Long-range sigma-pi interactions in tetrahydro-4H-thiopyran end-capped oligo(cyclohexylidenes). Photo-electron spectroscopy, ab initio SCF MO calculations, and natural bond orbital analyses

Long-range sigma-pi interactions in tetrahydro4H-thiopyran end-capped oligo(cyclohexylidenes) were identified by He(I) photoelectron spectroscopy (PES) and ab initio RHF/6-31G* calculations. The vertical ionization energies Ivj of the highest occupied molecular orbitals (MO's) were assigned using Koopmans' theorem (Iv,j = -epsilonj) and by correlation with the ionizations of related reference compounds. The experimental (PES) and theoretical (RHF/6-31G*) results are in good agreement. For tercyclohexylidene derivatives which contain two nonconjugated pi-bonds splittings deltaIv,j of the pi-bands in the range from approximately 0.5 to 0.7 eV (delta-epsilonj approximately 0.6 to 0.9 eV). For the bi- and tercyclohexylidene compounds containing two sulfur atoms at their alpha- and omega-end positions the pi-type sulfur lone pair bands [Lppi(S)] split significantly by deltaIvj approximately 0.3 to 0.4 eV (delta-epsilonj approximately 0.3 to 0.4 eV), i.e. sigma-pi interactions over distances of ca. 8 and 12 A, respectively, occur. The magnitude of the interactions and the observed splittings are independent of the anti and syn conformations of the oligo(cyclohexylidene) hydrocarbon skeletons. RHF/6-31G* Natural Bond Orbital analyses reveal that the Hax-C-C-Hax precanonical MO's (PCMO's) centered on the cyclohexyl-type rings are paramount for the relay of the through-bond sigma-pi interactions; no through-space sigma-pi interactions were identified.     

Molecular distribution of some commercial nonylphenol ethoxylates using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Nonylphenol ethoxylates (NPEs) belong to a group of nonionic surfactants that are collectively referred to as alkylphenol ethoxylates (APEs). APEs find widespread use in heavy-duty commercial and household cleaning formulations, shampoos, and industrial processing, i.e. textile manufacture. Their environmental impact depends on the molecular distribution and the extent of their biodegradation in municipal sewage systems, waterways and rivers. We have established two sample preparation methods that have enabled the determination of the molecular distributions of six commercial nonylphenol ethoxylates using matrix-assisted laser desorption/ionization (MALDI) time-of-flight (TOF) mass spectrometry (MS). In both methods, alpha-cyano-4-hydroxycinnamic acid, dissolved in acetonitrile/tetrahydrofuran, was used as the matrix. In one set of experiments, the NPEs were dissolved in an acetonitrile/tetrahydrofuran solvent system prior to mixing with the matrix solution, and the resulting MALDI-TOF mass spectra produced mostly sodiated molecules [M + Na](+). The NPEs, all having the formula 4-(C(9)H(19))-C(6)H(4)-(OCH(2)CH(2))(n)-OH, are Surfonic (R)N-95, N-100, N-102, N-120, N-150 and N-300. Surfonic N-95 and N-100 gave n values of 5-20; Surfonic N-102, N-120, N-150, and N-300 gave n values of 5-21, 5-22, 8-25 and 15-40, respectively. In order to develop a sample preparation method that could be used with less polar NPEs, we dissolved the NPEs (except N-300) in pentane prior to mixing with the matrix solution, and found that the MALDI spectral quality was unaffected by the solvent systems. Copyright 1999 John Wiley & Sons, Ltd.     

Understanding the interactions between artemisinin and cyclodextrins: spectroscopic studies and molecular modeling

Artemisinin extracted from Artemisia annua L. proved to be currently, with its derivatives, the most effective drugs against simple and severe malaria, and is also effective on the chloroquine-resistant forms. The advantageous effect of some cyclodextrins (CDs) on artemisinin solubilization was demonstrated by different authors. The present work aims to confirm the effect of several CDs on artemisinin solubilization and to analyse the complexes formed between these CDs and artemisinin in order to understand their solubilization capacities. In this context, solubility studies, liquid-state NMR spectroscopy (¹H NMR studies and ROESY experiments) as well as theoretical studies (molecular modeling) have been performed. Randomly methylated-βCD, Crysmeb^? and hydroxypropylated-γCD were also found to improve the aqueous solubilization of artemisinin as well as βCD, γCD and hydroxypropylated-βCD whose effects were already demonstrated. The best solubilization ability was found with Crysmeb^?. The spectroscopic studies showed a lot of interactions between artemisinin and all the CDs studied, but mainly outside the cavity. Molecular modeling confirmed that artemisinin and CDs formed non-inclusion complexes.     

Inverse opals of molecularly imprinted hydrogels for the detection of bisphenol A and pH sensing

Inverse opal films of molecularly imprinted polymers (MIP) were elaborated using the colloidal crystal template method. The colloidal crystals of silica particles were built by the Langmuir-Blodgett technique, allowing a perfect control of the film thickness. Polymerization in the interspaces of the colloidal crystal in the presence of bisphenol A (BPA) and removal of the used template provides 3D-ordered macroporous methacrylic acid-based hydrogel films in which nanocavities derived from bisphenol A are distributed within the thin walls of the inverse opal hydrogel. The equilibrium swelling properties of the nonimprinted (NIPs) and molecularly imprinted polymers (MIPs) were studied as a function of pH and bisphenol A concentration, while the molecular structures of the bulk hydrogels were analyzed using a cross-linked network structure theory. This study showed an increase in nanopore (mesh) size in the MIPs after BPA extraction as compared to NIPs, in agreement with the presence of nanocavities left by the molecular imprints of the template molecule. The resulting inverse opals were found to display large responses to external stimuli (pH or BPA) with Bragg diffraction peak shifts depending upon the hydrogel film thickness. The film thickness was therefore shown to be a critical parameter for improving the sensing capacities of inverse opal hydrogel films deposited on a substrate.     

The effect of an electric field on the local stoichiometry of front waves in an ionic chemical system

A model based on an autocatalytic, two-step reaction mechanismincluding two ionic components (of the same charge) and twonon-ionic components, where both reactions are of second orderoverall, is considered when an electric field is applied tothe system. The model is motivated by experimental observationson the iodate-arsenous acid system. The travelling wave equationsare examined first and conditions obtained for the existenceand form of these waves. These conditions are then used to interpretthe results obtained from numerical simulations of the fullsystem. These results display all the main features observedexperimentally, the change in the local stoichiometry and thepossible wave annihilation for sufficiently strong fields. Themodel provides a clear explanation for these features as wellas predicting new features not reported from the experiments.The main one of which is the occurrence of an internal wavepropagating in the reacted part of the system in the directioninduced by the applied field.     

Introduction of a planar defect in a molecularly imprinted photonic crystal sensor for the detection of bisphenol A

This paper reports the preparation of a molecularly imprinted inverse opal hydrogel containing a 2D defect layer, by combining the Langmuir-Blodgett technique and the photonic crystal template method. By coupling the exceptional characteristics of molecularly imprinted polymers, sensitive to the presence of a target molecule, and those of photonic crystals in a single device, we could obtain a defect-embedded imprinted photonic polymer consisting in a three-dimensional, highly-ordered and interconnected macroporous array, where nanocavities complementary to analytes in shape and binding sites are distributed. As a proof of concept, we prepared a three-dimensional macroporous array of poly(methacrylic acid) (PMAA) containing molecular imprints of bisphenol A (BPA) and a planar defect layer consisting in macropores of different size. The optical properties of the resulting inverse opal were investigated using reflection spectroscopy. The defect layer was shown to enhance the sensitivity of the photonic crystal material, opening new possibilities towards the development smart optical sensing devices.     

Octopamine increases the excitability of neurons in the snail feeding system by modulation of inward sodium current but not outward potassium currents

Background  

Although octopamine has long been known to have major roles as both transmitter and modulator in arthropods, it has only recently been shown to be functionally important in molluscs, playing a role as a neurotransmitter in the feeding network of the snail Lymnaea stagnalis. The synaptic potentials cannot explain all the effects of octopamine-containing neurons on the feeding network, and here we test the hypothesis that octopamine is also a neuromodulator.     

The effects of an electric field on an autocatalytic ionic reaction in a system with high ionic strength

The effects of an applied electric field on an ionic autocatalyticreaction with a quadratic rate law are considered, where thereacting species, A⁺ and B⁺, are present in a system which alsoincludes non-reacting species C^- and D⁺. The conditions areestablished under which the general terms which describe theelectric field effects in the reaction-diffusion equations canbe simplified to those used in previous studies, where theseeffects are modelled by linear advection terms. The resultingequations are then studied in detail by first obtaining conditionsfor the existence of travelling waves of permanent form. Thisdiscussion shows that _B, the ratio of the diffusion coefficientsof B⁺ and A⁺, is a critical parameter, with different formsof behaviour arising for _B < 1 and _B > 1. This analysisis augmented by obtaining solutions valid for large times andlarge values of (the dirnensionless applied field). Numericalsolutions of initial-value problems are obtained for a rangeof values of and _B, guided by and interpreted through the analysispreviously obtained. These numerical integrations show the formationof reaction fronts, with the possibility of greatly increasedreaction rates caused by the applied electric field, as wellas propagating electrophoretic fronts in B⁺ being formed incases where a reaction front is also initiated. There is alsothe possibility of separate electrophoretic fronts in A⁺ andB⁺ being formed, which become increasingly separated as timeincreases with the reaction being completely inhibited.