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Direct non-oxidative methane conversion (DNMC) has been recognized as a single-step technology that directly converts methane into olefins and higher hydrocarbons. High reaction temperature and low catalyst durability, resulting from the endothermic reaction and coke deposition, are two main challenges. We show that a millisecond catalytic wall reactor enables stable methane conversion, C2+ selectivity, coke yield, and long-term durability. These effects originate from initiation of the DNMC on a reactor wall and maintenance of the reaction by gas-phase chemistry within the reactor compartment. The results obtained under various temperatures and gas flow rates form a basis for optimizing the process towards lighter C2 or heavier aromatic products. A process simulation was done by Aspen Plus to understand the practical implications of this reactor in DNMC. High carbon and thermal efficiencies and low cost of the reactor materials are realized, indicating the technoeconomic viability of this DNMC technology.

Background Mixed matrix membranes (MMM)s for CO2/N2 separation still suffer from interfacial defects. Method To address this, a series of MMMs were prepared using polyethersulfone-g-poly (ethylene glycol) (PES-g-PEG) comb-like copolymer to tune the interfacial interaction with a pillared MFI (PMFI) zeolite nanosheets, which has a hierarchical porous structure to improve permeance. The composite membranes were examined by SEM, EDX and XRD. The dependence of gas permeabilities, diffusion and solubility coefficients of CO2 and N2 were determined by the time-lag method. Results The increase in PMFI zeolite loading led to an increase in the permeability coefficient of CO2, which is mainly caused by the increase in CO2 diffusion coefficient. The CO2/N2 gas separation was optimized at a loading of 20wt% PMFI zeolite, which produces a composite membrane with a CO2 permeability of 66.9 Barrer and an ideal permeability selectivity coefficient of 9.6.

This paper describes the design, characterization, and metal-binding properties of a 32-residue polypeptide called AQ-C16C19. The sequence of this peptide is composed of four repeats of the seven residue sequence Ile-Ala-Ala-Leu-Glu-Gln-Lys but with a Cys-X-X-Cys metal-binding motif substituted at positions 16-19. Size exclusion chromatography with multiangle light scattering detection (SEC-MALS) and circular dichroism (CD) spectroscopy studies showed that the apo peptide exhibits a pH-dependent oligomerization state in which a three-stranded α-helical coiled coil is dominant between pH5.4 and 8.5. The Cd(2+)-binding properties of the AQ-C16C19 peptide were studied by ultraviolet-visible spectroscopy (UV-vis), electrospray ionization mass spectrometry (ESI MS), and (113)Cd NMR techniques. The holoprotein was found to contain a polynuclear cadmium-thiolate center formed within the hydrophobic core of the triple-stranded α-helical coiled-coil structure. The X-ray crystal structure of the Cd-loaded peptide, resolved at 1.85A resolution, revealed an adamantane-like configuration of the polynuclear metal center consisting of four cadmium ions, six thiolate sulfur ligands from cysteine residues and four oxygen-donor ligands. Three of these are from glutamic acid residues and one is from an exogenous water molecule. Thus, each cadmium ion is coordinated in a distorted tetrahedral S(3)O geometry. The metal cluster was found to form cooperatively at pH5.4 but in a stepwise fashion at pH>7. The results demonstrate that synthetic coiled-coils can be designed to incorporate multinuclear metal clusters, a proof-of-concept for their potential use in developing synthetic metalloenzymes and multi-electron redox agents.

The emerging field of metalloprotein design seeks to prepare artificial proteins whose properties can mimic, enhance, and perhaps improve upon many features found in natural metalloenzymes. This review summarizes our recent efforts to prepare synthetic metalloproteins built from alpha-helical coiled-coils and to incorporate electron-transfer functionality within these systems. We have recently designed a cysteine-containing random-coil peptide which forms a alpha-helical coiled-coil upon binding various metals. The CuI adduct can serve as photoinduced electron-transfer agent to exogenous acceptors and undergoes collisional electron-transfer in the inverted Marcus region to various ruthenium ammine acceptors. It is speculated that this unexpected result might be due to the positioning of the CuI cofactor within the hydrophobic core of the protein which prohibits close approach between the donor and acceptor to slow the high driving force reaction rates below the diffusion limit. O campo emergente da engenharia molecular de metaloproteínas visa preparar proteínas artificiais, cujas propriedades podem imitar e talvez até mesmo melhorar várias características encontradas nas metaloenzimas naturais. Este artigo de revisão resume nossos esforços recentes na preparação de metaloproteínas sintéticas, construídas a partir de "coiled-coils" alfa-hélices, e na incorporação de grupos de transferência de elétrons nesses sistemas. Recentemente, concebemos uma cisteína contendo um peptídeo com hélice randômica, o qual forma uma estrutura "coiled-coil" alfa-helicoidal ao se ligar a vários metais. O aduto de CuI pode atuar como agente fotoindutor de transferência de elétrons para receptores exógenos, e transfere elétrons por colisão na região invertida de Marcus para várias aminas de rutênio, as quais atuam como receptores. Especula-se que este resultado inesperado advenha do posicionamento do cofator de CuI no interior da porção hidrofóbica da proteína, o qual proíbe a aproximação entre o doador e o receptor, diminuindo a velocidade de transferência eletrônica daquelas reações termodinamicamente muito favorecidas, para velocidades inferiores à do limite difusional.

The effect of compressed CO2 on the properties of sodium bis(2-ethylhexyl) sulfosuccinate/water/isooctane reverse micelles was investigated by steady-state and time-resolved fluorescence spectrosco...

An intramolecular electron transfer compound (4-(10-cyano-9-anthracenylmethyl)- N , N -dimethylaniline) has been studied under different pressure up to about 6 GPa. The electron transfer (ET) rate constants ( k et ) with pressure have been obtained from its fluorescence emission and decay processes at different pressures. By analogy with the theory of optical transition, the free energy change (Δ G ) and solvent reorganization energy ( λ ) during the ET process can be expressed by the functions including the variable pressure. The experimental results can be understood well by analyzing the influence of Δ G and λ on the k et with pressure.

Combination of reverse micellar solutions and supercritical or compressed carbon dioxide (CO2) is a new and interesting topic. This work conducted the first study on the effect of compressed CO2 on the micro-properties (e.g., micropolarity, ionic strength, pH) of the sodium bis(2-ethylhexyl) sulfosuccinate reverse micelles in isooctane by phase behavior measurement, Fourier transform infrared and UV–vis spectroscopic techniques. The results show that CO2 can dissolve in both the organic-continuous phase and the water cores of the reverse micelles. The properties of the reverse micelles can be tuned continuously by changing the pressure of CO2 because the solubility of CO2 in the solution and in the water cores depends on the pressure. CO2 in the water cores can be ionized to produce HCO3−1 and H+. The micropolarity and ionic strength of the water cores increase with the pressure of CO2. Accordingly, the pH is reduced as the pressure and water-to-surfactant molar ratio (w0) are increased.