at high magnetic fields and under MAS to maximize sensitivity and resolution, EPR is usually measured at low magnetic fields and, with the exception of the Spiess group work in the late 1990s, never under MAS, due to great instrumentational challenges. This hampers the investigation of DNP mechanisms, in which electron spin dynamics play a central role, because no experimental data about the latter under DNP-characteristic conditions are available. We hereby present our dedicated, homebuilt MAS-EPR probehead and show the pulsed MAS-EPR spectra of P1 center diamond defect recorded at 7 tesla. Our results reveal unique effects of MAS on EPR line shape, intensity, and signal dephasing. Time-domain simulations reproduce the observed changes in the line shapes and the trends in the signal intensity. [ABSTRACT FROM AUTHOR]

A new Mannich base (2-(4-(2-hydroxy-3-methoxy-5-methylbenzyl)-piperazin-1-yl)methyl)-6-methoxy-4-ethylphenol (H2L) and its tetranuclear NiII complex [Ni4L2(μ1,1-Cl)2(H2O)4]Cl2 (compound 1) are characterised using single-crystal X-ray diffraction measurements. Compound 1 contains four different NiII centres in a rhombus-like structure. Two Ni atoms (Ni1 and Ni2) have a NiN2O4 coordination sphere, while the other two (Ni3 and Ni4) have a NiO4Cl2 coordination environment and Ni–Cl–Ni bridges connect them. Ni1 and Ni2 are linked to Ni3 and Ni4 by phenoxide bridges. Variable temperature magnetic susceptibility measurements of 1 indicate the presence of alternating antiferromagnetic coupling (J1 = −6.6(1) cm−1) through the phenoxide bridge along the sides of the rhombus and ferromagnetic coupling (J2 = 8.4(1) cm−1) through the double Cl bridge along the short diagonal of the rhombus with a zero-field splitting of ‖D‖ = 2.7(1) cm−1. Compound 1 shows oxidase (catecholase-like and phenoxazinone synthase-like) activity. The oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) gives 3,5-di-tert-butylquinone (3,5-DTBQ) and H2O2 and the oxidation of o-aminophenol (OAP) produces 2-aminophenoxazin-3-one (APX) and H2O with turnover numbers of 28.32 and 17.52 h−1, respectively, under aerobic conditions. A mechanism for the oxidase activity catalysed by compound 1 is proposed in line with ESI-mass spectrometry, EPR spectroscopy, and electrochemical data. The reaction involves the cleavage of the tetranuclear Ni4-core to form a mononuclear NiII complex in the presence of the substrate (3,5-DTBC/OAP). This NiII complex is reduced to NiI with the concomitant oxidation of the substrate (3,5-DTBQ/APX). Formation of a radical intermediate is confirmed using EPR. In the catecholase-like activity, O2 is reduced to H2O2 while in the phenoxazinone synthase-like activity O2 produces H2O. Compound 1 participated in oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in a strongly basic medium with an onset potential of 418 mV and a Tafel slope of 121 mV dec−1 for OER and an onset potential of 477 mV and Tafel slope of 146 mV dec−1 for HER. [ABSTRACT FROM AUTHOR]

Understanding the electronic structure of active sites is crucial in efficient catalyst design. The spin state, spin configurations of d-electrons, has been frequently discussed recently. However, its systematic depiction in electrocatalysis is lacking. In this tutorial review, a comprehensive interpretation of the spin state of metal centers in electrocatalysts and its role in electrocatalysis is provided. This review starts with the basics of spin states, including molecular field theory, crystal field theory, and ligand field theory. It further introduces the differences in low spin, intermediate spin, and high spin, and intrinsic factors affecting the spin state. Popular characterization techniques and modeling approaches that can reveal the spin state, such as X-ray absorption microscopy, electron spin resonance spectroscopy, Mössbauer spectroscopy, and density functional theory (DFT) calculations, are introduced as well with examples from the literature. The examples include the most recent progress in tuning the spin state of metal centers for various reactions, e.g., the oxygen evolution reaction, oxygen reduction reaction, hydrogen evolution reaction, carbon dioxide reduction reaction, nitrogen reduction reaction, nitrate reduction reaction, and urea oxidation reaction. Challenges and potential implications for future research related to the spin state are discussed at the end. [ABSTRACT FROM AUTHOR]

The neutral three-coordinated imino(silyl)silyl radical was isolated from the reaction of N-heterocyclic iminosilicon tribromide (ItBuN-SiBr3) with NaSitBu2Me. The radical was fully characterized by X-ray crystallography and electron paramagnetic resonance spectroscopy and supported by quantum chemical calculations. [ABSTRACT FROM AUTHOR]

Molecular catalysts based on abundant elements that function in neutral water represent an essential component of sustainable hydrogen production. Artificial hydrogenases based on protein-inorganic hybrids have emerged as an intriguing class of catalysts for this purpose. We have prepared a novel artificial hydrogenase based on cobaloxime bound to a de novo three alpha-helical protein, α3C, via a pyridyl-based unnatural amino acid. The functionalized de novo protein was characterised by UV-visible, CD, and EPR spectroscopy, as well as MALDI spectrometry, which confirmed the presence and ligation of cobaloxime to the protein. The new de novo enzyme produced hydrogen under electrochemical, photochemical and reductive chemical conditions in neutral water solution. A change in hydrogen evolution capability of the de novo enzyme compared with native cobaloxime was observed, with turnover numbers around 80% of that of cobaloxime, and hydrogen evolution rates of 40% of that of cobaloxime. We discuss these findings in the context of existing literature, how our study contributes important information about the functionality of cobaloximes as hydrogen evolving catalysts in protein environments, and the feasibility of using de novo proteins for development into artificial metalloenzymes. Small de novo proteins as enzyme scaffolds have the potential to function as upscalable bioinspired catalysts thanks to their efficient atom economy, and the findings presented here show that these types of novel enzymes are a possible product. [ABSTRACT FROM AUTHOR]

Developing high mass‐loading electrodes is crucial for enhancing the energy density of current batteries, yet challenges such as poor rate performance and cycling instability must be addressed. Spin charge storage on transition metal nanoparticle surfaces, characterized by rapid charging and the absence of phase transitions, offers an ideal storage behavior for high mass‐loading electrodes. In this study, electrospinning is utilized to fabricate free‐standing carbon nanofibers incorporating Co nanoparticles for high‐mass loading and high‐performance anodes. The resulting anode, with a maximum mass loading of 6.8 mg cm−2, exhibits remarkable cycle stability and high‐rate performance of 2 A g−1 at a capacity over 3 mAh cm−2, superior than reported results. Magnetometry and electron paramagnetic resonance spectroscopy are employed to monitor the charge storage mechanism of the Co@CNFs, involving both the reversible formation of a spin capacitance and the growth of radical anions in the solid electrolyte interface. Additionally, in situ X‐ray diffraction and optical microscopy provide direct evidence of the absence of mechanical stress‐induced phenomena within the spin charge process, attributed to high‐rate capable lithium storage under high mass loading. The strategic approach presented herein offers a reliable methodology for engineering high‐energy‐density lithium‐ion batteries. [ABSTRACT FROM AUTHOR]

Novel and highly stable nitronyl nitroxide radical (NIT) derivatives were synthesized and coated on the surface of multi-walled carbon nanotubes (MWCNTs) to improve their desulfurization performance. They were characterized by FTIR, UV-vis, SEM, XRD, Raman spectroscopy and ESR. Thiophene in fuel was desulfurized by molecular O2, and the oxidation activity of these compounds was evaluated. At a normal temperature and pressure, the degradation rates of thiophene by four compounds in 4 h can reach 92.66%, 96.38%, 93.25% and 89.49%, respectively. The MWCNTs/NIT-F have a high special activity for the degradation of thiophene, and their desulfurization activity can be recycled for five times without a significant reduction. The mechanistic studies of MWCNTs/NIT composites show that the ammonium oxide ion is the key active intermediate in catalytic oxidative desulfurization, which provides a new choice for fuel oxidative desulfurization. The results show that NIT significantly improves the photocatalytic performance of MWCNTs. [ABSTRACT FROM AUTHOR]

IQ-1 (11H-indeno[1,2-b]quinoxalin-11-one oxime) is a specific c-Jun N-terminal kinase (JNK) inhibitor with anticancer and neuro- and cardioprotective properties. Because aryloxime derivatives undergo cytochrome P450-catalyzed oxidation to nitric oxide (NO) and ketones in liver microsomes, NO formation may be an additional mechanism of IQ-1 pharmacological action. In the present study, electron paramagnetic resonance (EPR) of the Fe2+ complex with diethyldithiocarbamate (DETC) as a spin trap and hemoglobin (Hb) was used to detect NO formation from IQ-1 in the liver and blood of rats, respectively, after IQ-1 intraperitoneal administration (50 mg/kg). Introducing the spin trap and IQ-1 led to signal characteristics of the complex (DETC)2-Fe2+-NO in rat liver. Similarly, the introduction of the spin trap components and IQ-1 resulted in an increase in the Hb-NO signal for both the R- and the T-conformers in blood samples. The density functional theory (DFT) calculations were in accordance with the experimental data and indicated that the NO formation of IQ-1 through the action of superoxide anion radical is thermodynamically favorable. We conclude that the administration of IQ-1 releases NO during its oxidoreductive bioconversion in vivo. [ABSTRACT FROM AUTHOR]

[Display omitted] Transition-metal-atom anchored graphdiynes (TM@GDY, TM = Mn, Fe, Co, Ni and Cu) have already been synthesized and found applications in hydrogen evolution, nitrogen fixation and etc. By means of first-principle predictions and test experiments, we propose here that Fe@GDY and Co@GDY are efficient catalysts for the sustainable conversion of O 3 to O 2. These two catalysts can spontaneously chemisorb O 3 with zero reaction barrier and have low O 3 conversion barriers (0.31 eV and 0.19 eV, respectively). The O 3 decomposition experiment in a continuous flow membrane reactor and electron paramagnetic resonance results verify that Fe@GDY and Co@GDY are efficient catalysts under humid conditions. Raman spectra prove the formation of the key Fe-O/Co-O and Fe O O and Co O O intermediates. The hydrophobic nature of graphdiyne and the strongest chemisorption of O 3 among tested ambient gases, make Fe@GDY and Co@GDY ideal catalysts under both dry and humid conditions. These findings would stimulate future explorations on metal anchored GDY-based catalysts for applications of toxic gas decomposition or fixation. [ABSTRACT FROM AUTHOR]

Herein, a series of pincer–Mn complexes based on bis(imino)pyridine ligands of the type R2NNN (R = tBu, iPr, Cy and Ph) were synthesized and characterized using various spectroscopic techniques. SCXRD studies revealed a trigonal bipyramidal geometry around the metal center in all the complexes. EPR spectroscopy confirmed the presence of high-spin Mn(II) centers with the consistent observation of sextets in EPR spectra. Additionally, solution magnetic moment measurement exhibited values ranging from 5.8 to 6.2 BM for all the complexes, which are in accordance with the theoretical value of 5.92 BM. HRMS analysis complemented structural characterization, showing fragments corresponding to various solvent adducts and derivatives of the complexes. Subsequently, the synthesized complexes were investigated for their catalytic activity in the transfer dehydrogenation of glycerol to lactic acid in the presence of acetone. Among the considered complexes, the catalyst Ph2NNNMnCl2 was found to be highly efficient. Remarkably, a yield of 92% LA was observed with >99% selectivity at 0.5 mol% loading of Ph2NNNMnCl2 in the presence of 1 equivalent of NaOH at 140 °C in 24 h, surpassing the yield obtained from its precursor MnCl2·4H2O, where a yield of 72% LA was observed with 96% selectivity under similar reaction conditions. This catalytic system was further investigated with a range of acceptors, and good to moderate yields were observed in most cases. Moreover, several control experiments, including reaction with PPh3, CS2 and Hg, highlighted the major involvement of molecular species in the reaction medium. Deuterium labelling studies indicated the involvement of C–H bond activation in the catalytic cycle but not in the rate-determining step (RDS), with a secondary kinetic isotope effect (KIE) of 1.25. [ABSTRACT FROM AUTHOR]

The nitrido‐ate complex [(PN)2Ti(N){μ2‐K(OEt2)}]2 (1) (PN−=(N‐(2‐PiPr2‐4‐methylphenyl)‐2,4,6‐Me3C6H2) reductively couples CO and isocyanides in the presence of DME or cryptand (Kryptofix222), to form rare, five‐coordinate TiII complexes having a linear cumulene motif, [K(L)][(PN)2Ti(NCE)] (E=O, L=Kryptofix222, (2); E=NAd, L=3 DME, (3); E=NtBu, L=3 DME, (4); E=NAd, L=Kryptofix222, (5)). Oxidation of 2–5 with [Fc][OTf] afforded an isostructural TiIII center containing a neutral cumulene, [(PN)2Ti(NCE)] (E=O, (6); E=NAd (7), NtBu (8)) and characterization by CW X‐band EPR spectroscopy, revealed unpaired electron to be metal centric. Moreover, 1e− reduction of 6 and 7 in the presence of Kryptofix222cleanly reformed corresponding discrete TiII complexes 2 and 5, which were further characterized by solution magnetization measurements and high‐frequency and ‐field EPR (HFEPR) spectroscopy. Furthermore, oxidation of 7 with [Fc*][B(C6F5)4] resulted in a ligand disproportionated TiIV complex having transoid carbodiimides, [(PN)2Ti(NCNAd)2] (9). Comparison of spectroscopic, structural, and computational data for the divalent, trivalent, and tetravalent systems, including their 15N enriched isotopomers demonstrate these cumulenes to decrease in order of backbonding as TiII→TiIII→TiIV and increasing order of π‐donation as TiII→TiIII→TiIV, thus displaying more covalency in TiIII species. Lastly, we show a synthetic cycle whereby complex 1 can deliver an N‐atom to CO and CNAd. [ABSTRACT FROM AUTHOR]

Neuronal exocytosis requires the assembly of three SNARE proteins, syntaxin and SNAP25 on the plasma membrane and synaptobrevin on the vesicle membrane. However, the precise steps in this process and the points at which assembly and fusion are controlled by regulatory proteins are unclear. In the present work, we examine the kinetics and intermediate states during SNARE assembly in vitro using a combination of time resolved fluorescence and EPR spectroscopy. We show that syntaxin rapidly forms a dimer prior to forming the kinetically stable 2:1 syntaxin:SNAP25 complex and that the 2:1 complex is not diminished by the presence of excess SNAP25. Moreover, the 2:1 complex is temperature-dependent with a reduced concentration at 37 (C. The two segments of SNAP25 behave differently. The N-terminal SN1 segment of SNAP25 exhibits a pronounced increase in backbone ordering from the N- to the C-terminus that is not seen in the C-terminal SNAP25 segment SN2. Both the SN1 and SN2 segments of SNAP25 will assemble with syntaxin; however, while the association of the SN1 segment with syntaxin produces a stable 2:2 (SN1:syntaxin) complex, the complex formed between SN2 and syntaxin is largely disordered. Synaptobrevin fails to bind syntaxin alone but will associate with syntaxin in the presence of either the SN1 or SN2 segments; however, the synaptobrevin:syntaxin:SN2 complex remains disordered. Taken together, these data suggest that synaptobrevin and syntaxin do not assemble in the absence of SNAP25 and that the SN2 segment of SNAP25 is the last to enter the SNARE complex. [ABSTRACT FROM AUTHOR]

The widely discussed phenomenon of flame propagation without self-heating is considered using as examples the combustion of carbon disulfide and the decomposition of nitrogen trichloride. It is shown that, in the nonthermal propagation of a carbon disulfide flame and in its combustion, a determining role is played by a new type of elemental reaction: the displacement of an atom from a molecule by an attacking atomic reactant. For nitrogen trichloride as an example, an unambiguous quantitative relationship between the flame speed and the nonlinear branching rate constant is shown. In both processes, the proposed mechanisms are confirmed by the identification, using EPR and optical spectroscopy, of atoms and radicals that play the main role in the process. The equations corresponding to the identified mechanisms of the processes are confirmed by experiments. [ABSTRACT FROM AUTHOR]

Pulsed electron–electron double resonance (PELDOR) spectroscopy is a powerful method for determining nucleic acid (NA) structure and conformational dynamics. PELDOR with molecular dynamics (MD) simulations opens up unique possibilities for defining the conformational ensembles of flexible, three-dimensional, self-assembled complexes of NA. Understanding the diversity and structure of these complexes is vital for uncovering matrix and regulative biological processes in the human body and artificially influencing them for therapeutic purposes. To explore the reliability of PELDOR and MD simulations, we site-specifically attached nitroxide spin labels to oligonucleotides, which form self-assembled complexes between NA chains and exhibit significant conformational flexibility. The DNA complexes assembled from a pair of oligonucleotides with different linker sizes showed excellent agreement between the distance distributions obtained from PELDOR and calculated from MD simulations, both for the mean inter-spin distance and the distance distribution width. These results prove that PELDOR with MD simulations has significant potential for studying the structure and dynamics of conformational flexible complexes of NA. [ABSTRACT FROM AUTHOR]

In contrast to corresponding nitrosyl compounds, thionitrosyl complexes of rhenium and technetium are rare. Synthetic access to the thionitrosyl core is possible by two main approaches: (i) the treatment of corresponding nitrido complexes with S2Cl2 and (ii) by reaction of halide complexes with trithiazyl chloride. The first synthetic route was applied for the synthesis of novel rhenium and technetium thionitrosyls with the metals in their oxidation states "+1" and "+2". [MVNCl2(PPh3)2], [MVNCl(PPh3)(LOMe)] and [MVINCl2(LOMe)] (M = Re, Tc; {LOMe}− = (η5-cyclopentadienyl)tris(dimethyl phosphito-P)cobaltate(III)) complexes have been used as starting materials for the synthesis of [ReII(NS)Cl3(PPh3)2] (1), [ReII(NS)Cl3(PPh3)(OPPh3)] (2), [ReII(NS)Cl(PPh3)(LOMe)]+ (4a), [ReII(NS)Cl2(LOMe)] (5a), [TcII(NS)Cl(PPh3)(LOMe)]+ (4b) and [TcII(NS)Cl2(LOMe)] (5b). The triphenylphosphine complex 1 is partially suitable as a precursor for ongoing ligand exchange reactions and has been used for the synthesis of [ReI(NS)(PPh3)(Et2btu)2] (3a) (HEt2btu = N,N-diethyl-N′-benzoyl thiourea) containing two chelating benzoyl thioureato ligands. The novel compounds have been isolated in crystalline form and studied by X-ray diffraction and spectroscopic methods including IR, NMR and EPR spectroscopy and (where possible) mass spectrometry. A comparison of structurally related rhenium and technetium complexes allows for conclusions about similarities and differences in stability, reaction kinetics and redox behavior between these 4d and 5d transition metals. [ABSTRACT FROM AUTHOR]

In this study we demonstrated for the first time synthetic procedures for composites of salinomycin (SalH) and two-line ferrihydrite. The products were characterized by various methods such as elemental analysis, attenuated total reflectance–Fourier-transform spectroscopy (ATR-FTIR), electron paramagnetic resonance spectroscopy (EPR), powder X-ray diffraction analysis (XRD), electrospray-ionization mass spectrometry (ESI-MS), thermogravimetric analysis with differential thermal analysis (DTA) and mass spectrometry (TG-DTA/MS). The EPR spectra of the isolated compounds consisted of signals associated with both isolated Fe3+ ions and magnetically coupled Fe3+ ions. Powder XRD analyses of the isolated products showed two intense and broad peaks at 9° and 15° 2Θ, corresponding to salinomycinic acid. Broad peaks with very low intensity around 35°, assigned to two-line ferrihydrite, were also registered. Based on the experimental results, we concluded that salinomycin sodium reacted with Fe(III) chloride to form composites consisting of two-line ferrihydrite and salinomycinic acid. One of the composites exerted pronounced antitumor activity in the sub-micromolar concentration range against human cervical cancer (HeLa), non-small-cell lung cancer (A549), colon cancer (SW480), and ovarian teratocarcinoma (CH1/PA1) cells. [ABSTRACT FROM AUTHOR]

The combination of planar‐directing, strong‐field [N4] ligands with a weak axial field component is known to stabilize five‐coordinate iron(III) complexes in otherwise uncommon spin states. In this work, a series of axially perturbed iron(III) complexes of an [N4] macrocyclic ligand of the Jäger type, [Fe(L)X] (with X: Cl, Br, I, NCS) gave intermediate‐spin ground states with axially steered admixture of the high‐spin state, S=3/2; 5/2. The nature of the electronic ground‐state as deduced from SQUID magnetometry, 57Fe Mössbauer spectroscopy in the solid, and 1H NMR and EPR spectroscopies in (frozen) solutions was discussed in the light of the solid‐state structures, which were obtained from single‐crystal X‐ray diffraction. A DFT‐based protocol was established to quantify the axial field effects and, by including relevant [N4] systems, predict the differential equatorial ligand field components. [ABSTRACT FROM AUTHOR]

A relationship between EPR and spectrophotometric parameters related to beer staling and antioxidant activity, was identified. AUC (area under the curve), intensity at 150 min (T150), radical scavenging activity (RSA), total phenolic compounds (TPC), hydroxyl radical scavenging capacity (HRSC) and one parameter linked to staling degree of beers (thiobarbituric index, TBI) were related. Temperature was modified to find the proper working conditions for EPR spin-trapping experiments and it was found that it affected the kinetic of PBN adduct evolution. For the samples reaching a maximum intensity signal, the higher the heating temperature, the shorter the time interval needed to reach it. No linear relationship was detected among parameters obtained with EPR spin trapping experiments and RSA, TPC, TPI, and HRSC when correlating one parameter with another. On the contrary, a good linear relationship was found among AUC or T150 and a combination of RSA, TPC, TPI, and HRSC (R2 = 0.9562 and 0.9694, respectively). The goodness of fit increased to R2 = 1 when a combination of AUC and T150 was related to a combination of RSA, TPC, and TPI, and HRSC. [ABSTRACT FROM AUTHOR]

High abundance and low toxicity make zinc oxide very attractive for broad application in the field of photocatalysis for remediation of toxic compounds from water. Its performance could be elegantly improved by inducing native defects into ZnO semiconductor nanocrystals. However, this typically requires post-processing at high temperatures, during which many of the benefits of the original batch of monodisperse small grains are lost due to agglomeration and/or crystal growth. Within this research we show how variations in defect population are inherent to recrystallization process and that they can be tuned to some extent by choosing optimal pathways. The defects were studied by Raman, photoluminescence and EPR spectroscopy, while the surface chemistry of the ZnO nanorods, solvothermally recrystallized from ZnO nanodots, was evaluated by X-ray photoelectron spectroscopy. The produced nanorods with different dimensions were also utilized to show how effective the samples are for degradation of a model pollutant, namely caffeine. Unexpectedly, we found that the surface chemistry of our samples is not the main factor in photocatalytic efficiency. Instead, we show that the differences in photocatalytic activity are mainly determined by the defect population within the bulk formed during the recrystallization process under altered solvothermal conditions. [ABSTRACT FROM AUTHOR]

Bacterial small laccases (SLAC) are promising industrial biocatalysts due to their ability to oxidize a broad range of substrates with exceptional thermostability and tolerance for alkaline pH. Electron transfer between substrate, copper centers, and O2 is one of the key steps in the catalytic turnover of SLAC. However, limited research has been conducted on the electron transfer pathway of SLAC and SLAC-catalyzed reactions, hindering further engineering of SLAC to produce tunable biocatalysts for novel applications. Herein, the combinational use of electron paramagnetic resonance (EPR) and ultravioletevisible (UV evis) spectroscopic methods coupled with redox titration were employed to monitor the electron transfer processes and obtain further insights into the electron transfer pathway in SLAC. The reduction potentials for type 1 copper (T1Cu), type 2 copper (T2Cu) and type 3 copper (T3Cu) were determined to be 367 ± 2 mV, 378 ± 5 mV and 403 ± 2 mV, respectively. Moreover, the reduction potential of a selected substrate of SLAC, hydroquinone (HQ), was determined to be 288 mV using cyclic voltammetry (CV). In this way, an electron transfer pathway was identified based on the reduction potentials. Specifically, electrons are transferred from HQ to T1Cu, then to T2Cu and T3Cu, and finally to O2. Furthermore, superhyperfine splitting observed via EPR during redox titration indicated a modification in the covalency of T2Cu upon electron uptake, suggesting a conformational alteration in the protein environment surrounding the copper sites, which could potentially influence the reduction potential of the copper sites during catalytic processes. The results presented here not only provide a comprehensive method for analyzing the electron transfer pathway in metalloenzymes through reduction potential measurements, but also offer valuable insights for further engineering and directed evolution studies of SLAC in the aim for biotechnological and industrial applications. [ABSTRACT FROM AUTHOR]

The high‐resolution X‐ray structures of the model protein lysozyme in the presence of the potential drug [VIVO(acetylacetonato)2] from crystals grown in 1.1 M NaCl, 0.1 M sodium acetate at pH 4.0 reveal the binding to the protein of different and unexpected mixed‐valence cage‐like polyoxidovanadates (POVs): [V15O36(OH2)]5−, which non‐covalently interacts with the lysozyme surface, [V15O33(OH2)]+ and [V20O51(OH2)]n− (this latter based on an unusual {V18O43} cage) which covalently bind the protein. EPR spectroscopy confirms the partial oxidation of VIV to VV and the formation of mixed‐valence species. The results indicate that the interaction with proteins can stabilize the structure of unexpected – both for dimension and architecture – POVs, not observed in aqueous solution. [ABSTRACT FROM AUTHOR]

Rigorous comparisons between single site-and nanoparticle (NP)-dispersed catalysts featuring the same composition, in terms of activity, selectivity, and reaction mechanism, are limited. This limitation is partly due to the tendency of single metal atoms to sinter into aggregated NPs at high loadings and elevated temperatures, driven by a decrease in metal surface free energy. Here, we have developed a unique two-step method for the synthesis of single Cu sites on ZSM-5 (termed CuS/ZSM-5) with high thermal stability. The atomic-level dispersion of single Cu sites was confirmed through scanning transmission electron microscopy, X-ray absorption fine structure (XAFS), and electron paramagnetic resonance spectroscopy. The CuS/ZSM-5 catalyst was compared to a CuO NP-based catalyst (termed CuN/ZSM-5) in the oxidation of NH3 to N2, with the former exhibiting superior activity and selectivity. Furthermore, operando XAFS and diffuse reflectance infrared Fourier transform spectroscopy studies were conducted to simultaneously assess the fate of the Cu and the surface adsorbates, providing a comprehensive understanding of the mechanism of the two catalysts. The study shows that the facile redox behavior exhibited by single Cu sites correlates with the enhanced activity observed for the CuS/ZSM-5 catalyst. [ABSTRACT FROM AUTHOR]

With rational designability, versatile tunability, and quantum coherence, molecular electron spin qubits could offer new opportunities for quantum information science, enabling simplified implementation of quantum algorithms and chemical‐specific quantum sensing. The development of these transformative technologies relies on coherent addressing of single molecular electron spin qubits with high initialization, manipulation, and readout fidelities. This is unfeasible to conventional electron spin resonance spectroscopy, which is widely used for coherent addressing of ensemble electron spins, due to its low initialization efficiency and readout sensitivity. Taking advantage of single spin detectability of single‐molecule spectroscopy, scanning tunneling microscopy, atomic force microscopy, and quantum metrology, several strategies have been developed to empower electron spin resonance spectroscopy with single qubit addressability. In this Emerging Topic, we introduce principles and technical implementation of strategies for coherent addressing of single molecular electron spin qubits, discuss their potential applicability in quantum technologies, and point out their challenges in terms of scalability, molecular design, and/or decoherence suppression. We discuss future directions to overcome these challenges and to improve single qubit addressing technologies, which will facilitate the advancement of molecular quantum information science. [ABSTRACT FROM AUTHOR]

Rigorous comparisons between single site-and nanoparticle (NP)-dispersed catalysts featuring the same composition, in terms of activity, selectivity, and reaction mechanism, are limited. This limitation is partly due to the tendency of single metal atoms to sinter into aggregated NPs at high loadings and elevated temperatures, driven by a decrease in metal surface free energy. Here, we have developed a unique two-step method for the synthesis of single Cu sites on ZSM-5 (termed CuS/ZSM-5) with high thermal stability. The atomic-level dispersion of single Cu sites was confirmed through scanning transmission electron microscopy, X-ray absorption fine structure (XAFS), and electron paramagnetic resonance spectroscopy. The CuS/ZSM-5 catalyst was compared to a CuO NP-based catalyst (termed CuN/ZSM-5) in the oxidation of NH3 to N2, with the former exhibiting superior activity and selectivity. Furthermore, operando XAFS and diffuse reflectance infrared Fourier transform spectroscopy studies were conducted to simultaneously assess the fate of the Cu and the surface adsorbates, providing a comprehensive understanding of the mechanism of the two catalysts. The study shows that the facile redox behavior exhibited by single Cu sites correlates with the enhanced activity observed for the CuS/ZSM-5 catalyst. [ABSTRACT FROM AUTHOR]

Carbon–phosphorus bond formation is of great importance in synthetic chemistry. A versatile strategy for the formation of carbon–phosphorus bonds involves the addition of phosphorus radicals to π-systems. However, the generation methods of phosphorus radicals are primarily restricted to homolytic cleavage of phosphorus–hydrogen bonds with excess peroxides or toxic metal salts as oxidants. Herein, we introduce a photoinduced palladium-catalyzed generation of phosphorus radicals using inexpensive and readily available Cl–phosphine oxides and Cl–phosphates as the phosphorus radical precursors. The key step for this strategy lies in the reductive activation of phosphorus–chloride bonds with the excited palladium complex under visible light irradiation. The involvement of phosphorus radicals has been evidenced by EPR spectroscopy and radical trapping experiments. Based on this strategy, both phosphinyl and phosphonyl groups could be regiospecifically incorporated into simple alkenes and heteroaromatic compounds via radical mediated carbon–phosphorus bond formation. Besides, carbon–phosphorus difunctionalization of alkenes was also achieved to afford phosphorylated oxindoles. [ABSTRACT FROM AUTHOR]

To generate red emissions, manganese (IV) ions have recently gained recognition as potent non-rare-earth activators. However, the oxide and fluoride hosts that offer suitable environments for Mn4+ require careful preparation, involving precise control of reaction parameters like redox equilibrium and temperature. In the current work, we show simultaneous oxidation of Mn2+ to Mn4+ by devitrification of glassy Na 2 Ge 4 O 9 : Mn under moderate atmospheric conditions and under the argon atmosphere. The G-sample was devitrified via thermal treatment after the parent glass, which shares the same chemical formula as dilithium tetragermanate (Na 2 Ge 4 O 9), was created through the use of traditional melt-quenching (MQ). Optical spectroscopy and electron paramagnetic resonance (EPR) spectroscopic are utilized to confirm the Mn2+ oxidation to Mn4+ from glass stat to glass ceramic after thermal treatment. Due to the transition from Mn2+ to Mn4+, a sharp 668 nm emission peak is recorded whereas the red emission peaking at 611 nm monitored in glass is steadily reduced. The temperature-dependent PL spectra of the Na 2 Ge 4 O 9 :0.1Mn+4, red-emitting GC in the temperature range ∼295–490 K were recorded. The PL emission intensity decreases gradually with increasing the temperature. The technique showcased for producing Na 2 Ge 4 O 9 :Mn4+ phosphors could be expanded to synthesize other phosphors incorporating activators possessing a high oxidation state. [ABSTRACT FROM AUTHOR]

Nitrenes are a highly reactive, yet fundamental, compound class. They possess a monovalent nitrogen atom and usually a short life span, typically in the nanosecond range. Here, we report on the synthesis of a stable nitrene by photolysis of the arylazide MSFluindN3 (1), which gave rise to the quantitative formation of the arylnitrene MSFluindN (2) (MSFluind is dispiro[fluorene-9,3′-(1′,1′,7′,7′-tetramethyl-s-hydrindacen-4′-yl)-5′,9′′-fluorene]) that remains unchanged for at least 3 days when stored under argon atmosphere at room temperature. The extraordinary life span permitted the full characterization of 2 by single-crystal x-ray crystallography, electron paramagnetic resonance spectroscopy, and superconducting quantum interference device magnetometry, which supported a triplet ground state. Theoretical simulations suggest that in addition to the kinetic stabilization conferred by the bulky MSFluind aryl substituent, electron delocalization across the central aromatic ring contributes to the electron stabilization of 2. [ABSTRACT FROM AUTHOR]

The metal-free porphyrins protonation has gained interest over five decades because its structure modification and hardly monoacid intermediate isolation. Here, upon the hydrogen atom abstraction processes, one step diproptonated H3STTP(BF4)2 (STTP = 5,10,15,20-tetraphenyl-21-thiaporphyrin) (3) and stepwise protonated HS2TTPSbCl6 (5) and diprotonated H2S2TTP(BF4)2 (6) (S2TTP = 5,10,15,20-tetraphenyl-21,23-thiaporphyrin) compounds were obtained using HSTTP and S2TTP with oxidants. The closed-shell protonated compounds were fully characterized using XRD, UV-vis, IR and NMR spectra. In addition, the reduced 19π compounds [K(2,2,2)]HSTTP (2) and [K(2,2,2)]S2TTP (7) were synthesized by the ligands with reductant KC8 in THF solution. These two open-shell compounds were characterized with UV-vis, IR and EPR spectroscopies. The semiempirical ZINDO/S method was employed to analyze the HOMO/LUMO gap lever and identify the electronic transitions of the UV-vis spectra of the closed- and open-shell porphyrin compounds. [ABSTRACT FROM AUTHOR]

[Display omitted] • Co 2 Mn-LDH efficiently activates CaSO 3 for rapid degradation of MNZ. • Co 2 Mn-LDH exhibits superior stability and reusability in the degradation process. • SO 4 •− and 1O 2 are the major radicals in MNZ degradation process. • The redox cycle of Co2+/Co3+ and Mn3+/Mn4+, and O v enhance the ROS generation. • Co 2 Mn-LDH/CaSO 3 system shows excellent anti-resistance to water matrix. Metronidazole (MNZ), a commonly used antibiotic, poses risks to water bodies and human health due to its potential carcinogenic, mutagenic, and genotoxic effects. In this study, mesoporous cobalt-manganese layered double hydroxides (Co x Mn y -LDH) with abundant oxygen vacancies (O v) were successfully synthesized using the co-precipitation method and used to activate calcium sulfite (CaSO 3) with slight soluble in water for MNZ degradation. The characterization results revealed that Co 2 Mn-LDH had higher specific areas and exhibited good crystallinity. Co 2 Mn-LDH/CaSO 3 exhibited the best catalytic performance under optimal conditions, achieving a remarkable MNZ degradation efficiency of up to 98.1 % in only 8 min. Quenching experiments and electron paramagnetic resonance (EPR) tests showed that SO 4 •− and 1O 2 played pivotal roles in the MNZ degradation process by activated CaSO 3 , while the redox cycles of Co2+/Co3+ and Mn3+/Mn4+ on the catalyst surface accelerated electron transfer, promoting radical generation. Three MNZ degradation routes were put forward based on the density functional theory (DFT) and liquid chromatography-mass spectrometer (LC-MS) analysis. Meanwhile, the toxicity analysis result demonstrated that the toxicity of intermediates post-catalytic reaction was decreased. Furthermore, the Co 2 Mn-LDH/CaSO 3 system displayed excellent stability, reusability, and anti-interference capability, and achieved a comparably high removal efficiency across various organic pollutant water bodies. This study provides valuable insights into the development and optimization of effective heterogeneous catalysts for treating antibiotic-contaminated wastewater. [ABSTRACT FROM AUTHOR]

The double S-scheme electron transfer pathway of the Cu 2−x Se/T-Cd 0.5 Zn 0.5 S system leverages the synergistic effect of interface and bulk phase S-scheme homo-heterojunctions, along with the utilization of "hot electrons" generated by the LSPR effect, to facilitate efficient charge separation and transfer, thereby achieving enhanced performance in H 2 evolution. [Display omitted] • The twinned-Cd 0.5 Zn 0.5 S, composed of zinc blende and wurtzite Cd 0.5 Zn 0.5 S have excellent H 2 evolution activity. • Cu 2−x Se can further promote charge separation and enhance the H 2 evolution kinetics. • The Cu 2−x Se/T-Cd 0.5 Zn 0.5 S homo-heterojunctions with interface and bulk synergistic double S-scheme. • The injection of "hot electrons" generated by the LSPR effect of Cu 2−x Se into the T-Cd 0.5 Zn 0.5 S. The enhancement of charge separation and utilization efficiency in both the bulk phase and interface of semiconductor photocatalysts, as well as the expansion of light absorption range, are crucial research topics in the field of photocatalysis. To address this issue, twinned Cd 0.5 Zn 0. 5S (T -CZS) homojunctions consisting of wurtzite Cd 0.5 Zn 0.5 S (WZ-CZS) and zinc blende Cd 0.5 Zn 0.5 S (ZB-CZS) were synthesized via a hydrothermal method to facilitate the bulk-phase charge separation. Meanwhile, Cu 2−x Se with localized surface plasmon resonance effect (LSPR) generated by Cu vacancies was also obtained through a hydrothermal process. Due to their opposite electronegativity, a solvent evaporation strategy was employed to combine Cu 2−x Se and T -CZS by intermolecular electrostatic. After optimization, the photocatalytic hydrogen (H 2) evolution rate of 5 wt% Cu 2−x Se/ T -CZS reached an impressive value of 60 mmol∙h−1∙g−1, which was 4.6 and 66.6 times higher than that of pure Cu 2−x Se and T -CZS, respectively. Furthermore, this composites demonstrated a remarkable rate of 0.46 mmol∙h−1∙g−1 under near-infrared (NIR) wavelength (>800 nm). The enhanced performance observed in Cu 2−x Se/ T -CZS can be attributed to its unique and efficient double S-scheme charge transfer mechanism which effectively suppresses rapid recombination of electron-hole pairs both within the bulk phase and at the surface interfaces; this conclusion is supported by Density Functional Theory (DFT) calculations as well as electron paramagnetic resonance spectroscopy analysis. Moreover, incorporation of Cu 2−x Se enables effective utilization ultraviolet visible-near infrared (UV–Vis-NIR) light by the composites while facilitating injection "hot electrons" into T -CZS for promoting photocatalytic reactions. This study provides a potential strategy for achieving efficient solar energy conversion through synergistic integration of non-stoichiometric plasmonic materials with photocatalysts with twinned-twinned structures. [ABSTRACT FROM AUTHOR]

Kadavur is a significant Proterozoic anorthosite-gabbro complex, located within the Madurai block of the southern granulite terrain, India. In Kadavur complex, the marginal zone is made up of rapakivi granites and dolerite dykes and the core of this complex is made up of late-stage intruded pegmatites. Tantalum-niobium (Ta-Nb)-rich pegmatites (n = 20) and barren pegmatites (n = 5) were studied for fluid inclusion and electron paramagnetic resonance (EPR) characterization. Five and two distinct fluid inclusions are identified in the Ta-Nb-rich pegmatites, and barren pegmatites respectively. In the mineralized samples, carbonic inclusions show depression in the CO2 melting temperature indicating the presence of volatile phases of N2, C and CH4, which is also confirmed by a laser Raman microprobe. The similar range of trapping temperatures and different modes of homogenization (liquid and vapour) are attributed to the fluid immiscibility process for Kadavur Ta-Nb mineralization. The EPR is one of the exploration tools for many mineral deposits. EPR spectra signals for mineralized pegmatite and barren pegmatite samples show the paramagnetic induced defect centres of E1 and peroxyl types identified in Kadavur, India. [ABSTRACT FROM AUTHOR]

Li-excess cathode materials with a disordered rock-salt structure (DRX) Li1.2Ti0.4Mn0.4O2 and Li1.3Nb0.3Mn0.4O2 were prepared by mechanochemically assisted solid-state synthesis at various synthesis conditions using different lithium sources (Li2O and LiOH). As-prepared samples were characterized by X-ray powder diffraction (XRD), thermal analysis in combination with mass spectrometry (DSC/TG/MS), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), electron paramagnetic resonance spectroscopy (EPR), in situ time-resolved synchrotron powder X-ray diffraction (SPXRD) and galvanostatic cycling. The effects of different lithium sources and synthesis temperature on the crystal and local structure and the impact of additional thermal treatment (re-heating) on electrochemical performance of the DRX oxides were investigated. The results obtained show that the optimal synthesis temperature is 950 °C and the use of LiOH as a lithium source leads to the synthesis of the DRX oxides with a fully disordered structure, which is stable when re-heated at a temperature of 600 °C. In addition, re-heating leads to further optimization of the properties of the DRX oxides; this results in a significant improvement of their electrochemical properties. [ABSTRACT FROM AUTHOR]

The paper reports the first comprehensive physicochemical study of minerals of the amblygonite LiAlPO4F–montebrasite LiAlPO4(OH) series. An EPR spectroscopic and calorimetric study of montebrasite LiAlPO4(OH)0.9F0.1 from the Shuk-Byul rare-metal granite pegmatites (Sangilen Highlands, Tuva) and amblygonite LiAlPO4F0.5(OH)0.5 from pegmatites of the Voron'i Tundras (Kola Peninsula) was carried out. Using the EPR method, the radiation-sensitive paramagnetic O– centers were discovered. They were formed without participation of impurity elements in the regular sites of crystal lattice. The possibility use of minerals of the amblygonite–montebrasite series for EPR geochronometry has been demonstrated for the first time. Using the method of high-temperature melt dissolution calorimetry on a Tian-Calvét microcalorimeter, the enthalpies of formation from elements (298.15 K) = –2326.3 ± 2.2 kJ/mol for montebrasite with the composition LiAl(PO4)(OH)0.9F0.1 and for amblygonite with the composition LiAl(PO4)F0.5(OH)0.5 (‒2347.9 ± 3.1 kJ/mol) are obtained; and the values of this parameter are calculated for the end members with an ideal composition of the series: for montebrasite (–2315.5 ± 2.2 kJ/mol) and for amblygonite (–2401.6 ± 3.1 kJ/mol). The values of the standard entropy S0 (298.15 K) and the Gibbs energy of formation (298.15 K) for intermediate and end members of the amblygonite–montebrasite series are estimated. [ABSTRACT FROM AUTHOR]

The reaction of sodium 2,4‐di‐tert‐butyl‐6‐(diphenylphos‐phino)phenolate (1, NaOArP) with TiIVCl4(THF)2 in a 2 : 1 molar ratio yielded TiIV(OArP)2Cl2 (2). The reduction of 2 with magnesium gave the dimeric titanium(III) compound [TiIII(OArP)2Cl]2 (3). In the presence of magnesium, compound 2 was found to catalyse the cyclotrimerization, acyclic oligomerisation, and hydrogenation of terminal alkynes. The complexes were characterised by single‐crystal X‐ray diffraction, optical spectroscopy, elemental analysis, and NMR or EPR spectroscopy, respectively. [ABSTRACT FROM AUTHOR]

Self‐assembly of new donor‐acceptor systems based on (5,10,15,20‐tetraphenylporphinato)manganese(III)/(5,10,15,20‐tetra‐4‐tert‐butylphenylporphinato)manganese(III)/(octakis(4‐tert‐butylphenyl)tetraazaporphinato)manganese(III) acetate ((AcO)MnTPP/(AcO)MnTBPP/(AcO)MnTAP) and 4‐(10‐phenylanthracen‐9‐yl)pyridine (PyAn) was studied using fluorescence spectroscopy and mass spectrometry. It was found that the coordination complexes of 1 : 1 composition (dyads) are formed in toluene. The spectral properties, the chemical structures and redox behavior of the dyads were described using 1H NMR, IR, ESR spectroscopy and cyclic voltammetry, respectively. The dynamic processes and the characteristics in the excited state of the dyads were obtained using the femtosecond transient absorption spectroscopy method. Density functional theory (DFT), time‐dependent DFT methods were used to elucidate the dyad electronic structures and to establish the differences in their frontier molecular orbitals. The analysis of the lambda parameter and the distance of hole‐pair interaction was indicated more favorable charge transfer between the macrocycle and the axial PyAn fragment in (AcO)(PyAn)MnTAP. The calculated values of the zero‐field splitting parameters D and E/D, together with the g tensors of the lowest spin‐orbit state for (AcO)MnTPP and (AcO)(PyAn)MnTPP were obtained using the combination of DFT and Multireference Perturbation Theory (CASSCF/NEVPT2) simulations. The data obtained develop the fundamental basis in the field of photovoltaics and show the prospects for the study of molecular systems of this class. [ABSTRACT FROM AUTHOR]

A series of five 3,6‐divinyl‐N‐arylcarbazoles‐bridged diruthenium complexes with a general formula of [{Ru(CO)Cl(PiPr3)2}2(μ‐(CH=CH)2‐(N‐arylcarbazole)‐3,6); aryl = 4‐anisyl; [1a], 4‐tolyl; [1b], phenyl; [1c], 4‐(trifluoromethyl)phenyl; [1d], and 4‐nitrophenyl; [1e]] were successfully synthesized. These new square‐pyramidal bis(ruthenium‐vinyl)‐type complexes were characterized in their neutral state via classical NMR, UV/Vis, and IR spectroscopic techniques and in their three various accessible oxidized states via electrochemical techniques and ESR spectroscopy along with UV/Vis/NIR and IR spectroelectrochemistry as well as with DFT calculations. Our obtained results were compared with the closely related bis(ruthenium‐vinyl)‐appended N‐(4‐anisyl)diphenylamine TAARu2 counterpart of [1a]. Electrochemical studies on complexes [1a]–[1e] revealed three consecutive, chemically and electrochemically, well‐separated, reversible one‐electron oxidation processes at low and well‐accessible potentials. Their half‐wave potential separations ΔE½ between the individual redox waves and the derived comproportionation constants Kc1–Kc3 attribute to noteworthy stability of every oxidized intermediate state. The concert electrochemical and UV/Vis/NIR/IR spectro(electro)scopic results on these rotationally restricted N‐arylcarbazoles‐bridged bis(ruthenium‐alkenyl)‐type complexes [1a]–[1e] confirmed the relative weakness influence of altering the para‐substituent on the peripheral aryl ring. This is most probably due to the sizable torsion with nearly 55° between the co‐planarity of the carbazole heterocycle core and the peripheral N‐bound aryl ring. In their mixed‐valent (MV) radical states [1a]+–[1e]+, the observed pattern of two well‐separated Ru(C≡O) bands mirrors the uneven distribution of the uni‐positive charge over the two chemically equivalent bis(ruthenium‐vinyl) moieties as indicated by classical class II of Robin–Day classification of MV states. [ABSTRACT FROM AUTHOR]

Two novel metal complexes, C1 and C2, were synthesized through the reaction of an azo dye ligand, obtained by coupling 4‐chloroaniline with 1,3‐dimethyl barbituric acid. The structure of the ligand was confirmed using Fourier‐transform infrared spectroscopy (FTIR) and Nuclear magnetic resonance (NMR). UV–Vis spectroscopy was employed to assess the ligand's sensing ability toward six different metal ions. Comprehensive characterization of the synthesized metal complexes was conducted using elemental analysis, X‐ray photoelectron spectroscopy (XPS), thermogravimetric analysis–difference thermogravimetry (TGA‐DTG), FTIR, UV–Vis spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, and single‐crystal X‐ray diffraction (SC‐XRD). X‐ray analysis revealed octahedral coordination geometry with a 2:1 ligand‐to‐metal ratio and dimethylformamide (DMF) coordination with the metal atom in both complexes. Hirshfeld analysis and 2D fingerprint plots were employed to investigate supramolecular and intermolecular interactions within the crystal system. Density functional theory (DFT/B3LYP) calculations were utilized to compute energy gaps and other important theoretical features. Sensing experiments with tetrabutylammonium fluoride (TBAF) were conducted at a concentration of 1 × 10−5 M. Furthermore, the bioactivity of the synthesized metal complexes and ligand L was evaluated through molecular docking studies against Protein Data Bank (PDB IDs) 4XUY (Staphylococcus aureus) and 3BQW (Aspergillus niger). Also, antimicrobial activity was assessed using the agar well diffusion technique, revealing that complexes C1 and C2 exhibited enhanced antimicrobial activities against the tested organisms compared to the parent azo dye ligand. The computational and experimental bioactivity data are in good agreement with each other. [ABSTRACT FROM AUTHOR]

The role of manganese in photo‐induced organometallic‐mediated radical polymerization (photo‐OMRP) under LED (light‐emitting diode) irradiation has not been previously explored. In this study, four manganese (II) complexes, namely [Mn(6‐tert‐butyl‐N,N′‐propanebis [salicylimine])] (Mn‐Bu), [Mn(6,3‐di‐tert‐butyl‐N,N′‐propanebis [salicylimine])] (Mn‐Bu2), [Mn(6‐ethoxy‐N,N′‐propanebis [salicylimine])] (Mn‐Ethoxy), and [Mn(6,3‐di‐ethoxy‐N,N′‐propanebis [salicylimine])] (Mn‐Ethoxy2), were synthesized using both symmetrical and non‐symmetrical tetradentate N2O2 Schiff base ligands. The Schiff base ligands were characterized by Fourier transform infrared spectroscopy (FTIR), ultraviolet–visible spectroscopy (UV–Vis), and nuclear magnetic resonance spectroscopy (NMR). The Mn (II) complexes were characterized by FTIR, UV–Vis, elemental analysis, molar conductivity, cyclic voltammetry, MALDI‐TOF mass spectrometry, electron paramagnetic resonance, and rationalized with density functional theory (DFT) studies. All complexes were evaluated as photo‐OMRP mediators under LED irradiation at 390 nm and in the 400–800 nm range. The photopolymerization utilized methyl acrylate (MA) and diphenyl(2,4,6‐trimethylbenzoyl)phosphine oxide (TPO) in varying molar ratios of [MA]/[MnII]/[TPO] (900/1/1, 600/1/1, and 600/1/0.5). The photo‐OMRP of MA mediated by Mn‐Bu2 showed the best control over molecular weight (Mn matching Mn,th) and dispersity (Ð < 1.30) at a [MA]/[MnII]/[TPO] = 600/1/0.5 M ratio. The polymerization system demonstrated a living character, as evidenced by reversible "on/off" light source switching. Furthermore, a block copolymer of poly (methyl acrylate)‐b‐poly (butyl acrylate) was successfully synthesized employing a sequential visible‐light‐induced process, with the Mn‐Bu2 system showing the best results. [ABSTRACT FROM AUTHOR]