Mass spectra of bile acid methyl ester acetate derivatives

Deuterium labeling in the acetate derivatives of cholic acid demonstrates that electron impact induced consecutive loss of HOAc from the molecular ion occurs in the following order of decreasing preference: 12α-OAc > 7α-OAc > 3α-OAc. Numerous examples are presented showing that consecutive loss of HOAc from a common ion generally increases progressively with relative intensity. In the acetate pregnan-20-one derivatives of cholic acid, loss of 43 mass units from the molecular ion comes from the 12α-OAc and not the 17β-acetyl sidechain. Ketene is ejected from an acetoxy group located in an α position to a carbonyl on which an ion-radical charge is localized.     

Studies directed toward synthesis of quassinoids. VI—mass spectral fragmentation of D-ring seco esters and δ-lactone derivatives of cholic acid

Analogy and deuterium labeling demonstrate that considerable remote group interaction occurs between functional groups at positions 7 and 16 in 16, 17-secosteroids. It is proposed that ion-dipole interact?ions separations of distances of 10 to 2 Å will involve energies of 1–30 kcal mol^?1 and can play a significant role in fragmentation processes. Successive loss of one, two and three HOAc molecules from a milecular or daughter ion increase progressively in relative intensity; irregularity in this pattern indicates the operation of special factors or multiple genesis of daughter ions having the same m/e. Evidence is presented which suggests that facile ketene ejection from the acetate functional group only occurs from a radical ion and must be preceded by transfer of a hydrogen radical from the acetate group to the site of charge localization.     

Green synthesis and characterization of monodispersed silver nanoparticles obtained using oak fruit bark extract and their antibacterial activity

Green synthesis of silver nanoparticles (Ag NPs) has been achieved using oak fruit bark extract as a reducing, capping and stabilizing agent. The biosynthesized Ag NPs were characterized using various techniques. UV–visible spectrum of prepared silver colloidal solution showed absorption maximum at 433 nm. X‐ray diffraction and transmission electron microscopy analysis revealed that Ag NPs have a face‐centred cubic structure being spherical in shape with an average particle size of 20–25 nm. The toxicity of the Ag NPs was tested on bacterial species such as Staphylococcus aureus, Bacillus subtilis, Pseudomonas aeruginosa and Escherichia coli by comparison based on diameter of inhibition zone in disc diffusion tests and minimum inhibitory concentration and minimum bactericidal concentration of NPs dispersed in liquid cultures. The antimicrobial activity of Ag NPs was greater towards Gram‐positive bacteria (S. aureus and B. subtilis) compared to Gram‐negative bacteria as determined using standard Kirby–Bauer disc diffusion assay and serial dilution. Copyright © 2016 John Wiley & Sons, Ltd.     

Palladium on magnetic Irish moss: A new nano‐biocatalyst for suzuki type cross‐coupling reactions

A novel heterogeneous magnetic palladium nano‐biocatalyst was designed by utilizing Irish moss, a family of sulfated polysaccharides extracted from algae, as a natural biopolymer. This magnetic Irish moss decorated with palladium (Pd–Fe₃O₄@IM) to form a biomagnetic catalytic system was synthesized and well characterized by FT–IR analysis, X‐ray powder diffraction, field emission scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, atomic absorption spectroscopy and transmission electron microscopy. The catalyst was stable to air and moisture and displayed high catalytic activity in ligand‐free Suzuki–Miyaura cross‐coupling reactions conducted under green chemistry reaction conditions. The aromatic ketones are produced by the cross‐coupling reaction between acid chlorides and aryl boronic acid derivatives in high yields.     

Biosynthesis of gold nanoparticles using Allium noeanum Reut. ex Regel leaves aqueous extract; characterization and analysis of their cytotoxicity,antioxidant, and antibacterial properties

Gold nanoparticles have unique and excellent medical and nonmedical properties and application compared with other metallic nanoparticles. Recently, they have been used for the prevention, control, and treatment of bacterial and fungal diseases. In the recent study, fresh and clean leaves of Allium noeanum Reut. ex Regel leaves have been used for the synthesis of gold nanoparticles. Also, we evaluated the cytotoxicity, antioxidant, and antibacterial properties of HAuCl₄, A. noeanum, and the synthesized nanoparticles (Au NPs). These nanoparticles were analyzed by FT‐IR, UV, XRD, EDS, FE‐SEM, and TEM tests. FTIR results offered antioxidant compounds in the plant were the sources of reducing power, reducing gold ions to Au NPs. In TEM images revealed an average diameter of 10‐30 nm. At the beginning of biological experiments, DPPH free radical scavenging test was carried out to examine the antioxidant property. Also, in the bacterial part of this study, the concentration of HAuCl₄, A. noeanum, and AuNPs with minimum dilution and no turbidity was considered MIC. To determine MBC, 60 μL of MIC and three preceding chambers were cultured on Muller Hinton Agar. The minimum concentration with no bacterial growth was considered MBC. Au NPs revealed excellent antioxidant potential against DPPH, non‐toxicity property against human umbilical vein endothelial cells, and antibacterial activities against Streptococcus pneumonia, Bacillus subtilis, Staphylococcus aureus, Staphylococcus saprophyticus, Salmonella typhimurium, Pseudomonas aeruginosa, Shigella flexneri, and Escherichia coli O157:H7. These findings show that the inclusion of A. noeanum extract improves the solubility of Au NPs, which led to a notable enhancement in the antioxidant and antibacterial effects.     

Palladium nanoparticles‐decorated triethanolammonium chloride ionic liquid‐modified TiO2 nanoparticles (TiO2/IL‐Pd): A highly active and recoverable catalyst for Suzuki–Miyaura cross‐coupling reaction in aqueous medium

In this work, an easily obtained procedure was successfully implemented to prepare novel palladium nanoparticles decorated on triethanolammonium chloride ionic liquid‐functionalized TiO₂ nanoparticles [TiO₂/IL‐Pd]. Different methods were carried out for characterizations of the synthesized nanocatalyst (HR‐TEM, XPS, XRD, FE‐SEM, EDX, FT‐IR and ICP). TiO₂/IL‐Pd indicated good catalytic activity for the Suzuki–Miyaura cross‐coupling reaction of arylboronic acid with different aryl halides in aqueous media at ambient temperature. The recycled catalyst was investigated with ICP to amount of Pd leaching after 6 times that had diminished slightly, Thus, was confirmed that the nanocatalyst has a good sustainability for C–C Suzuki–Miyaura coupling reaction. The catalyst can be conveniently separated by filtration of the reaction mixture and reused for 6 times without significant loss of its activity. It supplies an environmentally benign alternative path to the existing protocols for the Suzuki–Miyaura reaction.     

Risk externalities and too big to fail

This paper establishes the case for a fallacy of economies of scale in large aggregate institutions and the effects of scale risks. The problem of rogue trading and excessive risk taking is taken as a case example. Assuming (conservatively) that a firm exposure and losses are limited to its capital while external losses are unbounded, we establish a condition for a firm not to be allowed to be too big to fail. In such a case, the expected external losses second derivative with respect to the firm capital at risk is positive. Examples and analytical results are obtained based on simplifying assumptions and focusing exclusively on the risk externalities that firms too big to fail can have.     

Luciferin‐Regenerating Enzyme Mediates Firefly Luciferase Activation Through Direct Effects of D‐Cysteine on Luciferase Structure and Activity

Luciferin‐regenerating enzyme (LRE) contributes to in vitro recycling of D‐luciferin. In this study, reinvestigation of the luciferase‐based LRE assay is reported. Here, using quick change site‐directed mutagenesis seven T‐LRE (Lampyris turkestanicusLRE) mutants were constructed and the most functional mutant of T‐LRE (T⁶⁹R) was selected for this research and the effects of D‐ and L‐cysteine on T⁶⁹R T‐LRE‐luciferase‐coupled assay are examined. Our results demonstrate that bioluminescent signal of T⁶⁹R T‐LRE‐luciferase‐coupled assay increases and then reach equilibrium state in the presence of 5 mm D‐cysteine. In addition, results reveal that 5 mm D‐ and L‐cysteine in the absence of T⁶⁹R T‐LRE cause a significant increase in bioluminescence intensity of luciferase over a long time as well as decrease in decay rate. Based on activity measurements, far‐UV CD analysis, ANS fluorescence and DLS (Dynamic light scattering) results, D‐cysteine increases the activity of luciferase due to weak redox potential, antiaggregatory effects, induction of changes in conformational structure and kinetics properties. In conclusion, in spite of previous reports on the effect of LRE on luciferase bioluminescent intensity, the majority of increase in luciferase light output and time‐course originate from the direct effects of D‐cysteine on structure and activity of firefly luciferase.