1,5-asymmetric induction in boron-mediated beta-alkoxy methyl ketone aldol addition reactions

This article presents studies that illustrate beta-alkoxy methyl ketone-derived boron enolates undergo diastereoselective aldol addition to afford the 1,5-anti diol relationship. The stereochemical outcome of this reaction is documented to be general for a variety of beta-alkoxy methyl ketone analogues and aldehyde partners. The double stereodifferentiating reactions of these enolates with chiral beta-alkoxy aldehydes have also been investigated in conjunction with the possibility of controlling the absolute stereochemistry of the aldol process. With the proper selection of reaction conditions, the proximal alkoxy substituent on either the aldehyde (1,3-induction) or the enolate fragment (1,5-induction) can be employed to control facial selectivity of the aldol addition. Selection of a boron enolate ensures dominant 1,5-anti induction from the beta-alkoxy methyl ketone-derived enolate partner while negating any influence of the beta-alkoxy aldehyde substituent. Conversely, if stereochemical control from the beta-alkoxy aldehyde is desired, a Lewis acid-catalyzed enolsilane addition ensures dominant 1,3-induction from the aldehyde beta-oxygen substituent.     

Enabling Aromatic Hydroxylation in a Cytochrome P450 Monooxygenase Enzyme through Protein Engineering

The cytochrome P450 (CYP) family of heme monooxygenases catalyse the selective oxidation of C−H bonds under ambient conditions. The CYP199A4 enzyme from Rhodopseudomonas palustris catalyses aliphatic oxidation of 4-cyclohexylbenzoic acid but not the aromatic oxidation of 4-phenylbenzoic acid, due to the distinct mechanisms of aliphatic and aromatic oxidation. The aromatic substrates 4-benzyl-, 4-phenoxy- and 4-benzoyl-benzoic acid and methoxy-substituted phenylbenzoic acids were assessed to see if they could achieve an orientation more amenable to aromatic oxidation. CYP199A4 could catalyse the efficient benzylic oxidation of 4-benzylbenzoic acid. The methoxy-substituted phenylbenzoic acids were oxidatively demethylated with low activity. However, no aromatic oxidation was observed with any of these substrates. Crystal structures of CYP199A4 with 4-(3′-methoxyphenyl)benzoic acid demonstrated that the substrate binding mode was like that of 4-phenylbenzoic acid. 4-Phenoxy- and 4-benzoyl-benzoic acid bound with the ether or ketone oxygen atom hydrogen-bonded to the heme aqua ligand. We also investigated whether the substitution of phenylalanine residues in the active site could permit aromatic hydroxylation. Mutagenesis of the F298 residue to a valine did not significantly alter the substrate binding position or enable the aromatic oxidation of 4-phenylbenzoic acid; however the F182L mutant was able to catalyse 4-phenylbenzoic acid oxidation generating 2′-hydroxy-, 3′-hydroxy- and 4′-hydroxy metabolites in a 83 : 9 : 8 ratio, respectively. Molecular dynamics simulations, in which the distance and angle of attack were considered, demonstrated that in the F182L variant, in contrast to the wild-type enzyme, the phenyl ring of 4-phenylbenzoic acid attained a productive geometry for aromatic oxidation to occur.     

Unweaving the rainbow: a review of the relationship between single-walled carbon nanotube molecular structures and their chemical reactivity

Single-walled carbon nanotubes (SWNTs) are a fundamental family of distinct molecules, each bearing the possibility of different reactivities due to their intrinsically distinct chemical properties. SWNT syntheses generate a heterogeneous mixture of species with varying electronic character, lengths, diameters and helicities, (n,m), as well as other amorphous, graphitic and metal catalyst impurities. In recent years, selective syntheses and post-synthetic separation strategies have advanced, driven by the requirement for pure SWNTs displaying particular features. Covalent surface modifications are widely-used to adapt SWNTs for specific applications with modified solubility, compatibility and specific functionalities. In many cases, such reactions have been found to be selective, illuminating the fundamentally distinct chemistry of each (n,m) species. This differential reactivity has found immediate utility in facilitating the sorting of nanotubes according to specific diameter, electronic properties and, most importantly, helicity. In this tutorial review, we discuss a wide range of selective reactions, the mechanisms that are thought to govern selectivity, and the challenges of separating, characterising and regenerating the modified SWNTs.     

Characterization of solution-synthesized CdTe and HgTe

We report the characterization of solution-synthesized CdTe and HgTe nanocrystals by X-ray diffraction, transmission electron microscopy, and photoluminescence. Methanol solutions of sodium telluride and cadmium iodide or mercury iodide, respectively, are reacted to precipitate the nanocrystalline metal tellurides, while the sodium iodide byproduct remains in solution. The existence of crystalline CdTe, HgTe, and ternary HgCdTe compounds has been demonstrated by powder X-ray diffraction after a post-synthesis sintering process. Precipitated crystallites from this synthesis were analyzed by transmission electron microscopy, which revealed that crystal diameters can vary from approximately 1 nm to 100 nm and that crystals are stoichiometric within the detection limit of the electron microprobe technique. Narrow size ranges can be selected and investigated due to an in-situ separation process in the electron microscope. Photoluminescence is found at energies above the bulk exciton energy for CdTe and is attributed to near-band-gap recombination which is blue-shifted due to quantum confinement. Both low defect luminescence and dark field imaging suggest a high crystalline quality. A comparative characterization by photoluminescence, transmission electron microscopy, and X-ray diffraction evaluates the effects of heat treatments during and after synthesis.     

Ellipsometry studies of albumin films on tantalum oxide and SiO2

The adsorption of (1) bovine serum albumin in acetate buffer, (2) albumin followed by glutaraldehyde crosslinking, (3) albumin followed by exposure to an albumin/glutaraldehyde solution, and (4) albumin after the surface was subjected to treatment (3), has been studied using Ta oxide/Ta chips and SiO₂/Si wafers as substrates. The films were washed, air dried and measured in air using an automatic laser ellipsometer, 6328 Å. The films formed from treatment (3) and treatment (4) have a lower refractive index and are thicker than films formed from treatment (1) and treatment (2). The adsorption of albumin on SiO₂/Si wafers seems to be slower than that on the Ta oxide/Ta surfaces.     

Miscibility maps for copolymer - copolymer blends: A comparison of theoretical predictions to experimental studies of poly(styrene-co-vinyl phenol) blends with poly(ethylene-co-methyl acrylate)

We report the results of theoretical and experimental studies of random amorphous styrene-co-vinyl phenol (STVPh) copolymer blends with ethylene-co-methyl acrylate (EMA). This work is a natural extension to our recently reported studies of the phase behavior of analogous STVPh blends with an homologous series of poly(n-alkyl methacrylate) homopolymers, where we employed an association model together with parameters obtained from studies of miscible homopolymer blends. Here we emphasize that there is no conceptual difference between the average chemical repeat of a random copolymer and that of an analogous repeat unit of a homopolymer containing the same number and type of functional groups. The theoretically calculated miscibility maps for STVPh - EMA copolymer blends are in outstanding agreement with experiment.     

An infrared spectroscopic study of a hyperbranched,dendrimer-like,polyester and its blends with poly(4-vinyl phenol)

A dendrimer-like hyperbranched polyester is characterized by infrared spectroscopy. By converting and labeling the terminal groups by acetylation with ¹³C acetic anhydride, the relative accessibility of core and terminal functional groups to solvents and linear polymers can be measured by counting the number of hydrogen bonds formed between the complementary functional groups found in these materials. The terminal groups form hydrogen bonds as readily as the same groups in linear polymers, but the core groups are highly screened. These results suggest that in these mixtures the dendrimer is extended, with the terminal groups located near the periphery of the molecule.