On the possibility that cyclodextrins' chiral cavities can be available on AOT n-heptane reverse micelles. A UV-visible and induced circular dichroism study

The formation of reverse micelles (RMs) of sodium 1,4-bis(2-ethylhexyl)sulfosuccinate (AOT) in n-heptane including two different beta-cyclodextrin (beta-CD) derivatives (hydroxypropyl-beta-CD, hp-beta-CD, and decenyl succinyl-beta-CD, Mod-beta-CD) is reported. Both cyclodextrins can be incorporated into AOT RMs in different zones within the aggregate, while beta-CD cannot. Using UV-vis and induced circular dichroism (ICD) spectroscopy and different achiral molecular probes (some azo dyes, p-nitroaniline and ferrocene), it was possible to determine that Mod-beta-CD is located with its cavity at the oil side of the AOT RM interface, while for hp-beta-CD the cavity is inside the RM water pool. Among the molecular probes used, methyl orange (MO) was the only one which gave the ICD signal when dissolved in the AOT RMs with hp-beta-CD, so a detailed study of MO behavior in homogeneous media was also performed to compare with the microheterogeneous media. The solvatochromic behavior of the dye depends not only on the polarity of the media but also on other specific solvent properties. A Kamlet-Taft analysis shows that the MO absorption spectrum shifts to longer wavelength with an increase in the solvent polarity-polarizability (pi*) and the hydrogen donor ability (alpha) of the medium. MO appears to be almost 3 times more sensitive to the pi* parameter than to the alpha parameter. In addition, from the MO absorption spectral changes with the hp-beta-CD concentration, the association equilibrium constants in pure water (K11W) and inside the RMs (K11RM) were computed. The results show that K11W is almost 10 times larger than the value inside the RMs. The latter can be explained considering that MO resides anchored to the RM interface through hydrogen bond interaction with the hydration bound water. This study shows for the first time that the cyclodextrin chiral cavity is available for a guest in an organic medium such as the RMs; therefore, we have created a potentially powerful nanoreactor with two different confined regions in the same aggregate: the polar core of the RMs and the chiral hydrophobic cavity of cyclodextrin.     

The Crystal Structure of 3-Epismilagenin Acetate and 23-Oxo-3-epismilagenin Acetate

Abstract  

The crystal structure together with unambiguous assignation of ¹H and ¹³C NMR signals of 3-epismilagenin acetate 4 and 23-oxo-3-epismilagenin acetate 5 are described. Compound 4, crystallized as orthorhombic system a = 10.535(1) ?, b = 13.775 (1) ?, c = 18.347 (1) ?, α = β = γ = 90°; with space group P2 ₁ 2 ₁ 2 ₁ ; while compound 5 crystallized as a monoclinic system a = 10.380(1) ?, b = 7.327(1) ?, c = 17.881(1) ?, α = γ = 90°, β = 99.56(1)°, with a space group P2 ₁ . The presence a carbonyl group at C(23) in compound 5 produces a significant deviation from the chair conformation observed in compound 4. The effects of the side chain modifications on the puckering parameters derived from are discussed.     

Adiabatic parameter dynamics of perturbed solitary waves

The soliton perturbation theory is used to study the solitons that are governed by the generalized Korteweg–de Vries equation in the presence of perturbation terms. The adiabatic parameter dynamics of the solitons in the presence of the perturbation terms are obtained.     

The Mechanical Stability for the Hand-Arm System

The present paper contains a study regarding importance stability in the mechanical systems, mechanical systems are emerging under mechanical vibrations action, it referring especially to the human hand–arm system. Mechanical systems stability is directly influenced of the dumper and the elasticity factors. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structure of compact stars in <Emphasis Type="Italic">R</Emphasis>-squared Palatini gravity

We analyse configurations of neutron stars in the so-called R-squared gravity in the Palatini formalism. Using a realistic equation of state we show that the mass–radius configurations are lighter than their counterparts in General Relativity. We also obtain the internal profiles, which run in strong correlation with the derivatives of the equation of state, leading to regions where the mass parameter decreases with the radial coordinate in a counter-intuitive way. In order to analyse such correlation, we introduce a parametrisation of the equation of state given by multiple polytropes, which allows us to explicitly control its derivatives. We show that, even in a limiting case where hard phase transitions in matter are allowed, the internal profile of the mass parameter still presents strange features and the calculated \(\mathrm{mass}-\mathrm{radius}\) configurations also yield neutron stars lighter than those obtained in General Relativity.     

Modelling of sorbic acid diffusion through bacterial cellulose-based antimicrobial films

Antimicrobial packaging protects the product from the external environment and microbial contamination, conferring numerous advantages on human health. Interest in biopolymers as packaging materials has considerably increased recently. Bacterial cellulose is an interesting biomaterial produced as nanofibrils by Acetobacter xylinium and is a promising candidate due to its remarkable properties. New composite materials with antimicrobial properties were developed in this work, containing poly(vinyl alcohol) (PVA) as polymer matrix and ground bacterial cellulose (BC) as reinforcing fibres. Sorbic acid was used as an antimicrobial agent because it is a preservative recognised in the food industry. The materials obtained were studied using Fourier-transformed infrared spectroscopy (FTIR). The swelling rate of the composites was also measured. Release experiments of sorbic acid from the composite films into water were performed and the mass transfer phenomena were investigated using Fick’s law of diffusion. The antimicrobial effect was tested against Escherichia coli K12-MG1655. The results obtained indicated that the new biocomposite films could be promising antimicrobial food packaging materials.     

Hyper-generalized-gradient functionals constructed from the Lieb-Oxford bound: implementation via local hybrids and thermochemical assessment

In 2009 Odashima and Capelle (OC) showed a way to design a correlation-only density functional that satisfies a Lieb-Oxford bound on the correlation energy, without empirical parameters and even without additional theoretical parameters. However, they were only able to test a size-inconsistent version of it that employs total energies. Here, we show that their alternative size-consistent form that employs energy densities, when combined with exact or semilocal exchange, is a local hybrid (lh) functional. We test several variants of this nonempirical OC-lh functional on standard molecular test sets. Although no variant yields enthalpies of formation with the accuracy of the semilocal Tao-Perdew-Staroverov-Scuseria (TPSS) exchange-correlation, OC-lh correlation with exact exchange yields rather accurate energy barriers for chemical reactions. Our purpose here is not to advocate for a new density functional, but to explore a previously published idea. We also discuss the importance of near-self-consistency for fully nonlocal functionals.     

Vibrating Portable Machine-Tools Acting on Human Operator

This paper will be a short presentation of the specialized literature and international standards about the importance of vibration action of portable machine tools on human body and particularly on the hand-arm system. Exposure to harmful vibrations can lead to health problems and disorders, especially in the upper joints and dorsal region of the human body. A detailed understanding of the undesirable effects of vibration on the human body is essential to achieve administrative and technical prevention. In modern times, vibration studies become more frequent, decisive for the many machines, vehicles and construction. (© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)