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[Research about natural detoxification of Traditional chinese medicine that contains aristolochic acidity Any simply by ten microorganisms].
This article reports H-bonding driven supramolecular polymerization of naphthalimide (A)-thiophene (D)-naphthalimide (A) (AD n A, n = 1-4) conjugated ambipolar π-systems and its remarkable impact on room temperature ferroelectricity. Electrochemical studies confirm the ambipolar nature of these AD n A molecules with the HOMO-LUMO gap varying between 2.05 and 2.29 eV. Electron density mapping from ESP calculations reveals intra-molecular charge separation as typically observed in ambipolar systems. In the aggregated state, AD1A and AD2A exhibit bathochromically shifted absorption bands while AD3A and AD4A show typical H-aggregation with a hypsochromic shift. Polarization vs. electric field (P-E) measurements reveal stable room temperature ferroelectricity for these supramolecular assemblies, most prominent for the AD2A system, with a Curie temperature (T c) ≈ 361 K and saturation polarization (P s) of ∼2 μC cm-2 at a rather low coercive field of ∼2 kV cm-1. Control molecules, lacking either the ambipolar chromophore or the amide functionality, do not show any ferroelectricity, vindicating the present molecular and supramolecular design. Computational studies enable structural optimization of the stacked oligomer(s) of AD2A molecules and reveal a significant increase in the macro-dipole moment (in the range of 10-12 Debye) going from the monomer to the oligomer(s), which provides the rationale for the origin of ferroelectricity in these supramolecular polymers.An unprecedented redox-neutral annulation reaction of tertiary anilines with electron-deficient alkynes was developed that proceeds through a cascade Friedel-Crafts alkylation/[1,5]-hydride transfer/Mannich cyclization sequence. Under B(C6F5)3 catalysis, a range of functionalized 1,2,3,4-tetrahydroquinolines were facilely constructed in moderate to good yields with exclusive 3,4-anti-stereochemistry. The commercial availability of the catalyst and the high atom and step economy of the procedure, together with metal-free and external oxidant-free conditions, make this an attractive method in organic synthesis.Here we report a new series of hydrolytically stable chemotype heteroaromatic azoline thioethers (HATs) to achieve highly selective, rapid, and efficient covalent labeling of cysteine under physiological conditions. Although the resulting cysteine-azoline conjugate is stable, we highlight traceless decoupling of the conjugate to afford unmodified starting components in response to reducing conditions. We demonstrated that HAT probes reverse the reactivity of nucleophilic cysteine to electrophilic dehydroalanine (Dha) under mild basic conditions. We demonstrated the umpolung capability of HAT probes for the modification of cysteine on peptides and proteins with various nucleophiles. We demonstrated that HAT probes increase the mass sensitivity of the modified peptides and proteins by 100 fold as compared to the classical methods. Finally, we extended the application of HAT probes for specific modification of cysteines in a complex cell lysate mixture.Expediting the oxygen evolution reaction (OER) is the key to achieving efficient photocatalytic overall water splitting. Herein, single-atom Co-OH modified polymeric carbon nitride (Co-PCN) was synthesized with single-atom loading increased by ∼37 times with the assistance of ball milling that formed ultrathin nanosheets. The single-atom Co-N4OH structure was confirmed experimentally and theoretically and was verified to enhance optical absorption and charge separation and work as the active site for the OER. Co-PCN exhibits the highest OER rate of 37.3 μmol h-1 under visible light irradiation, ∼28-fold higher than that of common PCN/CoO x , with the highest apparent quantum yields reaching 4.69, 2.06, and 0.46% at 400, 420, and 500 nm, respectively, and is among the best OER photocatalysts reported so far. This work provides an effective way to synthesize efficient OER photocatalysts.Plastic ferroelectrics, featuring large entropy changes in phase transitions, hold great potential application for solid-state refrigeration due to the electrocaloric effect. Although conventional ceramic ferroelectrics (e.g., BaTiO3 and KNbO3) have been widely investigated in the fields of electrocaloric material and catalysis, organic plastic ferroelectrics with a high Curie point (T c) are rarely reported but are of great importance for the sake of environmental protection. Here, we reported an organic plastic ferroelectric, (-)-camphanic acid, which crystallizes in the P21 space group, chiral polar 2 (C2) point group, at room temperature. It undergoes plastic paraelectric-to-ferroelectric phase transition with the Aizu notation of 23F2 and high T c of 414 K, showing large entropy gain (ΔS t = 48.2 J K-1 mol-1). More importantly, the rectangular polarization-electric field (P-E) hysteresis loop was recorded on the thin film samples with a large saturated polarization (P s) of 5.2 μC cm-2. check details The plastic phase transition is responsible for its multiaxial ferroelectric feature. This work highlights the discovery of organic multiaxial ferroelectrics driven by the motive of combining chirality and plastic phase transition, which will extensively promote the practical application of such unique functional materials.The activation of dioxygen is the keystone of all forms of aerobic life. Many biological functions rely on the redox versatility of metal ions to perform reductive activation-mediated processes entailing dioxygen and its partially reduced species including superoxide, hydrogen peroxide, and hydroxyl radicals, also known as reactive oxygen species (ROS). In biomimetic chemistry, a number of synthetic approaches have sought to design, synthesize and characterize reactive intermediates such as the metal-superoxo, -peroxo, and -oxo species, which are commonly found as key intermediates in the enzymatic catalytic cycle. However, the use of these designed complexes and their corresponding intermediates as potential candidates for cancer therapeutics has scarcely been endeavored. In this context, a series of biomimetic first-row transition metal complexes bearing a picolylamine-based water-soluble ligand, [M(HN3O2)]2+ (M = Mn2+, Fe2+, Co2+, Cu2+; HN3O2 = 2-(2-(bis(pyridin-2-ylmethyl)amino)ethoxy)ethanol) were synthe2+ resulted in (i) the activation and/or production of ROS species, (ii) the induction of intracellular impaired redox balance, and (iii) the promotion of the mitochondrial apoptotic signaling pathway in colorectal cancer cells. The results have implications for developing novel biomimetic complexes in cancer treatments and for designing potent candidates with cancer-specific antitumor activity.The conventional P2-type cathode material Na0.67Ni0.33Mn0.67O2 suffers from an irreversible P2-O2 phase transition and serious capacity fading during cycling. Here, we successfully carry out magnesium and calcium ion doping into the transition-metal layers (TM layers) and the alkali-metal layers (AM layers), respectively, of Na0.67Ni0.33Mn0.67O2. Both Mg and Ca doping can reduce O-type stacking in the high-voltage region, leading to enhanced cycling endurance, however, this is associated with a decrease in capacity. The results of density functional theory (DFT) studies reveal that the introduction of Mg2+ and Ca2+ make high-voltage reactions (oxygen redox and Ni4+/Ni3+ redox reactions) less accessible. Thanks to the synergetic effect of co-doping with Mg2+ and Ca2+ ions, the adverse effects on high-voltage reactions involving Ni-O bonding are limited, and the structural stability is further enhanced. The finally obtained P2-type Na0.62Ca0.025Ni0.28Mg0.05Mn0.67O2 exhibits a satisfactory initial energy density of 468.2 W h kg-1 and good capacity retention of 83% after 100 cycles at 50 mA g-1 within the voltage range of 2.2-4.35 V. This work deepens our understanding of the specific effects of Mg2+ and Ca2+ dopants and provides a stability-enhancing strategy utilizing abundant alkaline earth elements.Prolonging the lifetime of Cu as a level 1 and level 2 interconnect metal in future nanoelectronic devices is a significant challenge as device dimensions continue to shrink and device structures become more complex. At nanoscale dimensions Cu exhibits high resistivity which prevents its functioning as a conducting wire and prefers to form non-conducting 3D islands. Given that changing from Cu to an alternative metal is challenging, we are investigating new materials that combine properties of diffusion barriers and seed liners to reduce the thickness of this layer and to promote successful electroplating of Cu to facilitate the coating of high-aspect ratio interconnect vias and to allow for optimal electrical conductance. In this study we propose new combined barrier/liner materials based on modifying the surface layer of the TaN barrier through Ru incorporation. Simulating a model Cu29 structure at 0 K and through finite temperature ab initio molecular dynamics on these surfaces allows us to demonstrate how the Ru content can control copper wetting, adhesion and thermal stability properties. Activation energies for atom migrations onto a nucleating copper island allow insight into the growth mechanism of a Cu thin-film. Using this understanding allows us to tailor the Ru content on TaN to control the final morphology of the Cu film. These Ru-modified TaN films can be deposited by atomic layer deposition, allowing for fine control over the film thickness and composition.Benzene imine (1) ⇌ 1H-azepine (2) isomerization occurs through sequential valence and endo-exo isomerism. Quantum chemical and quasiclassical trajectory (QCT) simulations reveal the coupled reaction pathway - ring-expansion followed by N-inversion to the most stable isomer, exo-1H-azepine (Exo-2). Direct-dynamics produce a mixture of endo- and exo-1H-azepine stereoisomers and govern the endo-1H-azepine (Endo-2) ⇌ exo-1H-azepine (Exo-2) ratio. Exo-2 is computationally identified as the most stable product while Endo-2 is fleetingly stable with a survival time (S T) ∼50 fs. N-Methyl substitution exclusively results in an exo-1-methyl-1H-azepine isomer. F-substitution at the N-site increases the barrier for N-inversion and alters the preference by stabilizing Endo-2. Interestingly, the exo-1-fluoro-1H-azepine (minor product) is formed through bifurcation via non-statistical dynamics. A highly concaved Arrhenius plot for 1a → 2a highlights the influence of heavy-atom tunneling on valence isomerism, particularly at low temperatures. Heavy-atom tunneling also results in a normal N-H(D) secondary KIE above 100 K even though the increase in hybridization from sp2 to sp3 at nitrogen should cause an inverse KIE classically.The decarbonylative-coupling reaction is generally promoted by transition metals (via organometallic complexes) or peroxides (via radical intermediates), often at high temperatures to facilitate the CO release. Herein, a visible-light-induced, transition metal and external photosensitizer free decarbonylative addition of benzaldehydes to ketones/aldehydes at room temperature is reported. Tertiary/secondary alcohols were obtained in moderate to excellent yields promoted by using CsF under mild conditions. The detailed mechanistic investigation showed that the reaction proceeded through photoexcitation-decarbonylation of the aldehyde to generate an aromatic anion, followed by its addition to ketones/aldehydes. The reaction mechanism was verified by the density functional theory (DFT) calculations.
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