Understanding the catalytic role of flexible chiral δ-amino alcohols: the 1-(2-aminoethyl)norbornan-2-ol model

An empiric first approach to the knowledge about the structural factors influencing the catalytic behavior of conformationally flexible δ-amino-alcohol-based ligands, for the enantioselective addition of dialkylzincs to prochiral carbonyl groups, has been applied using the 1-(2-aminoethyl)norbornan-2-ol moiety as the model chiral system, and the asymmetrically catalyzed addition of diethylzinc to benzaldehyde as the test reaction. For this purpose, a selected small library of seven norbornane-based chiral ligands, bearing well-defined structural variations to allow a comparative study, that is, variation of the relative configuration and steric hindrance at the C(2), C(3) and/or C(7) norbornane positions, has been synthesized and probed in the mentioned test reaction. The experimental results obtained have been rationalized empirically using diastereomeric Noyori-like transition states, demonstrating that the conformational flexibility of the δ-amino-alcohol ligands, contrary to the more studied and rigid β-amino-alcohols, plays a crucial role on the catalytic behavior of such ligands (stereochemical sense and degree of the stereodifferentiation in the asymmetric process), which makes such structural factors, important for the improved design of new related chiral catalysts. In this sense, a robust crude empirical model for the prediction of the catalytic behavior of such δ-amino-alcohol-based ligands is proposed.     

Volumes of activation for dissociation of pentacyanoferrates(II) through pressure and salt effects on reactivity

Summary Dependences of rate constants on pressure (up to 1 kbar) and on added salt concentration (up to 6.0 mol dm^–3 LiNO₃, NaNO₃, NaCl, Na₂SO₄ or KNO₃) have been established for dissociative substitution of pentacyanoferrates(II), [Fe(CN)₅L]^3– with L = 4-cyanopyridine, 4,4-bipyridyl, 4-phenylpyridine and 4-t-butylpyridine. Activation volumes derived directly from pressure effects, and indirectly from salt effects via surface tension dependences and derived surfaces of activation, are reported, compared and discussed.     

Comprehensive study of the methyl effect on the solvolysis rates of bridgehead derivatives

The effect of a bridgehead methyl group on the hydride ion affinity in the gas phase of bicyclo[1.1.1]pent-1-yl (1+), 1-norbornyl (3+), cubyl (5+), 1-adamantyl (7+), bicyclo[2.2.2]oct-1-yl (9+),and bicyclo[3.1.1]hept-1-yl (11+) cations has been studied using density functional theory and ab initio methods. It is concluded that the methyl group always increases the stability of the substituted cations. The effect of the solvent on the stability of methyl-substituted cations in relation to the unsubstituted cations has been studied using the polarizable continuum model of the self-consistent reaction field theory. In the case of rearranging cations, the nucleophilic assistance of the solvent is determined by means of the interaction energy of the corresponding water complexes. It is concluded that the solvent causes the relative stabilization of the parent cations. As a consequence, most of the methyl-substituted bridgehead derivatives show a lower solvolysis rate than the corresponding unsubstituted compounds. A nonqualitative explanation of the methyl effect on the relative stability of bridgehead cations in both gas phase and solution is given for the first time. The ratios of solvolysis products in the case of rearranging bridgehead cations have also been computed from the relative stability of the intermediate water complexes.     

A comparative investigation of the fatty acid compositions of the seeds of a number of lines of a genetic collection of Gossypium hirsutum

A comparative analysis has been made of the amounts of lipids and their fatty-acid compositions in the seeds of the lines of agenetic collection of cotton plants of the speciesGossypium hirsutum and their hybrids and the variety Tashkent-1. The results obtained on the fatty-acid compositions of some hybrids make it possible to recommend the use of individual lines of cotton plants as donors for improving the food-value indices of cottonseed oil.Institute of Chemsitry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. V. I. Lenin Tashkent State University. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 173–176, March–April, 1991.     

Growth of ZIF-8 MOF Films with Tunable Porosity by using Poly (1-vinylimidazole) Brushes as 3D Primers

This work reports on a novel and versatile approach to control the structure of metal–organic framework (MOFs) films by using polymeric brushes as 3D primers, suitable for triggering heterogeneous MOF nucleation. As a proof-of-concept, this work explores the use of poly(1-vinylimidazole) brushes primer obtained via surface-initiated atom transfer radical polymerization (SI-ATRP) for the synthesis of Zn-based ZIF-8 MOF films. By modifying the grafting density of the brushes, smooth porous films were obtained featuring inherently hydrophobic microporosity arising from ZIF-8 structure, and an additional constructional interparticle mesoporosity, which can be employed for differential adsorption of targeted adsorbates. It was found that the grafting density modulates the constructional porosity of the films obtained; higher grafting densities result in more compact structures, while lower grafting density generates increasingly inhomogeneous films with a higher proportion of interparticle constructional porosity.     

Generation of NOON States in Waveguide Arrays

A method to generate NOON states with three photons by injecting photons in an array of three waveguides is presented. Conditional measurements project the wave function in a given (desired) state. In passing, it is shown how the array of three waveguides, that effectively reproduces the interaction of three fields, may be reduced to the interaction of two fields.     

Stabilization of superparamagnetic nickel nanoparticles in a sepiolite matrix

Superparamagnetic nickel-rich nanoparticles at room temperature have been obtained in a silicate matrix (sepiolite) by a chemical route. During the synthesis process, the control of the acid treatment of the matrix allows nickel cations being incorporated in different locations, into the octahedral site of the structural channels or being deposited onto the sepiolite surface. Thus, two different types of nickel nanoparticles have been obtained depending on the nature of the acid attack: small (~7 nm) and embedded superparamagnetic, or large (~27 nm) deposited single domain nickel nanoparticles for strong or weak acid attack, respectively. Moreover, the embedded nanoparticles have been revealed to possess a remarkable stability against complete oxidation. According to the usage of characterization techniques (transmission electron microscopy, X-ray diffraction and magnetic measurements), embedded nanoparticles seem to be coated with a non-ferromagnetic coating that hinders the oxygen diffusion.     

“Click” Chemistry Mildly Stabilizes Bifunctional Gold Nanoparticles for Sensing and Catalysis

A large family of bifunctional 1,2,3‐triazole derivatives that contain both a polyethylene glycol (PEG) chain and another functional fragment (e.g., a polymer, dendron, alcohol, carboxylic acid, allyl, fluorescence dye, redox‐robust metal complex, or a β‐cyclodextrin unit) has been synthesized by facile “click” chemistry and mildly coordinated to nanogold particles, thus providing stable water‐soluble gold nanoparticles (AuNPs) in the size range 3.0–11.2 nm with various properties and applications. In particular, the sensing properties of these AuNPs are illustrated through the detection of an analogue of a warfare agent (i.e., sulfur mustard) by means of a fluorescence “turn‐on” assay, and the catalytic activity of the smallest triazole–AuNPs (core of 3.0 nm) is excellent for the reduction of 4‐nitrophenol in water.