Electrochemical investigations on stability and protonation behavior of pyridine-terminated aromatic self-assembled monolayers

Based on electrochemical methods such as cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), Au(111) electrodes modified by self-assembled monolayers (SAMs) of a homologous series of pyridine-terminated thiols with aromatic backbones have been investigated. An important correlation between the chain structure and film integrity in electrolytic media was found. Monolayers with odd numbers of methylene spacers in the molecular chain showed superior barrier properties compared to even numbered counterparts. A positive influence of an increase in the number of attached phenyl rings on the integrity of SAMs was observed. Furthermore, cathodic desorption of the investigated SAMs is characterized by multiwave desorption peaks and extraordinarily large cathodic charges indicating an unusual desorption process. Moreover, protonation behavior of the SAMs has been investigated by X-ray photoelectron spectroscopy (XPS) and electrochemical methods. Protonation has been found to be reversible and surface pK(a) values have been determined to be around 5 for all investigated monolayers.     

A microfabricated electrical differential counter for the selective enumeration of CD4+ T lymphocytes

We have developed a microfabricated biochip that enumerates CD4+ T lymphocytes from leukocyte populations obtained from human blood samples using electrical impedance sensing and immunoaffinity chromatography. T cell counts are found by obtaining the difference between the number of leukocytes before and after depleting CD4+ T cells with immobilized antibodies in a capture chamber. This differential counting technique has been validated to analyze physiological concentrations of leukocytes with an accuracy of ～9 cells per μL by passivating the capture chamber with bovine serum albumin. In addition, the counter provided T cell counts which correlated closely with an optical control (R(2) = 0.997) for CD4 cell concentrations ranging from approximately 100 to 700 cells per μL. We believe that this approach can be a promising method for bringing quantitative HIV/AIDS diagnostics to resource-poor regions in the world.     

A new enabling technology for convenient laboratory scale continuous flow processing at low temperatures

A new machine for conducting continuous flow processes at low temperatures on a laboratory scale is reported. The use of this cryogenic flow reactor has been demonstrated by the preparation of a variety of (hetero)aromatic boronic acids and esters via lithium halogen exchange chemistry. Furthermore, scale-up of the reaction conditions not only demonstrates the application of this device for the preparation of useful building blocks but also combines the ability to process n-butyllithium directly through pump heads attached to the unit.     

Management of Parthenium hysterophorus (Asteraceae) by Withania somnifera (Solanaceae)

This study was designed to evaluate the herbicidal activity of Withania somnifera (L.) Dunal against the noxious weed parthenium (Parthenium hysterophorus L.). In a laboratory bioassay, the effect of aqueous, methanol and n-hexane shoot and root extracts of 5%, 10%, 15% and 20% w/v concentrations (on a fresh weight basis) of W. somnifera were tested against the germination and seedling growth of parthenium. In general, aqueous and methanol extracts markedly suppressed the germination, root and shoot growth of parthenium. The shoot extracts were more inhibitory than the root extracts. In a foliar spray bioassay, the aqueous and methanol shoot extracts of 10% w/v (on a dry weight basis) concentration were sprayed on 1-week and 2-week-old pot-grown parthenium seedlings. Two subsequent sprays were carried out 5 and 10 days after the first spray. The aqueous and methanol extracts significantly reduced the length and biomass of parthenium shoots. In a soil amendment bioassay, the crushed shoots of W. somnifera were incorporated in the soil at 1-5% w/w. Parthenium seeds were sown one week after the residue incorporation and plants were harvested 40 days after sowing. All the soil amendment treatments significantly reduced seed germination by 43-89%. The highest dosages of 4% and 5% significantly suppressed the root and shoot biomasses of parthenium. This study concludes that foliar spray of aqueous and methanol extracts, and soil amendment with leaf residue of W. somnifera, can control the germination and growth of parthenium, one of the world's worst weeds.     

Comparison of bactericidal activities of silver nanoparticles with common chemical disinfectants

Engineered nanomaterials display significant advantages due to their unique nanostructure, along with their tuneable properties for the designed application. Silver nanoparticles (Ag-NPs) have drawn attention due to their use as potent bactericidal agents and were characterized in this research to provide an understanding of the interaction between nanomaterials and bacteria. This work presents the bactericidal performance of Ag-NPs using Escherichia coli (E. coli) as a model microorganism. Several state-of-the-art techniques, such as high-angle annular dark-field detector in scanning transmission electron microscopy, and energy filtered imaging in electron energy loss spectroscopy, were employed to obtain nanostructural and elemental information. The bactericidal activities of Ag-NPs were then compared with two commonly used disinfectants, sodium hypochlorite (NaClO) and phenol (C(6)H(5)OH). These two chemical disinfectants exhibited rapid bactericidal activity, showing a minimal bactericidal concentration (MBC) of 16 parts-per-million (ppm) and 16 part-per-thousand (ppth), respectively for NaClO and C(6)H(5)OH within about 10 min. In contrast, Ag-NPs exhibit slow but long-term bactericidal effect demonstrating MBCs of 0.6 parts-per-million (ppm) within 6h when used as disinfectant. An advantage using Ag-NPs to inactivate E coli at low dosages is negligible environmental waste or hazardous by-products. The results showed that Ag-NPs caused bacterial inactivation by a mechanism involving several steps, including cell wall and cytoplasmic membrane damage.     

The Effect of Pure Component Characteristic Parameters on Sanchez–Lacombe Equation‐of‐State Predictive Capabilities

The dependence of predictive capabilities of SL EOS on the pure characteristic parameters of monomers and polymers is investigated. A sensitivity analysis study is carried out to understand the effect of these parameters on the predictive capability of SL EOS for different α‐olefin/polyolefins systems. Among all pure component characteristic parameters, the monomer characteristic temperature (T*_monomer) has the largest impact on SL EOS predictive capability; whereas the polymer characteristic density (ρ*_polymer) is found to have the smallest impact.

     

Steady State Fluorescence Studies of Wild Type Recombinant Cinnamoyl CoA Reductase (Ll-CCRH1) and its Active Site Mutants

Fluorescence quenching and time resolved fluorescence studies of wild type recombinant cinnamoyl CoA reductase (Ll-CCRH1), a multitryptophan protein from Leucaena leucocephala and 10 different active site mutants were carried out to investigate tryptophan environment. The enzyme showed highest affinity for feruloyl CoA (K _a ?=?3.72?×?10⁵ M^?1) over other CoA esters and cinnamaldehydes, as determined by fluorescence spectroscopy. Quenching of the fluorescence by acrylamide for wild type and active site mutants was collisional with almost 100 % of the tryptophan fluorescence accessible under native condition and remained same after denaturation of protein with 6 M GdnHCl. In wild type Ll-CCRH1, the extent of quenching achieved with iodide (f _a?=?1.0) was significantly higher than cesium ions (f _a?=?0.33) suggesting more density of positive charge around surface of trp conformers under native conditions. Denaturation of wild type protein with 6 M GdnHCl led to significant increase in the quenching with cesium (f _a?=?0.54), whereas quenching with iodide ion was decreased (f _a?=?0.78), indicating reorientation of charge density around trp from positive to negative and heterogeneity in trp environment. The Stern-Volmer plots for wild type and mutants Ll-CCRH1 under native and denatured conditions, with cesium ion yielded biphasic quenching profiles. The extent of quenching for cesium and iodide ions under native and denatured conditions observed in active site mutants was significantly different from wild type Ll-CCRH1 under the same conditions. Thus, single substitution type mutations of active site residues showed heterogeneity in tryptophan microenvironment and differential degree of conformation of protein under native or denatured conditions.     

Sulfated Triterpenes from Lemon Balm

The hydroalcoholic (EtOH/H₂O) extract of matured leaf margins of lemon balm (Melissa officinalis L.) afforded a new 3,23‐disulfate of 2α,3β‐23,29‐tetrahydroxyolean‐12‐en‐28‐oic acid 28‐O‐β‐D ‐glucopyranoside ( 1 ) and a new 23‐monosulfate of 2α,23‐dihydroxyurs‐12‐en‐28‐oic acid 3‐O‐β‐D ‐glucopyranoside ( 2 ), along with six known compounds, i.e., 23‐monosulfate of 2α,3β,19α,23‐tetrahydroxyurs‐12‐ene‐28‐oic acid 28‐O‐β‐D ‐glucopyranoside ( 3 ), 3,5,6‐trihydroxydehydro‐α‐ionol 9‐O‐β‐D ‐glucopyranoside ( 4 ), quadranoside III ( 5 ), rosmarinic acid ( 6 ), caffeic acid ( 7 ), and luteolin ( 8 ). All the isolated compounds were evaluated for their antioxidant, antimicrobial, antimalarial, and cytotoxic activities. Only rosmarinic acid exhibited substantial antioxidant and antimicrobial activities, whereas sulfated terpenes showed considerably lower or no antimicrobial activity.     

Heterogeneous reusable catalyst,ultrasound energy,and no solvent: a quick and green recipe for one-pot synthesis of β-phosphonomalononitriles at room temperature

Clay-supported heteropolyacid catalyst has been prepared and investigated as a novel heterogeneous, reusable and efficient catalyst for the one-pot synthesis of β-phosphonomalononitriles under ultrasound irradiation at room temperature. Compared with traditional methods, the present method is solvent-free, works under milder and cleaner conditions, furnishes products with higher purity and yields, needs shorter reaction time, easier work-up procedure, and generates less waste. No column purification is required and the products can be purified by simple crystallization. The catalyst can be easily recovered and reused several times without significant loss of its catalytic activity. The catalyst was characterized by scanning electron microscopy, X-ray powder diffraction, and thermal gravimetric, surface area, and elemental analyses.     

Nickel(II) complexes of polyhydroxybenzaldehyde N4-thiosemicarbazones: synthesis, structural characterization and antimicrobial activities

Nickel(II) complexes with 2,3-dihydroxybenzaldehyde N4-substituted thiosemicarbazone ligands (H₃L¹–H₃L⁴) have been synthesized and characterized with the aim of evaluating the effect of N4 substitution in the thiosemicarbazone moiety on their coordination behavior and biological activities. Two series of nickel(II) complexes with the general formulae [Ni(H₃L)(H₂L)]ClO₄ and [Ni₂(HL)₂] were characterized by analytical and spectral techniques. The molecular structure of one of the complexes, namely, [Ni(H₃L⁴)(H₂L⁴)]ClO₄ was established by single crystal X-ray diffraction studies. The crystal structure of this complex revealed that two H₃L⁴ ligands are coordinated to nickel(II) in different modes; one as a neutral tridentate ONS ligand and the other is as a monoanionic tridentate (ONS^?) ligand. The antimicrobial activities of the compounds were tested against 25 bacterial strains via the disc diffusion method, and their minimum inhibitory concentration (MIC) and minimum microbicidal concentration were evaluated using microdilution methods. With a few exceptions, most of the compounds exhibited low-to-moderate inhibitory activities against the tested bacterial strains. However, the complexes [Ni₂(HL³)₂] (7) and [Ni₂(HL⁴)₂] (8) indicated higher inhibitory activity against Salmonella enterica ATCC 9068 (MIC values 15.7 and <15.7 μg/ml, respectively), compared with gentamicin as the positive control (MIC 25 μg/ml). Complex (7) also inhibited Streptococcus pneumoniae more efficiently (MIC 31.2 μg/ml), compared with gentamicin (MIC > 50 μg/ml). The toxicities of the compounds were tested on brine shrimp (Artemia salina), where no meaningful toxicity level was noted for both the free ligands and the complexes. The cytotoxicities of the compounds on cell viability were determined on MCF7, PC3, A375, and H413 cancer cells in terms of IC₅₀; complexes [Ni(H₃L³)(H₂L³)]ClO₄ (3), [Ni₂(HL³)₂] (7) and [Ni₂(HL⁴)₂] (8) exhibited significant cytotoxicity on the tested cell lines.