Studies on outer-sphere electron transfer reactions of surfactant–cobalt(III) complexes with iron(II) in liposome (dipalmitoylphosphotidylcholine) vesicles

The effect of unilamellar vesicles of dipalmitoylphosphotidylcholine (DPPC), both below and above the phase transfer region, on the second-order rate constants for outer-sphere electron transfer between Fe²⁺ and the surfactant?Ccobalt(III) complexes, cis-[Co(en)₂(C₁₂H₂₅NH₂)₂]³⁺ and cis-[Co(trien)(C₁₂H₂₅NH₂)₂]³⁺ (en?=?ethylenediamine, trien?=?triethylenetetramine, C₁₂H₂₅NH₂?=?dodecylamine) was studied by UV?CVis absorption spectroscopy. Below the phase transition temperature of DPPC, the rate decreased with increasing concentration of DPPC, while above the phase transition temperature the rate increased with increasing concentration of DPPC. It is concluded that below the phase transition temperature, there is an accumulation of surfactant?Ccobalt(III) complexes at the interior of the vesicle membrane through hydrophobic effects, and above the phase transition temperature the surfactant?Ccobalt(III) complex is released from the interior to the exterior surface of the vesicle. Through isokinetic plots, we have established that the mechanism of the reaction does not alter during the phase transition of DPPC.     

Electrochemical Behavior of an Anti-Viral Drug Valacyclovir at Carbon Paste Electrode and Its Analytical Application

Valacyclovir (VCH) is an antiviral drug, used in the management of viral infections such as herpes simplex and varicella-zoster in humans. It is rapidly converted to acyclovir which has antiviral activity against herpes simplex virus types 1 (HSV-1) and 2 (HSV-2) and Varicella-zoster virus (VZV) both in vitro and in vivo. Electrochemical behavior was studied using cyclic voltammetric method, and the analytical application was studied using differential pulse voltammetric technique. The process on the surface of electrode was found to be irreversible and diffusion controlled. The charge transfer coefficient, heterogeneous rate constant, the number of electron transferred and activation parameters were calculated. Possible free radical reaction mechanism taking place on the surface of electrode was proposed. Calibration plot constructed using differential pulse voltammetric technique and applied for quantitative analysis in pharmaceutical and human urine sample. Limit of detection (LOD) and limit of quantification (LOQ) were calculated and found to be 0.028 and 0.09 μM, respectively. The present work describes the electrochemical behavior of an antiviral drug, VCH and its determination in pharmaceutical samples. The method shows the development of a sensor for selective and sensitive determination of VCH.     

Synthesis and conformational studies of peptidomimetics containing furanoid sugar amino acids and a sugar diacid

Furanoid sugar amino acids (1) were synthesized and used as dipeptide isosteres to induce interesting turn structures in small linear peptides. They belong to a new variety of designed hybrid structures that carry both amino and carboxyl groups on rigid furanose sugar rings. Four such molecules, 6-amino-2,5-anhydro-6-deoxy-D-gluconic acid (3, Gaa) and its mannonic (4, Maa), idonic (5, Iaa), and a 3,4-dideoxyidonic (6, ddIaa) congeners were synthesized. The synthesis followed a novel reaction path in which an intramolecular 5-exo S(N)2 opening of the hexose-derived terminal aziridine ring in 2 by the gamma-benzyloxy oxygen with concomitant debenzylation occurred during pyridinium dichromate oxidation of the primary delta-hydroxyl group to carboxyl function, leading to the formation of furanoid sugar amino acid frameworks in a single step. Incorporation of these furanoid sugar amino acids into Leu-enkephalin replacing its Gly-Gly portion gave analogues 8-11. Detailed structural analysis of these molecules by circular dichroism (CD) and various NMR techniques in combination with constrained molecular dynamics (MD) simulations revealed that two of these analogues, 8a and 10a, have folded conformations composed of an unusual nine-membered pseudo beta-turn-like structure with a strong intramolecular H-bond between LeuNH --> sugarC3-OH. This, in turn, brings the two aromatic rings of Tyr and Phe in close proximity, a prerequisite for biological activities of opioid peptides. The analgesic activities of 8a,b determined by mouse hot-plate and tail-clip methods were similar to that of Leu-enkephalin methyl ester. The syn disposition of the beta-hydroxycarboxyl motif on the sugar rings appears to be the driving force to nucleate the observed turn structures in some of these molecules (8 and 10). Repetition of the motif on both sides of a furanose ring resulted in a novel molecular design of sugar diacid, 2,5-anhydro-D-idaric acid (7, Idac). Bidirectional elongation of the diacid moieties of 7 with identical peptide strands led to the formation of a C2-symmetric reverse-turn mimetic 12 which displayed a very ordered structure consisting of identical intramolecular H-bonds at two ends between LeuNH --> sugar-OH, the same as in 8 and 10.     

Tactile Response Characterization of a Dynamic System Using Craig-Bampton Method

Vibrational characteristics in small horizontal axis wind turbine system are presented in this study with a system concept called tactile response and substructuring. The main focus is on managing the dynamic properties like vibration, noise, and harshness that occur during the operational mode. Tactile response is defined as the response of subsystem which is induced when a human body touches a vibrating system. Sub structuring is a computational method used to reduce the dynamic behavior of a large complex system with a smaller number of degrees of freedom without disturbing the mesh size of the model. Sub structuring has the ability to combine numerical results along with the experimental results. Combination of substructuring and tactile response is applied in this study. Mode shapes of the system are analyzed and results obtained are correlated within this study to provide better optimization of the results. Wind turbine excited with wind energy depends on wind speed. Torsional vibration has a significant role in determining dynamic properties. Torsional vibration is caused as a result of the rotation of the turbine blade and depends on wind speed. The study gives importance to investigating the ability to simulate the numerical method and tactile response to predict and improve dynamic properties.     

A Nonlinear Generalization of Singular Value Decomposition and Its Applications to Mathematical Modeling and Chaotic Cryptanalysis

In this paper we are going to study the zero location and asymptotic behavior of extremal polynomials with respect to a generalized non-diagonal Sobolev norm in which the product of the function and its derivative appears. The orthogonal polynomials with respect to this Sobolev norm are a particular case of those extremal polynomials. The multiplication operator by the independent variable is the main tool in order to obtain our results.