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The complex interface reactions are crucial to the performance of the Li2MnO3 cathode material. Here, the interface reactions between the liquid electrolyte and the typical surfaces of Li2MnO3 during the charging process are systematically investigated by ab initio molecular dynamics (AIMD) simulation and first-principles calculation. The results indicate that these interface reactions lead to the formation of hydroxide radicals, oxygen, carbon dioxide, carbonate radicals, and other products, which are consistent with the experimental findings. These processes primarily result from the conversion of the stable closed-shell O2- into reactive oxygen ions by electron loss. All surfaces exhibit some degree of layered- and spinel-like phase transitions during the AIMD simulations, consistent with the experiment. This is mainly attributed to the decrease in the Mn-O bond strength and the increase in the Li/O ion vacancy concentration. This study offers valuable theoretical insights into the interface reaction between lithium-rich cathode materials and liquid electrolytes.
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The use of mixed halide perovskites in the preparation of blue light-emitting diodes (LEDs) is considered to be the most effective and direct approach. However, the introduction of chlorine (Cl) element might raise stability issues in the system and lead to low efficiency, thereby impeding the development of deep blue light-emitting diodes with high efficiency and stability. Determining the alloy concentration and the atomic distribution of bromine-chlorine (Br-Cl) mixed systems is essential for further application of deep blue light-emitting diodes. In this work, we have systematically investigated the stability of bromine-chlorine (Br-Cl) mixed alloy systems in various substitution configurations using high-throughput theoretical calculations. Based on this, we have examined the relationship between configuration stability and three aspects: the type of octahedra, the orientation of the octahedra and the Pb-X-Pb distortion angle in the configuration.
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Understanding the nonlinear response of light and materials is crucial for fundamental physics and next-generation electronic devices. In this work, we have investigated the second-order nonlinear bulk photovoltaic (BPV) and bulk spin photovoltaic (BSPV) effects in the piezoelectric binary materials T-IV-VI and T-V-V (IV = Ge, Sn; VI = S, Se; and V = P, As, Sb, Bi). The independent nonzero conductivity tensors of charge current are derived for these binaries through the symmetry analysis, along with the mechanism for generating pure spin current. These binaries, with their unique folded structure, exhibit significant charge and spin currents under illumination. Furthermore, we find that strain engineering can effectively modulate charge/spin currents by influencing charge density distribution and built-in electric field due to the piezoelectric effect. Our research suggests that the piezoelectric binary materials possess enormous and tunable charge/spin currents, underscoring their potential for applications in nonlinear flexible optoelectronics and spintronics.
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Semiconductor materials of abnormal stoichiometric ratio often exhibit unique properties, yet it is still a challenge to determine the structures of such materials in an efficient way. Herein, we propose a method for structurally biased screening according to the coordination numbers and the numbers of Wyckoff positions, balancing the atom local environment and the global symmetry of structures. Based on first-principles calculations, we have predicted two metastable peroxides P21/c-ScO2 and Pmmn-TiO3 with more than six coordination points. For these two structures, the most stable intrinsic defect is the oxygen vacancy (VO) at the peroxide anion (O2-2), which induces the absence of antibonding orbital formed by O2-2 near the valence band maximum. With the introduction of VO, the decrease of coordination numbers leads to charge recombination, and results in the appearance of an ordered phase TiO2.5 with stronger Ti-O orbital hybridization. The proposed method presents a promising and feasible approach for the screening of novel compounds.
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Finding tunable van der Waals (vdW) ferromagnets that operate at above room temperature is an important research focus in physics and materials science. Most vdW magnets are only intrinsically magnetic far below room temperature and magnetism with square-shaped hysteresis at room temperature has yet to be observed. Here, we report magnetism in a quasi-2D magnet Cr_{1.2}Te_{2} observed at room temperature (290 K). This magnetism was tuned via a protonic gate with an electron doping concentration up to 3.8×10^{21} cm^{-3}. We observed nonmonotonic evolutions in both coercivity and anomalous Hall resistivity. Under increased electron doping, the coercivities and anomalous Hall effects (AHEs) vanished, indicating a doping-induced magnetic phase transition. This occurred up to room temperature. DFT calculations showed the formation of an antiferromagnetic (AFM) phase caused by the intercalation of protons which induced significant electron doping in the Cr_{1.2}Te_{2}. The tunability of the magnetic properties and phase in room temperature magnetic vdW Cr_{1.2}Te_{2} is a significant step towards practical spintronic devices.
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MnSb2Te4 has a similar structure to an emerging material, MnBi2Te4. According to earlier theoretical studies, the formation energy of Mn antisite defects in MnSb2Te4 is negative, suggesting its inherent instability. This is clearly in contrast to the successful synthesis of experimental samples of MnSb2Te4. Here, the growth environment of MnSb2Te4 and the intrinsic defects are correspondingly investigated. We find that the Mn antisite defect is the most stable defect in the system, and a Mn-rich growth environment favors its formation. The thermodynamic equilibrium concentrations of the Mn antisite defects could be as high as 15% under Mn-poor conditions and 31% under Mn-rich conditions. It is also found that Mn antisite defects prefer a uniform distribution. In addition, the Mn antisite defects can modulate the interlayer magnetic coupling in MnSb2Te4, leading to a transition from the ideal antiferromagnetic ground state to a ferromagnetic state. The ferromagnetic coupling effect can be further enhanced by controlling the defect concentration.
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With the advancement of plant synthetic biology, plastids have emerged as an optimal platform for the heterologous production of numerous commercially valuable secondary metabolites and therapeutic proteins. In comparison on nuclear genetic engineering, plastid genetic engineering offers unique advantages in terms of efficient expression of foreign genes and biological safety. However, the constitutive expression of foreign genes in the plastid system may impede plant growth. Therefore, it is imperative to further elucidate and design regulatory elements that can achieve precise regulation of foreign genes. In this review, we summarize the progress made in developing regulatory elements for plastid genetic engineering, including operon design and optimization, multi-gene coexpression regulation strategies, and identification of new expression regulatory elements. These findings provide valuable insights for future research.
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Engenharia Genética , Plantas , Plantas/genética , Plastídeos/genética , Sequências Reguladoras de Ácido Nucleico , Transformação Genética , Plantas Geneticamente Modificadas/genéticaRESUMO
Magnetic topological materials have drawn markedly attention recently due to the strong coupling of their novel topological properties and magnetic configurations. In particular, the MnBi2Te4/(Bi2Te3)n family highlights the researches of multiple magnetic topological materials. Via first-principles calculations, we predict that Mn(Bi, Sb)4Se7, the close relatives of MnBi2Te4/(Bi2Te3)n family, are topological nontrivival in both antiferromagnetic and ferromagnetic configurations. In the antiferromagnetic ground state, Mn(Bi, Sb)4Se7 are simultaneously topological insulators and axion insulators. Massless Dirac surface states emerge on the surfaces parallel to the z axis. In ferromagnetic phases, they are axion insulators. Particularly, when the magnetization direction is along the x axis, they are also topological crystalline insulators. Mirror-symmetry-protected gapless surface states exist on the mirror-invariant surfaces. Hence, the behaviors of surface states are strongly dependent on the magnetization directions and surface orientations. Our work provides more opportunities for the study of magnetic topological physics.
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Polarized structured nitride semiconductors are attractive due to their unique and environment-friendly electronic properties. The stability, ferroelectricity and photocatalytic and photovoltaic properties of super-wurtzite Mg2XN3 (X = Bi, Mo, Nb, Sb, Ta, Tc and W) were determined based on first principles calculations in this study. The calculated results indicate that Mg2XN3 (X = Sb, Ta, Bi and Nb) are stable polar nitrides by phonon frequencies, elastic coefficients and ferroelectric analysis. Mg2XN3 (X = Sb, Ta and Nb) with large ferroelectric polarization strength could absorb ultraviolet light to promote photocatalytic water splitting for hydrogen production. Mg2BiN3 is a new excellent photovoltaic candidate due to its ideal energy band, high electron mobility, high absorption coefficient and large ferroelectric polarization strength.
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Searching for an earth-abundant and environment-friendly absorber for thin-film solar cells that provides similar power conversion efficiency to CdTe and Cu(In,Ga)Se2 is of great importance for large-scale applications. Success would change the world's solar energy supply to an even more sustainable material resource. In this paper, we have studied by first-principles calculations the electronic structure and defect properties of the promising absorber Cu3SbS4. Its electronic properties, like direct band gap, high absorption coefficient, and light carrier effective masses, satisfy the requirements for an absorber except for its somewhat too small band gap energy. Sulfur and copper vacancies are easily formed defects in Cu3SbS4, where the S vacancy shrinks the band gap and degrades the material. This probably explains the experimental findings of a rather poor device performance. The suitable preparation conditions for Cu3SbS4 as an absorber are anticipated to be Cu-poor, Sb-moderate, and S-rich conditions. Herein, isovalent element alloying is demonstrated to be an effective way to increase the gap energy and thereby improve the material properties.
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Manipulating the exchange bias (EB) effect using an electronic gate is a significant goal in spintronics. The emergence of van der Waals (vdW) magnetic heterostructures has provided improved means to study interlayer magnetic coupling, but to date, these heterostructures have not exhibited electrical gate-controlled EB effects. Here, we report electrically controllable EB effects in a vdW heterostructure, FePS3-Fe5GeTe2. By applying a solid protonic gate, the EB effects were repeatably electrically tuned. The EB field reaches up to 23% of the coercivity and the blocking temperature ranges from 30 to 60 K under various gate-voltages. The proton intercalations not only tune the average magnetic exchange coupling but also change the antiferromagnetic configurations in the FePS3 layer. These result in a dramatic modulation of the total interface exchange coupling and the resultant EB effects. The study is a significant step toward vdW heterostructure-based magnetic logic for future low-energy electronics.
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The first metallic glass of Au-Si alloy for over half a century has been discovered, but its atomic structure is still puzzling. Herein, Au8Si dodecahedrons with local five-fold symmetry are revealed as building blocks in Au-Si metallic glass, and the interconnection modes of Au8Si dodecahedrons determine the medium-range order. With dimensionality reduction, the surface ordering is attributed to the motif transformation of Au8Si dodecahedrons into planar Au5Si pyramids with five-fold symmetry, and thus the self-assembly of Au5Si pyramids leads to the formation of the ordered Au2Si monolayer with the lowest energy. Furthermore, structural similarity analysis is performed to unveil the physical origin of the structural characteristics in different dimensions. The amorphism of Au-Si is due to the smooth energy landscape around the global minimum, while the ordered surface structure occurs due to the steep energy landscape.
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Magnetic van der Waals (vdW) materials are poised to enable all-electrical control of magnetism in the two-dimensional limit. However, tuning the magnetic ground state in vdW itinerant ferromagnets by voltage-induced charge doping remains a significant challenge, due to the extremely large carrier densities in these materials. Here, by cleaving the vdW itinerant ferromagnet Fe5GeTe2 (F5GT) into 5.4 nm (around two unit cells), we find that the ferromagnetism (FM) in F5GT can be substantially tuned by the thickness. Moreover, by utilizing a solid protonic gate, an electron doping concentration of above 1021 cm-3 has been exhibited in F5GT nanosheets. Such a high carrier accumulation exceeds that possible in widely used electric double-layer transistors (EDLTs) and surpasses the intrinsic carrier density of F5GT. Importantly, it is accompanied by a magnetic phase transition from FM to antiferromagnetism (AFM). The realization of an antiferromagnetic phase in nanosheet F5GT suggests the promise of applications in high-temperature antiferromagnetic vdW devices and heterostructures.
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ETHNOPHARMACOLOGICAL RELEVANCE: Aconitum carmichaelii Debeaux, a famous traditional medicinal herb for collapse, rheumatic fever, and painful joints, always raises global concerns about its fatal toxicity from toxic alkaloids when improperly processed. Therefore, it is urgent to clarify the internal molecular mechanism of processing detoxification on Aconitum and develop simple and reliable approaches for clinical application, which is also of great significance to the rational medicinal use of Aconitum. AIM OF THE STUDY: The study aimed at developing a complete molecular mechanism exploration strategy in complex medicinal herb decocting system, clarifying the internal molecular mechanism of processing detoxification on Aconitum, and exploring valid approaches for detoxification. MATERIALS AND METHODS: Aconiti Lateralis Radix Praeparata (Fuzi) was selected as the model for exploring the complex Aconitum detoxification mechanism using an advanced online real-time platform based on extractive electrospray ionization mass spectrometry. The methods realized the sensitive capture of dynamic trace intermediates, accurate qualitative and quantitative analysis, and real-time and long-term monitoring of multi-components with satisfactory accuracy and resistance to complex matrices. RESULTS: Components in the complex Aconitum decocting system were real-timely characterized and fat meat was discovered and verified to directionally detoxify Aconitum while reserving the therapy effect. More importantly, the dynamic detoxification mechanism in the chemically complex Aconitum decoction was molecularly profiled. A novel reaction pathway based on nucleophilic substitution reaction mechanism was proposed. As confirmed by the theoretic calculations at DFT B3LYP/6-31G (d) levels, fatty acids (e.g., palmitic acid) acted as a green, cheap, and high-performance catalyst and promote the decomposition of toxic diester alkaloids to non-toxic and active benzoyl-monoester alkaloids through the discovered mechanism. CONCLUSION: The study exposed a novel detoxification molecular mechanism of Aconitum and provided an effective method for the safe use of Aconitum, which could effectively guide the development of traditional processing technology and compatibility regulation of the toxic herb and had great value to the modernization and standardization development of traditional medicine.
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Alcaloides/análise , Diterpenos/análise , Medicamentos de Ervas Chinesas/análise , Espectrometria de Massas por Ionização por Electrospray/métodos , Alcaloides/química , Alcaloides/toxicidade , Diterpenos/química , Diterpenos/toxicidade , Medicamentos de Ervas Chinesas/química , Medicamentos de Ervas Chinesas/toxicidade , Ácidos Graxos/metabolismo , Reprodutibilidade dos TestesRESUMO
ETHNOPHARMACOLOGICAL RELEVANCE: The genus Viscum comprises approximately 100 species that are mainly distributed across Africa, Asia and Europe. The extracts and preparations of Viscum species are widely used as common complementary and alternative medicines in the treatment of rheumatism and cancer. AIM OF THE REVIEW: This review aims to explore the medicinal properties of twelve species belonging to the genus Viscum for potential therapeutic applications. MATERIALS AND METHODS: We collected online information (including PubMed, CNKI, Google Scholar, and Web of Science) from January 1915 to April 2021 and knowledge from classical books on Chinese herbal medicines available for 12 species of the genus Viscum, including Viscum coloratum (Kom.) Nakai, Viscum album L., Viscum articulatum Burm. f., Viscum liquidambaricola Hayata, Viscum ovalifolium DC., Viscum capitellatum Sm., Viscum cruciatum Sieber ex Boiss., Viscum nudum Danser, Viscum angulatum B.Heyne ex DC., Viscum tuberculatum A.Rich., Viscum multinerve Hayata, and Viscum diospyrosicola Hayata. RESULTS: At least 250 different compounds have been reported across twelve Viscum species, including amino acid and peptides, alkaloids, phenolic acids, flavonoids, terpenoids, carbohydrates, fatty acids, lipids, and other types of compounds. In particular, for Viscum coloratum (Kom.) Nakai and Viscum album L., the plants, preparations, and bioactive components have been thoroughly reviewed. This has allowed to elucidate the role of active components, including lectins, viscotoxins, flavonoids, terpenoids, phenolic acids, and polysaccharides, in multiple bioactivities, such as anti-cancer, anti-rheumatism arthralgia, anti-inflammation, anti-cardiovascular diseases, enhancing immunity, and anti-chemotherapy side effects. We also evaluated quality control methods based on active compounds, in vivo exposure compounds, and discriminated chemical markers. CONCLUSIONS: This is the first report to systematically review the pharmaceutical development history, chemical composition, clinical evidence, pharmacological activity, discriminated chemical markers, in vivo exposure, and quality control on twelve distinct species of Viscum plants with medicinal properties. The significant safety and efficacy, along with the minor side effects are constantly confirmed in clinics. The genus Viscum is thus an important medicinal resource that is worth exploring and developing in future pharmacological and chemical studies.
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Compostos Fitoquímicos/farmacologia , Extratos Vegetais/farmacologia , Viscum/química , Animais , Etnofarmacologia , Humanos , Medicina Tradicional/métodos , Compostos Fitoquímicos/isolamento & purificação , Extratos Vegetais/efeitos adversosRESUMO
Ferromagnetism in all-boron planar clusters is revealed based on high-throughput first-principles calculations. Magnetic boron clusters induced from p electrons have been confirmed with large spins, e.g., S = 3 in a B34 cluster, which can be assembled to construct all-boron ferromagnetic monolayers. Notably, the ferromagnetic semiconductors of boron monolayers can be designed with the hybridization of a nonmagnetic B36 cluster in experimental synthesis. The ferromagnetism-paramagnetism transition and semiconductor-metal transition in these boron nanostructures will occur around 500 K according to ab initio molecular dynamics simulation, indicating the potential applications in nano-devices at room temperature. The coexisting ferromagnetic and semiconducting properties in boron monolayers are attributed to the unique multicenter bonds together with the modulation of structural symmetry, which might be worth experimental attempts in the future.
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Dirac semimetals associated with bulk Dirac fermions are well known in topological electronic systems. In sharp contrast, three-dimensional (3D) Dirac phonons in crystalline solids are still unavailable. Here we perform symmetry arguments and first-principles calculations to systematically investigate 3D Dirac phonons in all space groups with inversion symmetry. The results show that there are two categories of 3D Dirac phonons depending on their protection mechanisms and positions in momentum space. The first category originates from the four-dimensional irreducible representations at the high symmetry points. The second category arises from the phonon branch inversion, and the symmetry guarantees Dirac points to be located along the high symmetry lines. Furthermore, we reveal that nonsymmorphic symmetries and the combination of inversion and time-reversal symmetries play essential roles in the emergence of 3D Dirac phonons. Our work not only offers a comprehensive understanding of 3D Dirac phonons but also provides significant guidance for exploring Dirac bosons in both phononic and photonic systems.
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Two-dimensional transition metal dichalcogenide MnSe2(2D-MnSe2) with Curie temperature approximate to 300 K has a significant spintronic application on thin-film devices. We demonstrate theoretically a tunable magnetic transition of 2D-MnSe2between anti-ferromagnetic (AFM) metal and ferromagnetic (FM) half metal as strain increasing. Mechanism of that transition involves a competition betweend-p-dthrough-bond andd-ddirect interaction in 2D-MnSe2. Hole doping is an alternative way to enhance the stability of FM coupling. Adsorption (including Li, Na, Cl and F) and vacancy (Mn and Se) studies confirm that the controllable magnetism of 2D-MnSe2is related to both interaction competition and charge doping. Tensile strains can greatly amplify through-bond interaction and exchange parameters, resulting in a sharp increase of Curie temperature.
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The weak interlayer coupling in van der Waals (vdW) magnets has confined their application to two dimensional (2D) spintronic devices. Here, we demonstrate that the interlayer coupling in a vdW magnet Fe_{3}GeTe_{2} (FGT) can be largely modulated by a protonic gate. With the increase of the protons intercalated among vdW layers, interlayer magnetic coupling increases. Because of the existence of antiferromagnetic layers in FGT nanoflakes, the increasing interlayer magnetic coupling induces exchange bias in protonated FGT nanoflakes. Most strikingly, a rarely seen zero-field cooled (ZFC) exchange bias with very large values (maximally up to 1.2 kOe) has been observed when higher positive voltages (V_{g}≥4.36 V) are applied to the protonic gate, which clearly demonstrates that a strong interlayer coupling is realized by proton intercalation. Such strong interlayer coupling will enable a wider range of applications for vdW magnets.
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Two-dimensional boron structures, due to their diverse properties, have attracted great attention because of their potential applications in nanoelectronic devices. A series of TiBn (2 ≤ n ≤ 13) monolayers are efficiently constructed through our motif based method and theoretically investigated through high-throughput first-principles calculations. The configurations are generated based on the motifs of boron dimeric/triangular/quadrilateral fragments and multi-coordinate titanium-centered boron molecular wheels. Besides previously reported TiB4 and TiB9 which were discovered by the global search method, we predict that high symmetry monolayer TiB7 (Cmmm), which is octa-coordinate titanium boride, is dynamically stable. The TiB7 monolayer is a BCS superconductor with a transition temperature Tc of up to 8.3 K. The motif based approach is proved to be efficient in searching stable structures with prior knowledge so that the potentially stable transition metal monolayers can be quickly constructed by using basic cluster motifs. As an efficient way of discovering materials, the method is easily extended to predict other types of materials which have common characteristic patterns in the structure.