Investigation of Solution p<Emphasis Type="Italic">K</Emphasis><Subscript>a</Subscript> and Thermodynamic Values of Lamivudine and Pefloxacin Drugs by Ab initio and DFT Methods

In this work we investigate the thermodynamic properties and pK_a value of lamivudine and pefloxacin drugs, in aqueous solutions, by ab initio and density functional theory (DFT) methods at different temperatures. Molecular structures and solute–solvent effects of the anions, cations, and neutral molecules of lamivudine and pefloxacin were studied by the polarizable continuum model (PCM). The calculation was done at the DFT-B3LYP/6-31+G(d) level of theory using Tomasi’s method to analyze the formation of intermolecular hydrogen bonds (IHB) in aqueous solution. The pK_a1 values of lamivudine and pK_a2 values of pefloxacin increase with temperature increase. In contrast, the pK_a1 values of pefloxacin decrease when the temperature increases. Further, the thermodynamic properties of the ionization processes (?H, ?S and ?G) of the drugs in aqueous solution were determined and discussed. The results of this work are in good agreement with the literature data at 298.15 K.     

Effect of low-salinity water on asphaltene precipitation

The effect of low-salinity (1000 to 5000?ppm) and intermediate-salinity (5000 to 40000?ppm) water (MgSO₄, MgCl₂, Na₂SO₄, CaCl₂, NaCl and KCl) on asphaltene precipitation was investigated in this work. The results revealed that all brines intensify the amount of asphaltene precipitation. All cases exhibited initial downward trend followed by the upward trend for the amount of asphaltene precipitation with increasing the brine concentration. A similar trend was also observed for Interfacial Tension (IFT) between crude oil and brine in this study. IFT was tested for MgSO₄, MgCl₂, Na₂SO₄, CaCl₂, NaCl and KCl brines with concentrations of 1000 to 40000?ppm. Finally, experimental results showed that an increase in volume of all brines in the mixture (brine +oil) led to increase and decrease of the asphaltene precipitation in low and intermediate salinity regions, respectively.     

Scanning electrochemical microscopy. 59. Effect of defects and structure on electron transfer through self-assembled monolayers

Electron transfer (ET) rate kinetics through n-alkanethiol self-assembled monolayers (SAMs) of alkanethiols of different chain lengths [Me(CH2)nSH; n=8, 10, 11, 15] on Au and Hg surfaces and ferrocene (Fc)-terminated SAMs (poly-norbornylogous and HS(CH2)12CONHCH2Fc) on Au were studied using cyclic voltammetry and scanning electrochemical microscopy (SECM). The SECM results allow determination of the ET kinetics of solution-phase Ru(NH3)63+/2+ through the alkanethiol SAMs on Au and Hg. A model using the potential dependence of the measured rate constants is proposed to compensate for the pinhole contribution. Extrapolated values of koML for Ru(NH3)63+/2+ using the model follow the expected exponential decay (beta is 0.9) for different chain lengths. For a Fc-terminated poly-norbornyl SAM, the standard rate constant of direct tunneling (ko is 189+/-31 s(-1)) is in the same order as the ko value of HS(CH2)12CONHCH2Fc. In blocking and Fc SAMs, the rates of ET are demonstrated to follow Butler-Volmer kinetics with transfer coefficients alpha of 0.5. Lower values of alpha are treated as a result of the pinhole contribution. The normalized rates of ET are 3 orders of magnitude higher for Fc-terminated than for blocking monolayers. Scanning electron microscopy imaging of Pd nanoparticles electrochemically deposited in pinholes of blocking SAMs was used to confirm the presence of pinholes.     

Tuning Human Serum Albumin (HSA) Hydrogels through Albumin Glycation

The changes of technological properties of albumin-based hydrogels induced by increasing degrees of post-translational modification of the protein are reported. Maillard-type modification of amino acids arginine and lysine of albumin is achieved through glyoxal as an α-dicarbonyl compound. The degrees of modification are fine-tuned using different molar ratios of glyoxal. Hydrogels are thermally induced by heating highly concentrated precursor solutions above the protein's denaturation temperature. While the post-translational modifications are determined and quantified with mass spectrometry, continuous-wave (CW) electron paramagnetic resonance (EPR) spectroscopy shed light on the protein fatty acid binding capacity and changes thereof in solution and in the gel state. The viscoelastic behavior is characterized as a measure of the physical strength of the hydrogels. On the nanoscopic level, the modified albumins in low concentration solution reveal lower binding capacities with increasing degrees of modification. On the contrary, in the gel state, the binding capacity remains constant at all degrees of modifications. This indicates that the loss of fatty acid binding capacity for individual albumin molecules is partially compensated by new binding sites in the gel state, potentially formed by modified amino acids. Such, albumin glycation offers a fine-tuning method of technological and nanoscopic properties of these gels.     

Transgenic Artemisia dubia WALL showed altered phytochemistry and pharmacology

The rol genes have been shown to enhance the production of secondary metabolites in plants. This report examines the effect of trans-genes (rol ABC) on possible high production of biologically important phytochemicals and enhanced pharmacological activities. Three transgenic lines (1, 2 and 3) of Artemisia dubia WALL (transformed with Agrobacterium tumefaciens harboring rol ABC genes) were subjected to phytochemical analysis and pharmacological studies. A great variation in phytochemistry and the pharmacological activities was observed not only between the transgenic and non-transgenic control plants but also among the transgenic lines itself. Comparative chemical profile obtained via HPLC, TLC and spectrophotometry showed high degree of variations in the quantity of phytochemicals. An increased production of total flavonoids (71.1% in transgenic line 2) and total phenolics (110.8% in transgenic line 1), increase in caffeic acid and catechin and a decrease in gallic acid content in the extracts of transformed plants compared to the untransformed control plants was decreased. In case of pharmacological activities, moderate to high level increase in antimicrobial (antibacterial and antifungal) activities, cytotoxicity (14.1%), antitumor (29%) and antioxidant activities (23.9%) was observed (in transgenic line 2). In general all the three transgenic lines under study showed improvement in their pharmacological activities in the order of transgenic line 2 > 1 > 3 > control. The implication of these findings will help to meet the increasing demand of pharmacologically important compounds.     

Silica-bonded S-sulfonic acid as a recyclable catalyst for chemoselective synthesis of 1,1-diacetates

A simple and efficient procedure for the preparation of silica-bonded S-sulfonic acid (SBSSA) by reaction of 3-mercaptopropylsilica (MPS) and chlorosulfonic acid in chloroform is described. This solid acid is employed as a recyclable catalyst for the synthesis of 1,1-diacetates from aromatic aldehydes and acetic anhydride under mild and solvent-free conditions at room temperature.     

Maximal subgroups of <Emphasis Type="Italic">GL</Emphasis><Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>(<Emphasis Type="Italic">D</Emphasis>) with finite conjugacy classes

Let D be an infinite division ring. A famous result due to Herstein says that every non-central element of D has infinitely many conjugates and so, if D ^* is an FC-group, then D is a field. Let M be a maximal subgroup of GL _n (D), where n ≥ 1. In this paper, we prove that if M is an FC-group, then it is the multiplicative group of some maximal subfield of M _n (D). Moreover, if M is algebraic over Z(D), then [D : Z(D)] < ∞.     

Ultrasound assisted preparation of water in oil emulsions and their application in arsenic (V) removal from water in an emulsion liquid membrane process

Water in oil emulsions are prepared by using an ultra-sonication device and used in an emulsion liquid membrane process in order to recover arsenic (V) ions from an aqueous medium. The aim of this work is the investigation of the effect of emulsifier concentration and composition, and also sonication time on the emulsion droplet size and the extraction efficiency in order to obtain stable emulsions with small droplets that favor the extraction. Results show that ultrasonic waves reduce internal droplet size which enhances the extraction of arsenic. In addition, internal droplet size is decreased initially and then increased by increasing Span 80 concentration. On the other hand, by increasing Span 80 concentration, extraction amount is increased and then decreased. Furthermore, emulsifier blends provide more stability for the emulsion. Increasing concentration of Tween 20 as a hydrophilic emulsifier up to an optimum concentration decreases internal droplet size and increases extraction amount. By increasing sonication time up to 4 min, the internal droplet size is decreased and the extraction amount is increased. If sonication time is increased further, the internal droplet size is increased and the extraction amount is decreased.