Micro-scale membrane extraction of glyphosate and aminomethylphosphonic acid in water followed by high-performance liquid chromatography and post-column derivatization with fluorescence detector

A carrier-mediated supported liquid membrane micro-extraction using single hollow fiber membrane suitable for the determination of the herbicide glyphosate and its main metabolite aminomethylphosphonic acid in water is reported. A solution of 0.20 M Aliquat-336, a cationic carrier, in di-n-hexyl ether was selected as the supported liquid. A 20 microL of 1.0 M potassium chloride as the acceptor phase was filled in the membrane lumen. The membrane was immersed in a 20 mL of pH 9.0 sample solution. After 60-min extraction, the acceptor phase was analyzed by high-performance liquid chromatography with post-column derivatization. The enrichment factors were found to be 853 and 136 for glyphosate and aminomethylphosphonic acid, respectively. The method detection limits are 0.22 microg/L for glyphosate and 3.40 microg/L for aminomethylphosphonic acid. The procedure was validated and showed good accuracy and precision over a large linear dynamic range. The validated method was tested for the analysis of both analytes in spiked groundwater with good success.     

Synthesis of azirines containing aldehyde functionality and their utilization as synthetic tools for five membered oxazoles and isoxazoles

A simple and useful procedure for the synthesis of azirines containing aldehyde functionality from open chain bromo/chloro‐aldehydes at room temperature is reported. The scope of the ring expansion reaction of a number of 3‐substituted‐2‐formyl‐azirines has been examined using different oraganometallic catalysts and a variety of Lewis acids.     

Green synthesis of silver chloride nanoparticles using Prunus persica L. outer peel extract and investigation of antibacterial,anticandidal, antioxidant potential

The present study was conducted to synthesize silver chloride nanoparticles using the aqueous extract of outer peel of peach fruit (Prunus persica L.) and to evaluate its antibacterial activity, synergistic antibacterial and anticandidal potential against five foodborne pathogenic bacteria and five pathogenic Candida species respectively along with its antioxidant potential. The synthesized silver chloride nanoparticles (PE-AgClNPs) were visually confirmed with surface plasmon resonance peak at 440?nm upon UV–Vis spectroscopy analysis. Furthermore, the morphology, elemental composition and crystallinity nature were also characterized. PE-AgClNPs displayed strong antibacterial potentials (9.01–10.83?mm inhibition zone) against foodborne pathogenic bacteria and increased synergistic effect with kanamycin and rifampicin. PE-AgClNPs also displayed strong anticandidal synergistic activity with standard amphotericin b (10.51–14.01?mm inhibition zones), along with strong free radical scavenging and reducing power. Based on strong antibacterial and antioxidant capacities, PE-AgClNPs are anticipated to have potential applications in the biomedical and food sector industries.     

Solid-phase extraction for multiresidue determination of sulfonamides, tetracyclines, and pyrimethamine in Bovine's milk

This paper describes a systematic approach to the development of a solid-phase extraction method for simultaneous extraction of 10 antibiotic residues in bovine milk, belonging to groups of sulfonamides, tetracyclines, and pyrimethamine. The sample preparation steps include acidic deproteinization of milk proteins followed by sample enrichment and cleanup using a polymer-based Oasis HLB solid-phase extraction cartridge. The analyses were carried out by using a method based on liquid chromatography-electrospray ionisation-mass spectrometry with positive ion mode. The parameters affecting the extraction efficiency such as sample loading pH, SPE wash solvent composition, and eluting solution pH were carefully investigated and optimized. The developed solid-phase extraction procedure coupled to multiresidue liquid chromatography-electrospray ionization-mass spectrometry method was applied for the analysis of 10 antibiotic residues in milk samples, and it proved to be simple, sensitive, and selective providing a recovery ranging from 70 to 106%.     

Novel synthetic approach toward (+/-)-beta-cuparenone via palladium-catalyzed tandem Heck cyclization of 1-bromo-5-methyl-1-aryl-hexa-1,5-dien-3-ol derivatives

A novel and convenient synthetic route toward (+/-)-beta-cuparenone and many other sesquiterpene natural product precursors has been developed via palladium-catalyzed tandem Heck cyclization of 1-bromo-5-methyl-1-aryl-hexa-1,5-dien-3-ols. [reaction: see text].     

Ring‐Opening Polymerization of Prodrugs: A Versatile Approach to Prepare Well‐Defined Drug‐Loaded Nanoparticles

The synthesis of polymer–drug conjugates from prodrug monomers consisting of a cyclic polymerizable group that is appended to a drug through a cleavable linker is achieved by organocatalyzed ring‐opening polymerization. The monomers polymerize into well‐defined polymer prodrugs that are designed to self‐assemble into nanoparticles and release the drug in response to a physiologically relevant stimulus. This method is compatible with structurally diverse drugs and allows different drugs to be copolymerized with quantitative conversion of the monomers. The drug loading can be controlled by adjusting the monomer(s)/initiator feed ratio and drug release can be encoded into the polymer by the choice of linker. Initiating these monomers from a poly(ethylene glycol) macroinitiator results in amphiphilic diblock copolymers that spontaneously self‐assemble into micelles with a long plasma circulation, which is useful for systemic therapy.     

Hypersonic surface waves in 2D titanium nanostructure on silicon

The non‐destructive method of Brillouin spectroscopy was applied to investigate the vibrations of 2D titanium nanoislands. Simulations realized by the Finite Element Method permitted determination of the dispersion relations of the surface waves propagating in the island structure and silicon substrate as well as the width of the frequency gap for the system studied. 3D maps of unit cell deformation for the structure with nanoislands for individual modes were obtained. The Brillouin experiment is shown as an excellent tool for direct experimental determination of the presence of eigenvibrations and the frequency gap in phononic structures in the GHz range.

     

Conformational Transitions of the Catalytic Domain of Heme-Regulated Eukaryotic Initiation Factor 2α Kinase, a Key Translational Regulatory Molecule

In mammalian cells, the heme-regulated inhibitor (HRI) plays a critical role in the regulation of protein synthesis at the initiation step through phosphorylation of α-subunit of the eukaryotic initiation factor 2 (eIF2). In this study we have cloned and performed biophysical characterization of the kinase catalytic domain (KD) of rabbit HRI. The KD described here comprises kinase 1, the kinase insertion domain (KI) and kinase 2. We report here the existence of an active and stable monomer of HRI (KD). The HRI (KD) containing three tryptophan residues was examined for its conformational transitions occurring under various denaturing conditions using steady-state and time-resolved tryptophan fluorescence, circular dichroism (CD) and hydrophobic dye binding. The parameter A and phase diagram analysis revealed multi-state unfolding and existence of three stable intermediates during guanidine hydrochloride (Gdn-HCl) induced unfolding of HRI (KD). The protein treated with 6 M Gdn-HCl showed collisional and static mechanism of acrylamide quenching and the constants (K _sv  = 3.08 M⁻¹and K _s   = 5.62 M⁻¹) were resolved using time resolved fluorescence titration. Based on pH, guanidine hydrochloride and temperature mediated transitions, HRI (KD) appears to exemplify a rigid molten globule-like intermediate with compact secondary structure, altered tertiary structure and exposed hydrophobic patches at pH 3.0. The results indicate the inherent structural stability of HRI (KD), a member of the class of stress response proteins.     

Diethyl 1‐(4‐fluoro­phenyl)‐3‐(2‐furyl)‐5‐oxopyrrolidine‐2,2‐di­carboxyl­ate and diethyl 1‐(3,4‐di­chloro­phenyl)‐3‐(2‐furyl)‐5‐oxopyrrolidine‐2,2‐di­carboxyl­ate

The title compounds, C₂₀H₂₀FNO₆ and C₂₀H₁₉Cl₂NO₆, respectively, may exhibit bioactivity. In these compounds, the pyrrolidine ring adopts a conformation intermediate between envelope and half‐chair. Only one of the two ethoxy­carbonyl side chains is nearly planar. Centrosymmetric pairs are formed, and the crystal structure is stabilized by weak C—H⋯O hydrogen bonds and van der Waals interactions.     

The Strong Influence of Structure Polymorphism on the Conductivity of Peptide Fibrils

Peptide fibril nanostructures have been advocated as components of future biotechnology and nanotechnology devices. However, the ability to exploit the fibril functionality for applications, such as catalysis or electron transfer, depends on the formation of well‐defined architectures. Fibrils made of peptides substituted with aromatic groups are described presenting efficient electron delocalization. Peptide self‐assembly under various conditions produced polymorphic fibril products presenting distinctly different conductivities. This process is driven by a collective set of hydrogen bonding, electrostatic, and π‐stacking interactions, and as a result it can be directed towards formation of a distinct polymorph by using the medium to enhance specific interactions rather than the others. This method facilitates the detailed characterization of different polymorphs, and allows specific conditions to be established that lead to the polymorph with the highest conductivity.