Analytical evaluation of lower critical hydrostatic pressure for imperfect cylindrical shells of moderate length

The paper applies generalized power series to determine effectively the lower critical hydrostatic pressure for imperfect cylindrical shells. The basic equations were assumed in the form derived by W.A. Nash. Two variants as regards the number of circumferential half-wavelengths are discussed: m constant during buckling, thus corresponding to upper critical pressure, and m furnishing minimal value of lower critical pressure. It is found that the dependence of lower critical pressure on an imperfection parameter V is linear, i.e. smaller than in the case of the upper critical pressure which decreases with $\text{V}{}^{\mathrm{<mtext>2</mtext><mtext>3</mtext>}}$.     

Microsynthesis of Dianhydrohexitols

Abstract

Conditions have been established for the microsyntheses of dianhydro-hexitols by reaction of 1, 4-monoanhydro-D, L-galactitols and 1, 5-monoanhydro-D-galactitol as well as of 1, 4- and 1, 5-monoanhydro-D-glucitols and -D-mannitols with tosyl chloride in pyridine followed by cyclization of the resulting 6-O-tosyl derivatives in methanolic solution of sodium methoxide. The dianhydrohexitols were formed by intramolecular nucleophilic substitution of the C-6 O-tosyl group with a properly stereochemically oriented hydroxyl group.

Components of the mixtures were separated by capillary gas chromato-graphy using columns coated with SP-2340 and identified by GC-MS. The identities of the synthesized dianhydrohexitols were confirmed by comparison with the GC retention times and mass spectra of authentic samples.     

Direct Synthesis of Amphiphilic α-, β-, and γ-Cyclodextrins

ABSTRACT

The clean one step synthesis of the amphiphilic α-, β-, and γ-cyclodextrins starting from per-(6-bromo-6-deoxy)-α-, -β-, and -γ-cyclodextrins is described. The role of the lipophilic tail is played by various aryl groups (phenyl, p-bromophenyl, p-O-butoxyphenyl, p-pentylphenyl, and o-, m-, and p-nitrophenyl) linked by a thioether bridge to the position C-6 of each glucopyranose unit. The yields of the S-alkylation reactions were very high (85-95%).     

Alkali metal cation complexation by 1,3-alternate,mono-ionisable calix[4]arene-benzocrown-6 compounds

Alkali metal cation extraction behaviour for two series of 1,3-alternate, mono-ionisable calix[4]arene-benzocrown-6 compounds is examined. In Series 1, the proton-ionisable group (PIG) is a substituent on the benzo group of the polyether ring that directs it away from the crown ether cavity. In Series 2, the PIG is attached to one para position in the calixarene framework, thereby positioning it over the crown ether ring. Competitive solvent extraction of alkali metal cations from aqueous solutions into chloroform shows high Cs⁺ efficiency and selectivity. Single-species extraction pH profiles of Cs⁺ for Series 1 and 2 ligands with the same PIG are very similar. Thus, association of Cs⁺ with the calixcrown ring is more important than the position of the PIG relative to the crown ether cavity. Solid-state structures of two unionised ligands from Series 2 are presented. Also described is a crystal containing two different ionised ligand–Cs⁺ complexes.     

Application of reversed-phase high-performance liquid chromatography with fluorimetric detection for simultaneous assessment of global DNA and total RNA methylation in Lepidium sativum: effect of plant exposure to Cd(II) and Se(IV)

In the present work, application of the previously established reversed-phase liquid chromatography procedure based on fluorescent labeling of cytosine and methylcytosine moieties with 2-bromoacetophenone (HPLC-FLD) is presented for simultaneous evaluation of global DNA and total RNA methylation at cytosine carbon 5. The need for such analysis was comprehended from the recent advances in the field of epigenetics that highlight the importance of non-coding RNAs in DNA methylation and suggest that RNA methylation might play a similar role in the modulation of genetic information, as previously demonstrated for DNA. In order to adopt HPLC-FLD procedure for DNA and RNA methylation analysis in a single biomass extract, two extraction procedures with different selectivity toward nucleic acids were examined, and a simplified calibration was designed allowing for evaluation of methylation percentage based on the ratio of chromatographic peak areas: cytidine/5-methylcytidine for RNA and 2´-deoxycytidine/5-methyl-2′-deoxycytidine for DNA. As a proof of concept, global DNA and total RNA methylation were determined in Lepidium sativum hydroponically grown in the presence of different Cd(II) or Se(IV) concentrations, expecting that plant exposure to abiotic stress might affect not only global DNA but also total RNA methylation. The results obtained showed the increase of DNA methylation in the treated plants up to concentration levels 2 mg?L^?1 Cd and 1 mg?L^?1 Se in the growth medium. For higher stressors’ concentration, global DNA methylation tended to decrease. Most importantly, an inverse correlation was found between DNA and RNA methylation levels (r?=??0.6788, p?=?0.031), calling for further studies of this particular modification of nucleic acids in epigenetic context.     

Metal ion extraction by cone p-tert-butylcalix[4]arene-1,3-crown-5 with two N-(X)sulfonyl carbamoylmethoxy side arms and -1,3-monothiacrown-5 analogues

Four cone p-tert-butylcalix[4]arene-1,3-monothiacrown-5 ligands each with two N-(X)sulfonyl carbamoylmethoxy side arms are synthesized for comparison with analogs having only oxygen heteroatoms in the crown ether ring. Solvent extractions of hard alkali metal and alkaline earth metal cations, intermediate Pb²⁺, and soft Hg²⁺ from aqueous solutions into chloroform by these ligands are utilized to probe the effects of sulfur replacement in the crown ether ring on metal ion complexation.     

Intermolecular Interactions and Spectroscopic Signatures of the Hydrogen-Bonded System—n-Octanol in Experimental and Theoretical Studies

n-Octanol is the object of experimental and theoretical study of spectroscopic signatures and intermolecular interactions. The FTIR measurements were carried out at 293 K for n-octanol and its deuterated form. Special attention was paid to the vibrational features associated with the O-H stretching and the isotope effect. Density Functional Theory (DFT) in its classical formulations was applied to develop static models describing intermolecular hydrogen bond (HB) and isotope effect in the gas phase and using solvent reaction field reproduced by Polarizable Continuum Model (PCM). The Atoms in Molecules (AIM) theory enabled electronic structure and molecular topology study. The Symmetry-Adapted Perturbation Theory (SAPT) was used for energy decomposition in the dimers of n-octanol. Finally, time-evolution methods, namely classical molecular dynamics (MD) and Car-Parrinello Molecular Dynamics (CPMD) were employed to shed light onto dynamical nature of liquid n-octanol with emphasis put on metric and vibrational features. As a reference, CPMD gas phase results were applied. Nuclear quantum effects were included using Path Integral Molecular Dynamics (PIMD) and a posteriori method by solving vibrational Schrödinger equation. The latter applied procedure allowed to study the deuterium isotope effect.     

The Lagrange-Newton method for state constrained optimal control problems

Local convergence of the Lagrange-Newton method for optimization problems with two-norm discrepancy in abstract Banach spaces is investigated. Based on stability analysis of optimization problems with two-norm discrepancy, sufficient conditions for local superlinear convergence are derived. The abstract results are applied to optimal control problems for nonlinear ordinary differential equations subject to control and state constraints.This research was completed while the second author was a visitor at the University of Bayreuth, Germany, supported by grant No. CIPA3510CT920789 from the Commission of the European Communities.     

Sensitivity analysis for parametric control problems with control-state constraints

Parametric nonlinear control problems subject to vector-valued mixed control-state constraints are investigated. The model perturbations are implemented by a parameter p of a Banach-space P. We prove solution differentiability in the sense that the optimal solution and the associated adjoint multiplier function are differentiable functions of the parameter. The main assumptions for solution differentiability are composed by regularity conditions and recently developed second-order sufficient conditions (SSC). The analysis generalizes the approach in [16, 20] and establishes a link between (1) shooting techniques for solving the associated boundary value problem (BVP) and (2) SSC. We shall make use of sensitivity results from finite-dimensional parametric programming and exploit the relationships between the variational system associated to BVP and its corresponding Riccati equation.Solution differentiability is the theoretical backbone for any numerical sensitivity analysis. A numerical example with a vector-valued control is presented that illustrates sensitivity analysis in detail.