Role of the n+1 amino acid residue on the deamidation of asparagine in pentapeptides

Deamidation plays an important role in biochemical phenomena such as aging. The role of the n + 1 residue on the deamidation of asparagine (asparagine being the nth residue) in three pentapeptide chains (GGNGG, GGNMG and GGNIG) has been analysed with hybrid computational tools. Potentials of mean force at 300 K were calculated from the MD/replica exchange simulations using weighted histogram analysis (WHAM) in explicit water. The snapshots were clustered taking into account the requirements of the plausible deamidation mechanisms, as such the tautomerisation of the asparagine side chain as initial step has been confirmed, based on the proximity of water to the deamidation site. The ultimate goal being to gain an insight on the peptide backbone N-H acidity, quantum mechanical calculations have been carried out. For this purpose, the distribution of Φ/Ψ, Φ₂/Ψ and end-to-end distances deduced from the WHAM diagrams have been considered and a total of 110 structures have been sampled. These neutral pentapeptides as well as their corresponding anions have been optimised (B3LYP/6-31++G(d,p)) in implicit water in order to gain an insight on the peptide backbone N-H acidity. In this study, we have shown that the open conformations of the neutrals and the anions, which display a β sheet like structure are well populated and their pK_as rank in the same order as the deamidating half-lives, that is the peptides that deaminate fastest can more readily access conformations that are more acidic.     

Electrochemical behavior of anthraquinone in aqueous solution in presence of a non-ionic surfactant

Cyclic voltammetric behavior of anthraquinone in aqueous medium has been studied in presence of a non-ionic surfactant, Triton X-100 (TX-100) using sodium salt of anthraquinone-2-sulphonic acid (AQS) as the electro-active species. When cathodic potential is applied, the anthraquinone (AQ) group of AQS is reduced to its dianion. In the reverse scan, the oxidation of AQ²⁻ gives AQ. The electrochemical behavior shows a profound influence from the dissolved state of TX-100 in aqueous media. Spectrophotometric results indicate interaction between AQ and TX-100. A CEC (chemical–electrochemical–chemical) mechanism with the electrochemical reaction coupled with preceding interaction of AQS with TX-100 and following protonation reaction of reduced AQ has been proposed.     

Synthesis and solution properties of a pH‐responsive cyclopolymer of zwitterionic ethyl 3‐(N,N‐diallylammonio)propanephosphonate

The zwitterionic monomer, ethyl 3‐(N,N‐diallylammonio)propanephosphonate, was cyclopolymerized in aqueous solutions using t‐butylhydroperoxide or ammonium persulfate as initiators to afford a polyphosphonobetaine (PPB). The protonation of P(?O)OEtO^– and deprotonation of ? NH⁺ groups in PPB by HCl and NaOH, gave the corresponding cationic polyphosphononic acid (CPP) and anionic polyphosphonate (APP). The presence of two pH‐responsive functionalities in APP has led to establish the equilibria: APP ? PPB ? CPP, the position of which very much dictates the viscosity behavior of its aqueous solution. The PPB demonstrated “antipolyelectrolyte” viscosity behavior; however, in contrast to many polycarbo‐ and polysulfo‐betaines, it was found to be soluble in salt‐free water as well as in salt‐added solutions. Basicity constant (K₁) of the amine group in APP, as determined by potentiometric technique, were found to be “apparent,” and as such followed the modified Henderson‐Hasselbalch equation. The study demonstrated a correlation between the basicity constants and viscosity values. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Synthesis,microwave‐promoted catalytic activity in Suzuki–Miyaura cross‐coupling reactions and antimicrobial properties of novel benzimidazole salts bearing trimethylsilyl group

A mixture of benzimidazole salts (2–7), Pd(OAc)₂ and K₂CO₃ in DMF–H₂O catalyzes the Suzuki–Miyaura cross‐coupling reactions promoted by microwave irradiation resulting in high yield within a short time. In particular, the yield of the Suzuki–Miyaura reactions with aryl bromides was found to be nearly quantitative. The synthesized benzimidazole salts (2–7) were identified by ¹H‐¹³C, NMR, IR spectroscopic methods and microanalysis. The molecular structure of 1 was determined by X‐ray crystallography. The antibacterial and antifungal activities of the novel benzimidazole derivatives (1–7) were also tested against standard strains. Copyright © 2011 John Wiley & Sons, Ltd.     

Comment on “Isobaric (vapour + liquid) equilibria for the (1-propanol + 1-butanol) binary mixture at (53.3 and 91.3) kPa”

The (vapor + liquid) equilibrium values reported by Mohsen-Nia and Memarzadeh appear to be flawed. In particular, neither the reported experimental activity coefficients are consistent with the reported composition data nor the reported model parameters can be used to adequately represent their experimental data.     

Effect of artificial mucus properties on the characteristics of airborne bioaerosol droplets generated during simulated coughing

The effect of viscoelastic properties and surface tension of artificial mucus simulant samples on the size distribution and volume concentration of bioaerosol droplets generated during simulated coughing was investigated through in vitro experiments. The mucus simulant samples had viscoelastic properties in a similar range as those of real human airway mucus. The mucus simulant gels were prepared by mixing various proportions of 0.5–1.7% locust bean gum solution and 0.1 M sodium tetraborate (XLB) solution. Surface tension of one set of samples was varied by adding different amounts of SDS (sodium dodecyl sulfate) surfactant while the measurement of surface tension was performed using ADSA (axisymmetric drop shape analysis) method. The viscoelastic properties of the samples were measured using a Bohlin Gemini 200 HR (Malvern, UK) nano-rheometer with peltier plate assembly. An artificial cough machine was used to simulate human cough, generating aerosol droplets in a model trachea attached to the front of the cough machine. The size distribution and volume concentration of the droplets generated through simulated cough were measured using a laser diffraction particle sizer (SprayTec, Malvern, USA). The surface tension was found to have negligible effect on the characteristic of generated droplets within the range of this investigation. The experimental results showed a decrease in particle size as the samples changed from a viscous fluid type to a viscoelastic to an elastic solid type sample. The volume concentration also changed significantly as the viscoelasticity of the samples was varied.     

Synthesis and characterization of novel antimicrobial cationic polyelectrolytes

Cationic polyelectrolytes containing quaternary nitrogen atoms within the main chain were prepared via condensation polymerization of epichlorhydrin (ECH) with benzyl amine (BA). Polyelectrolytes having different molecular weights were obtained by varying the ECH/BA mole ratio. Cationic polymers were characterized by ¹H-NMR and gel permeation chromatography. The antimicrobial activity of the polymers was tested against bacteria, yeast, and fungi.     

The system of generalized vector equilibrium problems with applications

In this paper, we introduce the system of generalized vector equilibrium problems which includes as special cases the system of generalized implicit vector variational inequality problems, the system of generalized vector variational and variational-like inequality problems and the system of vector equilibrium problems. By using a maximal element theorem, we establish existence results for a solution of these systems. As an application, we derive existence results for a solution of a more general Nash equilibrium problem for vector-valued functions.     

The spherical spectrum of a graded ring

We introduce a functor Sph, the spherical spectrum, which assigns to a graded ringG a space Sph(G) of homogeneous orderings ofG. It combines ideas of concrete geometry in theN-sphere defined by positively homogeneous polynomial equations and inequalities with the abstract notion of the real spectrum of a ring to give a counterpart for real semialgebraic geometry of the functor Proj.     

Photoluminescence spectroscopy of carbon nanotube bundles: evidence for exciton energy transfer

We investigate photoluminescence of nanotube bundles. Their spectra are explained by exciton energy transfer between adjacent tubes, whereby excitation of large gap tubes induces emission from smaller gap ones. The consequent relaxation rate is faster than nonradiative recombination, leading to enhanced photoluminescence of acceptor tubes.