Electrospinning of poly(lactic acid): Theoretical approach for the solvent selection to produce defect‐free nanofibers

In this study an integrated methodology was proposed for the selection of solvent systems to produce electrospinnable solutions that form defect‐free poly(lactic acid) (PLA) fibers with narrow diameter distributions. The solvent systems were chosen using a thermodynamic approach, combined with electrical and rheological property criteria. More specifically, the three step methodology includes (1) initial choice of solvent by solubility evaluation to meet thermodynamic criteria, (2) electrical properties, that is, conductivity and dielectric constant adjustment by using solvent mixtures to meet electrical property criteria, and (3) critical entanglement concentration (C_e) determination by viscosity measurements, supported by elastic and plastic moduli measurements, followed by concentration adjustment to meet rheological criteria. All three criteria need to be met to ensure defect‐free nanofiber morphology. The methodology was demonstrated using PLA solutions that were characterized in terms of thermodynamic properties, conductivity, surface tension, and viscosity measurements. These data were analyzed and related to the nanofiber morphology and diameter as determined from scanning electron microscopy (SEM). Measurements of the elastic (G′) and the plastic (G″) moduli of PLA solutions showed a sharp increase of G′ at the chain entanglement concentration. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1483–1498     

Tuning the Triplet Excited State of Bis(dipyrrin) Zinc(II) Complexes: Symmetry Breaking Charge Transfer Architecture with Exceptionally Long Lived Triplet State for Upconversion

Zinc(II) bis(dipyrrin) complexes, which feature intense visible absorption and efficient symmetry breaking charge transfer (SBCT) are outstanding candidates for photovoltaics but their short lived triplet states limit applications in several areas. Herein we demonstrate that triplet excited state dynamics of bis(dipyrrin) complexes can be efficiently tuned by attaching electron donating aryl moieties at the 5,5′-position of the complexes. For the first time, a long lived triplet excited state (τ_T=296 μs) along with efficient ISC ability (Φ_Δ=71 %) was observed for zinc(II) bis(dipyrrin) complexes, formed via SBCT. The results revealed that molecular geometry and energy gap between the charge transfer (CT) state and triplet energy levels strongly control the triplet excited state properties of the complexes. An efficient triplet–triplet annihilation upconversion system was devised for the first time using a SBCT architecture as triplet photosensitizer, reaching a high upconversion quantum yield of 6.2 %. Our findings provide a blueprint for the development of triplet photosensitizers based on earth abundant metal complexes with long lived triplet state for revolutionary photochemical applications.     

Peptide structural analysis using continuous Ar cluster and C60 ion beams

A novel application of time-of-flight secondary ion mass spectrometry (ToF-SIMS) with continuous Ar cluster beams to peptide analysis was investigated. In order to evaluate peptide structures, it is necessary to detect fragment ions related to multiple neighbouring amino acid residues. It is, however, difficult to detect these using conventional ToF-SIMS primary ion beams such as Bi cluster beams. Recently, C₆₀ and Ar cluster ion beams have been introduced to ToF-SIMS as primary ion beams and are expected to generate larger secondary ions than conventional ones. In this study, two sets of model peptides have been studied: (des-Tyr)-Leu-enkephalin and (des-Tyr)-Met-enkephalin (molecular weights are approximately 400 Da), and [Asn¹ Val⁵]-angiotensin II and [Val⁵]-angiotensin I (molecular weights are approximately 1,000 Da) in order to evaluate the usefulness of the large cluster ion beams for peptide structural analysis. As a result, by using the Ar cluster beams, peptide molecular ions and large fragment ions, which are not easily detected using conventional ToF-SIMS primary ion beams such as Bi₃ ⁺, are clearly detected. Since the large fragment ions indicating amino acid sequences of the peptides are detected by the large cluster beams, it is suggested that the Ar cluster and C₆₀ ion beams are useful for peptide structural analysis.     

Water Structure Modification by Sugars and Its Consequence on Micellization Behavior of Cetyltrimethylammonium Bromide in Aqueous Solution

Water structure modification by sugars with a wide difference in stereoregular structures ranging from monosaccharide to trisaccharide and its consequence on the micellization behavior of cetyltrimethylammonium bromide (CTAB) in aqueous medium have been investigated. The characteristic variation in water absorption peaks in the presence of d(?)fructose has been studied by near-infrared spectroscopy. The analyses show that the hydrogen bonding capability of d(+)glucose, d(?)fructose, sucrose, trehalose and raffinose is mainly responsible for the variation in water-additive interactions. The critical micelle concentration determined by specific conductivity measurement and aggregation number determined by steady state fluorescence quenching method show significant variations in presence of additives for CTAB in aqueous solution. The sugars interact with the water structure to varying extents owing to differences in hydrogen bonding capability depending on the stereoregularity of the structure. This induces differences in the microenvironment for competition between the hydrophobic interaction and degree of hydration of the hydrophilic group of the surfactant to ultimately influence the micellization behavior in aqueous solution.     

Analysis of drug interactions with serum proteins and related binding agents by affinity capillary electrophoresis: A review

Biomolecules such as serum proteins can interact with drugs in the body and influence their pharmaceutical effects. Specific and precise methods that analyze these interactions are critical for drug development or monitoring and for diagnostic purposes. Affinity capillary electrophoresis (ACE) is one technique that can be used to examine the binding between drugs and serum proteins, or other agents found in serum or blood. This article will review the basic principles of ACE, along with related affinity-based capillary electrophoresis (CE) methods, and examine recent developments that have occurred in this field as related to the characterization of drug–protein interactions. An overview will be given of the various formats that can be used in ACE and CE for such work, including the relative advantages or weaknesses of each approach. Various applications of ACE and affinity-based CE methods for the analysis of drug interactions with serum proteins and other binding agents will also be presented. Applications of ACE and related techniques that will be discussed include drug interaction studies with serum agents, chiral drug separations employing serum proteins, and the use of CE in hybrid methods to characterize drug binding with serum proteins.     

Synthesis and biological studies of complexes of 2- amino-<Emphasis Type="Italic">N</Emphasis>(2-aminobenzoyl) benzohydrazide with Co(II), Ni(II), and Cu(II)

The present work is concerned with the synthesis and coordination compounds of 2-amino-N(2-aminobezoyl) benzohydrazide (ABH). The ligand was synthesized by the reaction of methylanthranilate and hydrazine in 2:1 molar ratio. It can be viewed as a modified form of hydrazide. The ligand was characterized by ¹H-NMR, ¹³C-NMR, mass spectrometry, elemental analysis, and infrared studies. The ligand has got -NH₂ moeity, the site for chelation. The complexes of Co(II), Ni(II), and Cu(II) chlorides and bromides were prepared. These complexes were characterized by elemental analysis, infrared, conductance, and magnetic susceptibility studies. Infrared spectra studies confirmed the formation of complexes, while elemental studies suggested the complexation of [M(ABH)X₂] (where X = Cl⁻ or Br⁻) composition.     

Armatans A and B,New Antimicrobial Isoflavans from Colutea armata

Chemistry of Natural Compounds - Armatans A (1) and B (2), new isoflavans, have been isolated from the EtOAc-soluble fraction of the MeOH extract of Colutea armata Hemsl. &amp; Lace, along with...     

SPE-GC-MS for the Determination of Halogenated Acetic Acids in Drinking Water

The development and optimization of analytical methods for the better monitoring of disinfection by-products especially haloacetic acids in water are key step in order to estimate human exposure to such products after chlorination. A reliable and accurate analytical method is needed in order to reach the levels of concentration required by United States Environmental Protection Agency regulations. In this study a method was developed for determining halogenated acetic acids in drinking water, involving solid phase extraction, methylation derivatization, and GC-MS. The new SPE-GC-MS-SIM method is capable of analyzing all nine acids at extremely low μg L^–1 level. Run time is significantly reduced without compromising analytical results. The major advantages of the method are the simplicity of the chromatography, short run time and low detection limits. The method performance, limits of detection and spiking recovery were evaluated and the results proved that the accuracy and precision were good. This method outperforms previous GC-MS methods especially for the determination of dibromoacetic, dibromochloroacetic, dichlorobromoacetic and tribromoacetic acids. The method has been used to analyse domestic tap water and water samples collected at a local water treatment plant.