Enantioselective Construction of Tertiary Boronic Esters by Conjunctive Cross‐Coupling

Catalytic enantioselective conjunctive cross‐coupling has been developed to construct tertiary alkylboronic esters. These reactions occur with good yield and enantioselectivity for a range of substrates. Mechanistic experiments reveal aspects of the catalytic cycle that allow hindered substrates to react without significant complicating side reactions.     

A hydrocarbon trinegative ion

Experimental values for ¹H and ¹⁹F nuclear shielding anisotropies obtained from solid state, nematic phase, and molecular beam measurements are reviewed. Certain discrepancies are pointed out. An anisotropy operator is defined as a sum of two operators corresponding to the Lamb and high frequency terms. Approximations to the high frequency operator are given. Scales of absolute shielding constants are obtained, so that the magnitudes of the anisotropies can be discussed on the basis of non-empirical and semi-empirical calculations, and of the experimental results. The hypothesis due to Ramsey that the potential is constant for a given nucleus in different molecules is used to obtain approximate values for the Lamb term in the nuclear shielding constant.

The distinction between shielding in large and small molecules is stressed. For the fluoromethanes and fluorobenzene the results of CNDO/2 molecular orbital calculations are used for a qualitative discussion of the anisotropies.     

Design of a High Throughput 25‐Well Parallel Electrolyzer for the Accelerated Discovery of CO2 Reduction Catalysts via a Combinatorial Approach

A combinatorial approach is described for screening homogeneous CO₂ reduction electrocatalysts by means of a high‐throughput 25‐well parallel electrolyzer. Active catalysts were then screened by three methods: (1) the presence of CO gas in the electrolyzer head space; (2) a pH change for the individual solutions before and after bulk electrolysis due to proton consumption during CO₂ reduction; and (3) other physical attributes. Based on these screening methods, two solutions out of the 25 were selected for further study. One out of two selected solutions, nickel cyclam, a well‐known CO₂ reduction electrocatalyst, was correctly identified to be the most active.     

Gas Phase Hydrolysis and Oxo-Exchange of Actinide Dioxide Cations: Elucidating Intrinsic Chemistry from Protactinium to Einsteinium

Gas-phase bimolecular reactions of metal cations with water provide insights into intrinsic characteristics of hydrolysis. For the actinide dioxide cations, actinyl(V) AnO₂⁺, melding of experiment and computation provides insights into trends for hydrolysis, as well as for oxo-exchange between actinyls and water that proceeds by a hydrolysis pathway. Here this line of inquiry is further extended into the actinide series with CCSD(T) computations of potential energy surfaces, for the reaction pathway for oxo-exchange through hydrolysis of nine actinyl(V) ions, from PaO₂⁺ to EsO₂⁺. The computed surfaces are in accord with previous experimental results for oxo-exchange, and furthermore predict spontaneous exchange for CmO₂⁺, BkO₂⁺, CfO₂⁺ and EsO₂⁺, but not for AmO₂⁺. Natural Bond Order analysis of the species involved in both hydrolysis and oxo-exchange reveals an inverse correlation between the barrier to hydrolysis and the charge on the actinide centre, q(An). Based on this correlation, it can be concluded that hydrolysis, and related phenomena such as oxo-exchange, become less favourable as the charge on the metal centre decreases. The new results provide a straightforward rationalization of trends across a wide swathe of the actinide series.     

Carrier gas attenuation in gamma assay of radioactive xenon samples

Journal of Radioanalytical and Nuclear Chemistry - Gamma attenuation attributable to xenon and carbon dioxide carrier gas in radioactive xenon assay samples has been calculated using Monte Carlo...     

Retention and selectivity properties of carbamate pesticides on novel polar-embedded stationary phases

This study describes the use of stationary phases with polar functionality suitable for the chemical analysis of carbamates pesticides and comparing with conventional alkyl C8 and C18 phases. The emphasis of this study was to compare the selectivity and retention of the pesticides on different stationary phases, bonded onto 1.7 μm partially porous silica particles under isocratic separation condition. Four stationary phases including: phenylaminopropyl (PAP) phase, bidentate propylurea-C18 (BPUC₁₈), C8 and C18, were successfully bonded on the partially porous silica spheres as evidenced by ²⁹Si and ¹³C solid-state NMR analysis. The phenylaminopropyl phase exhibited smaller retentivity and enhanced selectivity compared to the alkyl C8 phase; the analysis time to run separation of the six carbamate pesticides (i.e., methomyl, propoxur, carbofuran, carbaryl, isoprocarb, and promecarb) on the PAP phase was threefold faster than alkyl C8 phase. In a similar manner, the BPUC₁₈ phase shows similar selectivity to that of the PAP phase, but with longer retentivity; although the BPUC₁₈ phase is characterized with a lesser degree of retentivity for the carbamate pesticides than the conventional alkyl C18 phase. We propose that π–π and weak polar interactions between the carbamate pesticides and the PAP phase dominates the separation mechanism and providing a superior selectivity; faster separation time was also achieved as a result of smaller retentivity. Whereas the C8 and C18 bonded phases exhibits only hydrophobic interactions with the pesticides, leading to larger retentivity. The BPUC₁₈ phase is shown to interact via polar–polar interactions in addition to hydrophobic interactions with the pesticides, providing similar selectivity with the PAP phase but with larger retentivity.     

Partitioning of star branched polymers into pores at three chromatography conditions

The partitioning of star branched polymers into a slit pore at three different chromatography conditions, namely, size exclusion chromatography (SEC), liquid chromatography at the critical condition (LCCC), and liquid adsorption chromatography (LAC) have been investigated with lattice Monte Carlo simulations. Two different chain models are used: random walks (RW) that have no excluded volume interaction and self-avoiding walks (SAW) that have excluded volume interaction. The simulation data obtained for the two chain models are compared to illustrate the effect of excluded volume interactions on the partitioning of star branched polymers. The two most outstanding effects observed due to the introduction of excluded volume interactions are: (i) stars with a high number of arms can be excluded from the pore at condition corresponding to the LCCC of the linear polymers; (ii) the partition coefficient of stars in LAC mode is not dependent only on the total number of monomers on the chain. These effects illustrated by the current study should be taken into account when interpreting experimental chromatography data for branched polymers.     

Dynamic half-Fourier single-shot turbo spin echo for assessment of deep venous thrombosis: initial observations

Objective

The objective of this study was to retrospectively analyze the value of dynamic half-Fourier single-shot turbo spin echo (HASTE) imaging in patients with suspected deep venous thrombosis (DVT).

Materials and Methods

Fifty-five veins in 24 patients were interrogated using a HASTE sequence with the patients relaxed and in various degrees of Valsalva. Veins were analyzed for changes in caliber (+CAL) and signal intensity (+SI) or in their absence (−CAL and −SI, respectively) and compared with the presence of thrombus on gadolinium-enhanced magnetic resonance imaging.

Results

There was no thrombus in veins with the +CAL, +SI pattern (n=40) (P<.01). Five of seven veins (71.4%) with the −CAL, −SI pattern had thrombus (P<.01). A qualitative change in CAL had a sensitivity of 100% and a specificity of 91% for the presence of thrombus. An increase of 1.5 mm in CAL had a sensitivity of 100% and a specificity of 93% for this diagnosis.

Conclusion

Dynamic HASTE imaging offers a physiological method to evaluate veins for deep venous thrombosis.     

Relative rates for the amination of eta3-allyl and eta3-benzyl complexes of palladium

Reactions of nucleophiles with metal-bound hydrocarbyl pi-ligands bound in an eta3-fashion are key steps in a variety of carbon-carbon and carbon-heteroatom bond-forming reactions. To reveal factors that control the rates of reaction of nucleophiles with this type of ligand, the rates of reactions of an aromatic and an aliphatic amine with a series of eta3-allyl, eta3-benzyl, and eta3-phenethyl palladium complexes ligated by the bisphosphine (R)-BINAP to form allylic and benzylic amines were measured. These data showed that the less common addition to an eta3-benzyl complex is faster than the more common addition to an eta3-allyl complex. The relative rates of reaction followed the trend naphthylmethyl > naphthylethyl > benzyl > 1,1-dimethylallyl > allyl. Computational studies suggest that there is a correlation between the amount of positive charge at the site of nucleophilic attack and the rate of C-N bond formation.