Tantalum,easy as Pi: understanding differences in metal–imido bonding towards improving Ta/Nb separations

The separation and purification of niobium and tantalum, which co-occur in natural sources, is difficult due to their similar physical and chemical properties. The current industrial method for separating Ta/Nb mixtures uses an energy-intensive process with caustic and toxic conditions. It is of interest to develop alternative, fundamental methodologies for the purification of these technologically important metals that improve upon their environmental impact. Herein, we introduce new Ta/Nb imido compounds: M(^tBuN)(TriNOx) (1-M) bound by the TriNOx³⁻ ligand and demonstrate a fundamental, proof-of-concept Ta/Nb separation based on differences in the imido reactivities. Despite the nearly identical structures of 1-M, density functional theory (DFT)-computed electronic structures of 1-M indicate enhanced basic character of the imido group in 1-Ta as compared to 1-Nb. Accordingly, the rate of CO₂ insertion into the M N_imido bond of 1-Ta to form a carbamate complex (2-Ta) was selective compared to the analogous, unobserved reaction with 1-Nb. Differences in solubility between the imido and carbamate complexes allowed for separation of the carbamate complex, and led to an efficient Ta/Nb separation (S_Ta/Nb = 404 ± 150) dependent on the kinetic differences in nucleophilicities between the imido moieties in 1-Ta and 1-Nb.

A selective separation of the critical metals tantalum and niobium was accomplished from π-bonding-based reactivity differences of imido complexes. New insights into Ta/Nb separations were gained through detailed kinetic and computational studies.     

Conjugates of Iron-Transporting N-Hydroxylactams with Ciprofloxacin

Screening of a library of novel N-hydroxylactams amenable by the Castagnoli-Cushman reaction identified four lead compounds that facilitated ⁵⁵Fe transport into P. aeruginosa cells (one of these synthetic siderophores was found to be as efficient at promoting iron uptake as the natural siderophores pyoverdine, pyochelin or enterobactin). Conjugates of the four lead siderophores with ciprofloxacin were tested for antibacterial activity against P. aeruginosa POA1 (wild type) and the ∆pvdF∆pchA mutant strain. The antibacterial activity was found to be pronounced against the ∆pvdF∆pchA mutant strain grown in CAA medium but not for the POA1 strain. This may be indicative of these compounds being ‘Trojan horse’ antibiotics. Further scrutiny of the mechanism of the antibacterial action of the newly developed conjugates is warranted.     

Quantitative Raman Analysis of Carotenoid Protein Complexes in Aqueous Solution

Carotenoids are naturally abundant, fat-soluble pigmented compounds with dietary, antioxidant and vision protection advantages. The dietary carotenoids, Beta Carotene, Lutein, and Zeaxanthin, complexed with in bovine serum albumin (BSA) in aqueous solution, were explored using Raman spectroscopy to differentiate and quantify their spectral signatures. UV visible absorption spectroscopy was employed to confirm the linearity of responses over the concentration range employed (0.05–1 mg/mL) and, of the 4 Raman source wavelengths (785 nm, 660 nm, 532 nm, 473 nm), 532 nm was chosen to provide the optimal response. After preprocessing to remove water and BSA contributions, and correct for self-absorption, a partial least squares model with R² of 0.9995, resulted in an accuracy of the Root Mean Squared Error of Prediction for Beta Carotene of 0.0032 mg/mL and Limit of Detection 0.0106 mg/mL. Principal Components Analysis clearly differentiated solutions of the three carotenoids, based primarily on small shifts of the main peak at ~1520 cm⁻¹. Least squares fitting analysis of the spectra of admixtures of the carotenoid:protein complexes showed reasonable correlation between norminal% and fitted%, yielding 100% contribution when fitted with individual carotenoid complexes and variable contributions with multiple ratios of admixtures. The results indicate the technique can potentially be used to quantify the carotenoid content of human serum and to identify their differential contributions for application in clinical analysis.     

Yield and quality of bacterial cellulose from agricultural waste

Cellulose - The global abundance and availability of oat hulls make them a promising feedstock to produce a unique type of cellulose, the bacterial one. This is the first study examining how a...     

Magnetohydrodynamic thermochemotherapy and MRI of mouse tumors

A dextran-ferrite magnetic fluid was successfully tested as magnetic resonance imaging (MRI) contrast agent. The same magnetic fluid was then combined with Melphalan, a chemotherapeutic drug, and used for magnetohydrodynamic thermochemotherapy of different tumors. The placement of the tumors in an AC magnetic field led to hyperthermia at 46 °C for 30 min. In combination with tumor slime aspiration, a 30% regression of ∼130 mm³ non-metastatic P388 tumors in BDF₁ mice was reached, together with a life span increase of 290%. The same procedure associated with cyclophosphamide treatment of ∼500 mm³ metastases tumor increased the animal's life span by 180%.     

Energy-efficient dehydrogenation of methanol in a membrane reactor: a mathematical modeling

A two-dimensional non-isothermal stationary mathematical model of the catalytic membrane reactor for the process of methanol dehydrogenation is described. Copper supported on the carbonaceous support was considered as a catalyst. The reaction of methanol dehydrogenation was thermodynamically conjugated with a reaction of hydrogen oxidation taking place in a shell side of the membrane reactor. The effects of various parameters on the methanol conversion and the methyl formate yield have been calculated with the developed model and discussed. Two different types of heating the gas flow were considered and compared. In the case of conjugated dehydrogenation process, the methyl formate yield reaches 77%, when the reactor outer wall was heated up to 150 °C. When the inlet gas flows in the tube and shell sides were heated up to 100 and 83 °C, correspondingly, the yield was 72%.     

Synthesis of N-aminopyrazoles by Fe(II)-catalyzed rearrangement of 4-hydrazonomethyl-substituted isoxazoles

A novel effective method is reported for the preparation of 1-amino-1H-pyrazole-4-carboxylic acid derivatives by Fe(II)-catalyzed rearrangement of isoxazoles having (2,4-dinitrophenylhydrazono)methyl substituent at C4. The reaction proceeds smoothly for both E and Z isomers of 4-(hydrazonomethyl)isoxazoles, and this means it is not necessary to separate mixtures of E/Z-isomers of the hydrazones prepared by reaction of 5-methoxy/pirrolidino-4-carbonylisoxazoles and 2,4-dinitrophenylhydrazine. The rearrangement proceeds via the formation of an aziridine intermediate which can be isolated in certain cases. The 2-nitro group in the synthesized 1-[(2,4-dinitrophenyl)amino]-1H-pyrazole-4-carboxylic esters can be selectively reduced in two steps via acylation of the amino group followed by hydrogenation-deacylation using H₂-Pd/C.     

In situ EPR study of chemoselective hydrogenation of nitroarenes on Au/Al2O3 catalyst

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Hydroxyl-functionalized alkyl-terminated silsesquioxanes as surface modificators of friction geomodifiers

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