Analysis of endoproteinase Arg C action on adrenocorticotrophic hormone by capillary electrophoresis and reversed-phase high-performance liquid chromatography.

The specificity and rate of cleavage of adrenocorticotrophic hormone (ACTH) peptide bonds by endoproteinase Arg C were analyzed using capillary electrophoresis (CE) and reversed-phase (C18) high-performance liquid chromatography (HPLC). Acidic cleavage products were readily resolved by CE in uncoated capillaries using low ionic strength electrolytes. However, products predicted to have a net positive charge greater than 2 or more than 4 positively charged groups per peptide did not migrate out from the capillary at low ionic strength. Addition of salts and zwitterions to the electrolyte decreased capillary-peptide interactions such that all of the ACTH peptides examined were eluted with high efficiency separation by CE. Commercially obtained endoproteinase Arg C preparations exhibited peptidase activity at Lys-15-Lys16 and at Lys16-Arg17 in addition to the expected cleavage at Arg-X bonds. ACTH peptide bond cleavage rates for Arg8-Trp9, Arg17-Arg-18, Lys15-Lys16, and Lys16-Arg17 were 1.46, 0.096, 0.57, and 0.029 mumol min-1 mg-1 respectively. CE separations generally exhibited better resolution and were accomplished in shorter times than C18 HPLC separations. These properties make CE a particularly appropriate method for kinetic analysis of proteolytic enzyme action on peptide substrates.     

Complexes of Co (II) and Cu (II) with nonsteroidal anticancer drug Letrozole and their interaction with DNA and BSA by spectroscopic methods and cytotoxic activity

DNA and BSA binding properties of mononuclear Co (II) and Cu (II) complexes containing letrozole [M(Le)₄Cl₂]·(H2O)](Le=[4,4-(1H-1,2,4-triazol-1-ylmethylene)bisbenzonitrile] have been investigated under physiological conditions. The interaction ability of the two complexes with native calf thymus DNA(CT-DNA) has been monitored as a function of the metal complex-DNA molar ratio by UV–Vis absorption spectrophotometry, fluorescence spectroscopy, circular dichroism(CD) and thermal denaturation studies. The intrinsic binding constants, K_b, of complexes 1 and 2 with CT-DNA, obtained from UV–Vis absorption studies, were 3.15 ± 0.02 × 10⁴ and 4.37 ± 0.02 × 10⁴ M^?1, respectively. The addition of the complexes to CT-DNA (1:2) leads to an increase in the melting temperature of DNA up to around 4 °C, which has revealed that complexes could interact with DNA through intercalation mode. Fluorimetric studies have been performed using methylene blue (MB) as a fluorescence probe and competitive studies have shown the ability of the complexes to displace the DNA-bound MB, suggesting competition with MB. To explore the potential biological value of the complexes, the binding interaction between Co (II) and Cu (II) complexes and bovine serum albumin (BSA) has also been studied by fluorescence spectroscopy. The results indicate that the reaction between the complexes and BSA is a static quenching procedure. The site marker displacement experiment has suggested the location of the complexes binding to BSA at Sudlow’s site I in subdomain IIA. Finally, MTT assay studies have shown that the bioactive complexes exert significantly high selective dose-dependent cytotoxicity against a panel of cancer cell lines including MCF-7, JURKAT, SKOV3 and U87.     

Synthesis of benzo[f]isoindole-4,9-diones

A synthesis of benzo[f]isoindole-4,9-diones 1 is presented starting from the reaction of 2,3-bis(bromomethyl)-1,4-dimethoxynaphthalene 15 with primary amines affording 2,3-bis(aminomethyl)-1,4-dimethoxynaphthalenes 14, which could be converted by CAN-mediated oxidation in one step to benzo[f]isoindole-4,9-diones 1. An alternative synthesis of benzo[f]isoindole-4,9-diones 1 starts from 2,3-bis(bromomethyl)-1,4-naphthoquinone 9 via 2,3-dihydrobenzo[f]isoindoles 10 which spontaneously oxidize.     

Estimates at infinity for positive solutions to a class of p-Laplacian problems in RN

In this paper we consider a class of logistic-type problems for the p-Laplacian in the whole space. Using minimization we prove existence of a positive solution and its behavior at infinity. We also consider questions of uniqueness and sharp estimates at infinity.     

Energy harvesting using semi-active control

This paper presents the application of semi-active control for optimising the power harvested by an electro-mechanical energy harvester. A time-periodic damper, defined by a Fourier series, is introduced for energy harvesting in order to increase the performance of the device. An analytical solution for the transmissibility and the average absorbed power is derived based on the method of harmonic balance. The coefficients of the semi-active model are optimised to maximise the harvested power. The harvested power from the optimum periodic time-varying damper at a particular frequency is compared and is shown to be greater than that from an optimum passive damper and a semi-active on–off damper not only at that particular frequency but also at other frequencies. In addition, the performance of the optimised periodic time-varying damper is also compared with an arbitrary semi-active time-periodic damper, which has the same transmissibility at resonance. An optimisation is carried out to maximise the power in a frequency range and the optimum damper is derived as a function of the excitation frequency. The numerical results are validated with the analytical approach.     

Can anion interaction accelerate transformation of cytosine tautomers? Detailed view form QTAIM analysis

The relative stabilities and noncovalent interactions of the six low-lying energy tautomers of cytosine nucleobase with some biological anions (such as F^?, Cl^?, and CN^?) have been investigated in gas phase by density functional theory (DFT) method in conjunction with 6-311++G (d,p) atomic basis set. Furthermore, to systematically investigate all possible tautomerisms from cytosine induced by proton transfer, we describe a study of structural tautomer interconversion in the gas phase and in a continuum solvent using DFT calculation. We carried out geometrical optimizations with the integral equation formalism of polarizable continuum (IEF-PCM) model to account for the solvent effect, and the results were compared with those in the gas phase. The result of calculation revealed that anions bind mostly in a bidentate manner via hydrogen bond, and stabilization energies of these complexes are larger than those in the case when anions bind in a monodentate manner. The quantum theory of atoms in molecules (QTAIM), natural bonding orbital (NBO) and energy decomposition analysis (EDA) have also been applied to understand the nature of hydrogen bond interactions in these complexes. NBO analysis reveals that the interaction patterns between the anions and the tautomers are ??-type interaction between lone pairs and $ \sigma_{{_{{{\text{N}}--{\text{H}}}} }}^{*} $ , $ \sigma_{{_{{{\text{O}}--{\text{H}}}} }}^{*} $ and $ \sigma_{{_{{{\text{H}}--{\text{F}}}} }}^{*} $ antibonding orbitals. Also, according to these theories, the interactions are found to be partially electrostatic and partially covalent. EDA results identify that these bonds have less than 35% covalent character and more than 65% electrostatic, and the covalent character increases in different anions in the order F^??>?CN^??>?Cl^?. On the other hand, orbital interaction energies of complexes of F^? anion are more than those of Cl^? and CN^? complexes. The lower orbital interaction energies in complexes of Cl^? and CN^?anions imply less charge transfer and stronger ionic bond character. Furthermore, relationship between the orbital interaction energy (E ²) with hydrogen bonding energy (E _H···X) and the electron density (??(r)) with hydrogen bonding energy of F^?, Cl^? and CN^? complexes have also been investigated.     

Interactions of glutathione tripeptide with gold cluster: influence of intramolecular hydrogen bond on complexation behavior

Understanding the nature of the interaction between metal nanoparticles and biomolecules has been important in the development and design of sensors. In this paper, structural, electronic, and bonding properties of the neutral and anionic forms of glutathione tripeptide (GSH) complexes with a Au(3) cluster were studied using the DFT-B3LYP with 6-31+G**-LANL2DZ mixed basis set. Binding of glutathione with the gold cluster is governed by two different kinds of interactions: Au-X (X = N, O, and S) anchoring bond and Au···H-X nonconventional hydrogen bonding. The influence of the intramolecular hydrogen bonding of glutathione on the interaction of this peptide with the gold cluster has been investigated. To gain insight on the role of intramolecular hydrogen bonding on Au-GSH interaction, we compared interaction energies of Au-GSH complexes with those of cystein and glycine components. Our results demonstrated that, in spite of the ability of cystein to form highly stable metal-sulfide interaction, complexation behavior of glutathione is governed by its intramolecular backbone hydrogen bonding. The quantum theory of atom in molecule (QTAIM) and natural bond orbital analysis (NBO) have also been applied to interpret the nature of interactions in Au-GSH complexes. Finally, conformational flexibility of glutathione during complexation with the Au(3) cluster was investigated by means of monitoring Ramachandran angles.