Lithium and aluminium carbamato derivatives of the utility amide 2, 2, 6, 6- tetramethylpiperidide

Insertion of CO2 into the metal-N bond of a series of synthetically-important alkali-metal TMP (2,2,6,6-tetramethylpiperidide) complexes has been studied. Determined by X-ray crystallography, the molecular structure of the TMEDA-solvated Li derivative shows a central 8-membered (LiOCO)2 ring lying in a chair conformation with distorted tetrahedral lithium centres. While trying to obtain crystals of a THF solvated derivative, a mixed carbonato/carbamato dodecanuclear lithium cluster was formed containing two central (CO3)2- fragments and eight O2CTMP ligands with four distinct bonding modes. A bisalkylaluminium carbamato complex has also been prepared via two different methods (CO2 insertion into a pre-formed Al-N bond and ligand transfer from the corresponding lithium reagent) which adopts a dimeric structure in the solid state

Selective gas capture via kinetic trapping

Conventional approaches to the capture of CO_2 by metal-organic frameworks focus on equilibrium conditions, and frameworks that contain little CO_2 in equilibrium are often rejected as carbon-capture materials. Here we use a statistical mechanical model, parameterized by quantum mechanical data, to suggest that metal-organic frameworks can be used to separate CO_2 from a typical flue gas mixture when used under {\em nonequilibrium} conditions. The origin of this selectivity is an emergent gas-separation mechanism that results from the acquisition by different gas types of different mobilities within a crowded framework. The resulting distribution of gas types within the framework is in general spatially and dynamically heterogeneous. Our results suggest that relaxing the requirement of equilibrium can substantially increase the parameter space of conditions and materials for which selective gas capture can be effected.Comment: 12 pages, 10 figure

Evidence for product-specific active sites on oxide-derived Cu catalysts for electrochemical CO2 reduction

Carbon dioxide electroreduction in aqueous media using Cu catalysts can generate many different C2 and C3 products, which leads to the question whether all products are generated from the same types of active sites or if product-specific active sites are responsible for certain products. Here, by reducing mixtures of 13CO and 12CO2, we show that oxide-derived Cu catalysts have three different types of active sites for C–C coupled products, one that produces ethanol and acetate, another that produces ethylene and yet another that produces 1-propanol. In contrast, we do not find evidence of product-specific sites on polycrystalline Cu and oriented (100) and (111) Cu surfaces. Analysis of the isotopic composition of the products leads to the prediction that the adsorption energy of *COOH (the product of the first step of CO2 reduction) may be a descriptor for the product selectivity of a given active site. These new insights should enable highly selective catalysts to be developed

Characterization of a 50kW Inductively Coupled Plasma Torch for Testing of Ablative Thermal Protection Materials Using Non-Air Gases

Thermal protection systems have been a major area of study since the advent of space flight, but recent efforts towards crewed spaceflight missions have placed a new importance on the development of such systems. The 50 kW Inductively Coupled Plasma (ICP) Torch Facility at The University of Texas at Austin allows for rapid testing of high-temperature aerospace materials essential to the development of thermal protection systems in planetary re-entry applications. This ICP Torch Facility has been previously characterized using air as the test gas. However, planets of interest for future exploration have atmospheric compositions that differ from air, so testing heat shield materials in the presence of other gases is critical. To address this disparity between tested and actual environment, the current work characterizes the torch using various combinations of argon, CO2, and N2 by determining its operational range at various power settings, mass flow rates, and mixtures these gases. At each setting, the cold-wall heat flux is also measured to determine the range the torch is able to provide. Measurements indicate that using pure Ar gives the torch the largest operating range with regard to power setting and gas injection mass flow rate, and mixing argon into other gases drastically increases the stable operating range compared to the pure gas. Pure CO2 does not form a stable plasma discharge, but a mixture of 50% argon and 50% CO2 (by mass) provides stable operation up to 40 slpm total gas flow rate with a maximum heat flux of 98 W/cm2. Smaller percentages of CO2 allow the cold-wall heat flux to be increased to 110 W/cm2. Pure N2 forms a stable plasma discharge, but the operating range is very limited, providing stable operation up to 20 slpm total gas flow rate with a maximum heat flux of 110 W/cm2.Aerospace Engineering and Engineering Mechanic

Eigenspectra optoacoustic tomography achieves quantitative blood oxygenation imaging deep in tissues

Light propagating in tissue attains a spectrum that varies with location due to wavelength-dependent fluence attenuation by tissue optical properties, an effect that causes spectral corruption. Predictions of the spectral variations of light fluence in tissue are challenging since the spatial distribution of optical properties in tissue cannot be resolved in high resolution or with high accuracy by current methods. Spectral corruption has fundamentally limited the quantification accuracy of optical and optoacoustic methods and impeded the long sought-after goal of imaging blood oxygen saturation (sO2) deep in tissues; a critical but still unattainable target for the assessment of oxygenation in physiological processes and disease. We discover a new principle underlying light fluence in tissues, which describes the wavelength dependence of light fluence as an affine function of a few reference base spectra, independently of the specific distribution of tissue optical properties. This finding enables the introduction of a previously undocumented concept termed eigenspectra Multispectral Optoacoustic Tomography (eMSOT) that can effectively account for wavelength dependent light attenuation without explicit knowledge of the tissue optical properties. We validate eMSOT in more than 2000 simulations and with phantom and animal measurements. We find that eMSOT can quantitatively image tissue sO2 reaching in many occasions a better than 10-fold improved accuracy over conventional spectral optoacoustic methods. Then, we show that eMSOT can spatially resolve sO2 in muscle and tumor; revealing so far unattainable tissue physiology patterns. Last, we related eMSOT readings to cancer hypoxia and found congruence between eMSOT tumor sO2 images and tissue perfusion and hypoxia maps obtained by correlative histological analysis

The Generation of Successive Unmarked Mutations and Chromosomal Insertion of Heterologous Genes in Actinobacillus pleuropneumoniae Using Natural Transformation

We have developed a simple method of generating scarless, unmarked mutations in Actinobacillus pleuropneumoniae by exploiting the ability of this bacterium to undergo natural transformation, and with no need to introduce plasmids encoding recombinases or resolvases. This method involves two successive rounds of natural transformation using linear DNA: the first introduces a cassette carrying cat (which allows selection by chloramphenicol) and sacB (which allows counter-selection using sucrose) flanked by sequences to either side of the target gene; the second transformation utilises the flanking sequences ligated directly to each other in order to remove the cat-sacB cassette. In order to ensure efficient uptake of the target DNA during transformation, A. pleuropneumoniae uptake sequences are added into the constructs used in both rounds of transformation. This method can be used to generate multiple successive deletions and can also be used to introduce targeted point mutations or insertions of heterologous genes into the A. pleuropneumoniae chromosome for development of live attenuated vaccine strains. So far, we have applied this method to highly transformable isolates of serovars 8 (MIDG2331), which is the most prevalent in the UK, and 15 (HS143). By screening clinical isolates of other serovars, it should be possible to identify other amenable strains

Electrocarboxylation of chloroacetonitrile by a Cobalt(I) complex of terpyridine

The electrocarboxylation of chloroacetonitrile (NC–CH2–ClRCl) mediated by [CoIIL2]2+ (L = terpyridine) was investigated by cyclic voltammetry. Electrochemical studies under argon atmosphere showed that the monoelectronic reduction of [CoIIL2]2+ yielded a Cobalt(I) complex which after the loss of a terpyridine ligand reacted with chloroacetonitrile. The oxidative addition of chloroacetonitrile on [CoIL]+ gave an alkylCobalt(III) complex [R–CoIIIL]2+ which was reduced into an alkylCobalt(II) complex, highly unstable and decomposed into an alkyl anion and a Cobalt(II) complex. Under carbon dioxide atmosphere, Cobalt(I) complex was shown to be unreactive towards CO2 but CO2 insertion was observed in the alkylCobalt(III) complex [R–CoIIIL] 2+ giving probably a CO2 adduct [R–CoIIIL(CO2)]2+. This adduct presented a strong adsorption at the carbon electrode and was reduced at potential less cathodic than the one of alkylCobalt(III) complex. After reduction, the carboxylate RCO2− (NC–CH2–CO2−) was released and a catalytic bielectronic carboxylation of chloroacetonitrile took place. Controlled potential electrolyses confirmed the catalytic process and gave for cyanoacetic acid faradic yields up to 60% under low overpotential conditions

CO2 reduction with protons and electrons at a boron-based reaction center.

Borohydrides are widely used reducing agents in chemical synthesis and have emerging energy applications as hydrogen storage materials and reagents for the reduction of CO2. Unfortunately, the high energy cost associated with the multistep preparation of borohydrides starting from alkali metals precludes large scale implementation of these latter uses. One potential solution to this issue is the direct synthesis of borohydrides from the protonation of reduced boron compounds. We herein report reactions of the redox series [Au(B2P2)] n (n = +1, 0, -1) (B2P2, 9,10-bis(2-(diisopropylphosphino)phenyl)-9,10-dihydroboranthrene) and their conversion into corresponding mono- and diborohydride complexes. Crucially, the monoborohydride can be accessed via protonation of [Au(B2P2)]-, a masked borane dianion equivalent accessible at relatively mild potentials (-2.05 V vs. Fc/Fc+). This species reduces CO2 to produce the corresponding formate complex. Cleavage of the formate complex can be achieved by reduction (ca. -1.7 V vs. Fc/Fc+) or by the addition of electrophiles including H+. Additionally, direct reaction of [Au(B2P2)]- with CO2 results in reductive disproportion to release CO and generate a carbonate complex. Together, these reactions constitute a synthetic cycle for CO2 reduction at a boron-based reaction center that proceeds through a B-H unit generated via protonation of a reduced borane with weak organic acids