DC photoelectric signals from bacteriorhodopsin adsorbed on lipid monolayers and thiol/lipid bilayers supported by mercury

Purple membrane (PM) fragments were adsorbed on a dioleoylphosphatidylcholine (DOPC) monolayer and on a mixed alkanethiol/DOPC bilayer supported by mercury to investigate the kinetics of light-driven proton transport by bacteriorhodopsin (bR). The light-on and light-off capacitive currents on an alkanethiol/DOPC bilayer at pH 6.4 were interpreted on the basis of a simple equivalent circuit. The pH dependence of the biphasic decay kinetics of the light-on currents was analyzed to estimate the pK(a) values for the transitions releasing protons to, and taking up protons from, the solution. The linear dependence of the stationary light-on current of bR on a DOPC monolayer self-assembled on mercury upon the applied potential was interpreted on the basis of an equivalent circuit.     

Electrostatic effect of specifically adsorbed electroinactive ions upon electrode processes: Part VIII. Cu2+ reduction and Cu°(Hg) oxidation in perchloric acid

The effect of the specific adsorption of the ClO₄^? ion upon the kinetics of Cu²⁺ reduction and Cu⁰(Hg) oxidation in aqueous solutions of HClO₄ was investigated using chronocoulometry, d.c., normal pulse, and a.c. polarography. For this purpose three different sets of data for ClO₄^? adsorption were used. In the first set the absolute surface excess of water as reckoned at the outer Helmholtz plane (o.H.p.) was disregarded, in the second set it was accounted for by postulating a complete adsorbed monolayer of water molecules [32], whereas in the third set partial displacement of water molecules from this monolayer by adsorbed ClO₄^? ions was accounted for. Kinetic data were found to the compatible with the latter set, indicating that ClO₄^? adsorption affects the rate-determining step Cu²⁺+e→Cu⁺ only by altering the average electric potential σ_d-effect). The absence of any additional electrostatic effect points out that, in the transition state for Cu²⁺ reduction to Cu⁺, the centre of charge of the reacting particle falls in the proximity of the o.H.p.     

Sulphonium ions: Collision-activated dissociation using fast atom bombardment ionization and a triple quadrupole mass spectrometer

The low-energy collision-activated dissociation of sulphonium cations, including symmetrical trialkyl R³S⁺, dimethylalkyl (CH₃)₂RS⁺, diphenylalkyl Ph₂RS⁺ and cyclic (CH₂)_nS⁺R, has been recorded using fast atom bombardment ionization and a triple quadrupole mass spectrometer. The general trends are easy loss of sulphide to give [R]⁺, except for R ? CH₃, and loss of alkene to give protonated sulphide if β-hydrogens are available. Loss of alkane, generally found in ammonium compounds, is not observed.     

Traceless solid-phase synthesis of bicyclic dihydropyrimidones using multidirectional cyclization cleavage

Solid-phase and solution-phase protocols for the synthesis of furo[3,4-d]pyrimidines, pyrrolo[3,4-d]pyrimidines, and pyrimido[4,5-d]pyridazines are reported. The multistep solid-phase sequence involves the initial high-speed, microwave-promoted acetoacetylation of hydroxymethylpolystyrene resin with methyl 4-chloroacetoacetate. The immobilized 4-chloroacetoacetate precursor was subsequently subjected to three-component Biginelli-type condensations employing urea and a variety of aromatic aldehydes. The resulting 6-chloromethyl-functionalized resin-bound dihydropyrimidones served as common chemical platforms for the generation of the desired heterobicyclic scaffolds using three different traceless cyclative cleavage strategies. The corresponding furo[3,4-d]pyrimidines were obtained by microwave flash heating in a rapid, thermally triggered, cyclative release. Treatment of the chloromethyl dihydropyrimidone intermediates with a variety of primary amines followed by high-temperature microwave heating furnished the anticipated pyrrolo[3,4-d]pyrimidine scaffolds via nucleophilic cyclative cleavage. In a similar way, reaction with monosubstituted hydrazines resulted in the formation of pyrimido[4,5-d]pyridazines. All compounds were obtained in moderate to good overall yields and purities.     

Association of metal cations with alkanes: Na(CH4)+ versus Cu(CH4)+ as molecular models

Summary Ab initio molecular orbital calculations give small stabilization energies for the various Na(CH₄)⁺ adducts (less than 4 kcal mol^–1), but predict a stronger binding for the copper compounds (about 13 kcal mol^–1). The different behaviour of Na⁺ and Cu⁺, already present at the SCF level, is reinforced by electron correlation. This can be attributed to an important contribution of the dispersion energy to the binding energy of the copper ion: about 40% of the total, including basis set superposition corrections.Dedicated to Mrs A. Pullman     

Conformational distribution of a 14-residue peptide in solution: a fluorescence resonance energy transfer study

We demonstrate here that a nitrile-derivatized phenylalanine residue, p-cyanophenylalanine (Phe(CN)), and tryptophan (Trp) constitute a novel donor-acceptor pair for fluorescence resonance energy transfer (FRET). The F?rster distance of this FRET pair was determined to be approximately 16 A and hence is well suited for determining relatively short separation distances. To validate the applicability of this FRET pair in conformational studies, we studied the conformational heterogeneity of a 14-residue amphipathic peptide, Mastoparan X (MPx peptide), in water and 7 M urea solution as well as at different temperatures. Specifically, seven nitrile-derivatized mutants of the MPx peptide, each containing a Phe(CN) residue that replaces different positions along the peptide sequence (i.e., from position 5 to 11) and serves as a resonance energy donor to the native Trp residue at position 3, were studied spectroscopically. The FRET efficiencies obtained from these peptides allowed us to gain a global picture regarding the conformational distribution of the MPx peptide in different environments. Our results suggest that the MPx molecules exist in water as an ensemble of rather compact conformations, with a radius of gyration of approximately 4.2 A, whereas in 7 M urea the radius of gyration increases to approximately 6.5 A, indicating that the peptide conformations become more extended under this condition. However, we found that temperature had only a negligible effect on the size of the MPx peptide, underlining the difference between the thermally and chemically denatured states of polypeptides. The application of the Gaussian chain or the wormlike chain model allowed us to further obtain the probability distribution function of the separation distance between any two residues along the peptide sequence. We found that the effective bond length of the MPx peptide, obtained by using the Gaussian chain model, is 2.78 A in water and 4.28 A in 7 M urea.     

Mixed nests

t-nests witht=((q+1)/2+i) are constructed usingi André nets and (q + 1)/2 regulus nets constructed via a group of order ((q + 1)/2)². The constructed planes obtained using these mixed nests are characterized by the existence of two symmetric homology groups of order (q + 1)/2.The research for this article was partially supported by FONDECYT. This work was done during visits to the University of Iowa in 1993 by the second author and to University of Chile in 1994 by the first author. The authors gratefully acknowledge the support of the Universities of Chile and Iowa.     

Analytical results for 2‐D non‐rectilinear waveguides based on a Green's function

We consider the problem of wave propagation for a 2‐D rectilinear optical waveguide which presents some perturbation. We construct a mathematical framework to study such a problem and prove the existence of a solution for the case of small imperfections. Our results are based on the knowledge of a Green's function for the rectilinear case. Copyright © 2008 John Wiley & Sons, Ltd.     

An Artificial Disc: Chemical and Biomechanical Analysis

Summary: Degeneration of intervertebral discs is the most common cause of back pain. The first phase of this degenerative process involves the nucleus pulposus. A rapid recovery of this structure can prevent further degradation of the annulus fibrosus. Guar Gum is an hydrophilic polysaccharide extracted from the seed endosperm of a plant. Through a cross-linking procedure a Guar hydrogel was synthesized. The Guar hydrogel could be injected by a syringe and it is a good candidate as a nucleus pulposus substitute. For the preparation of the artificial fibrosus annulus, commercially available polymer materials are tuned to achieve suitable mechanical properties. To achieve this peculiar behaviour, the main strategy investigated is the dispersion of hollow polymer micro spheres in a thermoplastic polymer matrix. Processing conditions and particle content are finely tuned to get the target mechanical behaviour.