Computational Screening of 3 d Transition Metal Atoms Anchored on Defective Graphene for Efficient Electrocatalytic N2 Fixation

The synthesis of ammonia (NH₃) through the electrochemical reduction of molecular nitrogen (N₂) is a promising strategy for significantly reducing energy consumption compared to traditional industrial processes. Herein, we report the design of a series of monovacancy and divacancy defective graphenes decorated with single 3d transition metal atoms (TM@MVG and TM@DVG; TM=Sc−Zn) as electrocatalysts for the nitrogen-reduction reaction (NRR) aided by density functional theory (DFT) calculations. By comparing energies for N₂ adsorption as well as the free energies associated with *N₂ activation and *N₂H formation, we successfully identified V@MVG, with the lowest potential of −0.63 V, to be an effective catalytic substrate for the NRR in an enzymatic mechanism. Electronic properties, including Bader charges, charge density differences, partial densities of states, and crystal orbital Hamilton populations, are further analyzed in detail. We believe that these results help to explain recent observations in this field and provide guidance for the exploration of efficient electrocatalysts for the NRR.     

PROTECTION OF CHLOROPHYLL a BY CAROTENOID FROM PHOTODYNAMIC DECOMPOSITION

Abstract— The order of inhibition of the photooxidation of chlorophyll a in ethanol and ethanol-benzene is as follows: β-carotene, α-tocopherol, benzoquinone, DABCO, menadione, cholesterol and KI. The quenching of singlet oxygen by β-carotene occurs by a collisional quenching mechanism with a diffusion-controlled rate of 1.7 × 10¹⁰ M ^-1 s^-1. Photodecomposition of Chi a is faster in ethanol-D₂O than in ethanol-H₂O. Photoirradiation (660 nm) of the peridinin-Chl a -protein complex, a photosynthetic light-harvesting pigment isolated from marine dinoflagellates, did not show any photo-decomposition of its Chi a in H₂O or D₂O, even after an extended period (12 h) of irradiation. However, the carotenoid, peridinin, in the photosynthetic antenna pigment was photobleached (ca. 10%) during the irradiation. We conclude that the singlet oxygen formed as a result of the Chi photosensitization is immediately quenched by the low-lying triplet state of four peridinin molecules (per Chl a ) bound within the same protein crevice. The carotenoid thus effectively protects Chl a from photodynamic damage, providing a direct proof for the protective role of carotenoids in the photosynthetic pigment complex.     

Development of a peptide inhibitor-based cantilever sensor assay for cyclic adenosine monophosphate-dependent protein kinase

A highly sensitive nanomechanical cantilever sensor assay based on an electrical measurement has been developed for detecting activated cyclic adenosine monophosphate (cyclic AMP)-dependent protein kinase (PKA). Employing a peptide derived from the heat-stable protein kinase inhibitor (PKI), a magnetic bead system was first selected as a vehicle to immobilize the PKI-(5-24) peptide for capturing PKA catalytic subunit and the activity assay was applied for indirectly assessing the binding. Synergistic interactions of adenosine triphosphate (ATP) and the peptide inhibitor with the kinase were then investigated by a solution phase capillary electrophoretic assay, and by surface plasmon resonance technology which involved immobilization of the peptide inhibitor. After systemically evaluated by a homogeneous direct binding assay, the ATP-dependent recognition of the catalytic subunit of PKA by PKI-(5-24) was successfully transferred on to the nanomechanical cantilevers at protein concentrations of 6.6 pM-66 nM, exhibiting much higher sensitivity and wider dynamic range than the conventional activity assay. Thus, direct assessment of activated kinases using the cantilever sensor system functionalized with specific peptide inhibitors holds great promise in analytical applications and clinical medicine.     

Selective Oxidation of Alcohols Using Benzyldimethyltelluronium Dichromate

Selective oxidation of benzylic, allylic, and saturated secondary alcohols to the corresponding aldehydes or ketones by benzyldimethyltelluronium dichromate is described.     

“Super microcapsules” (SMC). I. Preparation and characterization of star polymethylene oxide (PEO)?polylactide (PLA) copolymers

A new model of molecular scale microcapsule named “super microcapsule” (SMC) obtained from a star copolymer consisting of hydrophilic and hydrophobic blocks was presented. As a first stage, 3 and 4-arm star polyethylene oxide-polylactide copolymers (s-PEO-PLA) were synthesized by the use of triethanolamine and pentaerythritol and initiating agent, respectively. The block length of PLA and PEO for the copolymers can be controlled by feed and reaction conditions. The molecular weight distributions found to be in the range of 1.3–1.7. The DTA data indicated that the phase separation behavior of s-PEO? PLA copolymers is different from that of linear PEO? PLA copolymers with comparable block length. As a evidence of SMC, the shell-core structure of s-PEO? PLA copolymers in solid state was observed by TEM. The SMC dimensions were estimated to be about 400–1000 Å     

Kinetics of the Reaction of Abstracting Hydrogen from Ethylene by Hydrogen Atom

Hydrogen abstraction reaction, H C2H4 --H2 C2H2 was studied by using A initio SCF method. Ge-ometries were fully optimized at SCF level and energies were computed at STO-3G basis set for reactants and transition state. Vibrational analysis was performed thereupon. Finally, the rate constant calculations were carried out at different temperatures for all range of reaction temperature according to Eyring's sbwlute reaction rate theory. The calculated activation energy is 12. 68 kcal/mol, lower than observed value (H. S kcal/mol) by 1. 82 kcal/mol only. The agreement of the calculated rate constants with the experiments is satisfactory.     

Effect of Calix[4]pyrrole as Addition Reagent on Anions Separation in Capillary Zone Electrophoresis (CZE)

Calixpyrroles, as new macrocyclic receptors, have gain increasing interest in host-guest chemistry. Pioneering work in this area by Sessler and co-workers have evidenced that calix[4]pyrroles are effective anion binding agents and have used for anion binding, sensing and new anion separation technologies1, 2. In this letter, we report that calix[4]pyrroles A, B and C3,4 (Scheme 1) can serve as additives in CZE for the separa- tion of halide ions. Scheme 1 A B C When analyzing anions with…     

对DNA具有识别和断裂功能的金属插入剂的研究

本文详尽介绍了国际上对金属配合物与DNA 以插入方式进行识别和反应的前瞻性的工作,为设计能够与特定序列的DNA 进行识别和反应的金属配合物提供了多种策略。     

Magnetism‐Tunable Oligoacene Dioxide Diradicals: Promising Magnetic Oligoacene‐Like Molecules

Graphene oxide has attracted intense research interest recently because the graphene oxide synthesis route, as a promising alternative for cost‐effective mass production of graphene, has been explored. To further study the oxidation process and possible mechanism and to explore applicability of the oxidized products, we have performed a computational study on three series of oligoacene dioxides, focusing on their structures and electronic properties. Taking 1,5‐dioxidized naphthalene as a starting point, three series of oligoacene dioxides are considered as follows: 1) middle insertion by 1–2 benzene rings; 2) single‐side expansion using 1–2 benzene rings; 3) double‐side expansion using two benzene rings. On the basis of density functional theory and complete active space self‐consistent field (CASSCF) calculations, we reveal that oligoacene dioxides in the middle insertion series have a triplet ground state, whereas those in the single‐side expansion series and the double‐side expansion series have open‐shell broken‐symmetry singlet diradical ground states except for their common origin naphthalene‐1,5‐dioxide whose ground state is triplet and which is also viewed as the origin of the middle insertion series. Magnetic coupling interactions of these oligoacene dioxides are also determined. This work should help people toward an atomistic understanding of the electronic structures and properties of possible intermediates or products and even the oxidation mechanism of graphene sheets, and provides a reasonable strategy of designing novel graphene‐oxide‐based magnetic materials.     

A One‐Pot Organometallic Route from a 4‐Alkenylpyridine to a 4,4‐Spiro‐Linked Ethyl 1,4‐Dihydropyridine‐1‐carboxylate

In a one‐pot process without isolation of intermediates, (but‐3‐en‐1‐yl)pyridine ( 13 ) is treated sequentially with dicyclohexylborane, trimethylaluminium, and ethyl carbonochloridate yielding ethyl 1,4‐dihydro‐4,4‐(tetramethylene)pyridine‐1‐carboxylate (=ethyl 8‐azaspiro[4.5]deca‐6,9‐diene‐8‐carboxylate; 2 ) in 46% yield based on starting alkenylpyridine 13 (Scheme 5).