Slight Structural Disorder in Bithiophene-based Random Terpolymers with Improved Power Conversion Efficiency for Polymer Solar Cells

A series of random terpolymers P2-P5 were designed and synthesized by randomly embedding 5 mol%, 10 mol%, 15 mol%and 25 mol% feed ratios of low cost 2,2-bithiophene as the third monomer to the famous donor-acceptor(D-A) type copolymer PTB7-Th(P1). All polymers showed similar molecular weight with number-average molecular weight(Mn) and weight-average molecular weight(Mw) in the range of(59-74) and(93-114) kg·mol~(-1), respectively, to ensure a fair comparison on the structure-property relationships.Compared with the control copolymer PTB7-Th, the random terpolymers exhibited enhanced absorption intensity in a wide range from400 nm to 650 nm in both solution and film as well as in polymer/PC71 BM blends. From grazing incident wide-angle X-ray diffraction(GIWAXS), compared with the regularly alternated copolymer PTB7-Th, the random terpolymers demonstrated mild structural disorder with reduced(100) lamellar stacking and slightly weakened(010) π-π stacking for the polymers as well as slightly reduced PC71 BM aggregation in polymer/PC71 BM blends. However, the measured hole mobility for terpolymers((1.20-3.73) × 104-cm2·V-1·s~(-1)) was evaluated to be comparable or even higher than 1.35 × 10~(-4) cm~2·V~(-1)·s-1 of the alternative copolymer. Enhanced average power conversion efficiency(PCE) from 7.35% to 8.11% and 7.79% to 8.37% was observed in both conventional and inverted device architectures from copolymer P1 to terpolymers P4, while further increasing the 2,2-bithiophene feed ratio decreased the PCE.     

Liquid analysis dielectric capillary barrier discharge

In this study a simple micro-tube-based system for analysis of metal-containing liquids is introduced and its analytical performance is evaluated. It is based on a miniaturised dielectric barrier discharge driven at atmospheric pressure. The emission lines of various elements are observed. The system is developed for quantitative measurements and the limits of detection are determined. Because of very low flow rates of just μL min⁻¹ the approach requires extremely low sample volumes.     

Sonic spray ionization interface for liquid chromatography-mass spectrometry

A sonic spray ionization (SSI) interface for liquid chromatography-mass spectrometry (LC-MS) analysis was optimized for analysis of 2-[(1R)-3-[bis(1-methylethyl)amino]-1-phenylpropyl]-4-methyl-phenol (tolterodine), used as a model drug substance, and the influence of different parameter settings was evaluated using factorial design. A comparison between SSI and electrospray ionization (ESI) was made for tolterodine, tolterodine metabolites, and a set of steroids.SSI was found to give slightly poorer repeatability and broader peaks for tolterodine compared to ESI. However, there was no significant difference in chromatographic peak shape, and the repeatability using SSI was similar to that obtained using ESI if a ratio (area of tolterodine/area of metabolite) was used. In this study, the sensitivity was higher using SSI. For the analysis of pregnanolone, less water loss was obtained using SSI, probably due to less energy being transferred to the analyte upon ionization.     

Rearrangement of 2-aryl-3,3-dichloroazetidines: intermediacy of 2-azetines

An easy synthesis of 2-aryl-3,3-dichloroazetidines, a rather unexplored class of azaheterocycles, is described. The title compounds were easily obtained by reduction of the corresponding 4-aryl-3,3-dichloro-2-azetidinones with monochloroalane, which in turn were synthesized by a ketene-imine [2 + 2] cycloaddition. The reactivity of 3,3-dichloroazetidines with bases was investigated, yielding 2-[dimethoxy(aryl)methyl]aziridines by ring contraction when treated with sodium methoxide. Furthermore, reacting the 3,3-dichloroazetidines with sodium hydride in DMSO, followed by aqueous workup, afforded 1-alkyl-2-aroylaziridines, by hydrolysis of the intermediate 2-azetines and ring closure of the transient 3-amino-2-chloro-1-phenyl-1-propanone derivatives. Monitoring this reaction in an NMR tube, using sodium hydride in DMSO-d(6), allowed the characterization of the intermediate strained heterocyclic enamines, i.e., 2-azetines, by (1)H and (13)C NMR.     

GnRH binding RNA and DNA Spiegelmers: a novel approach toward GnRH antagonism

Mirror-image oligonucleotide ligands (Spiegelmers) that bind to the pharmacologically relevant target gonadotropin-releasing hormone I (GnRH) with high affinity and high specificity have been identified using the Spiegelmer technology. GnRH is a decapeptide that plays an important role in mammalian reproduction and sexual maturation and is associated with several benign and malignant diseases. First, aptamers that bind to D-GnRH with dissociation constants of 50-100 nM were isolated out of RNA and DNA libraries. The respective enantiomers of the DNA and RNA aptamers were synthesized, and their binding to L-GnRH was shown. These Spiegelmers bind to L-GnRH with similar affinity to that of the corresponding aptamers that bind to D-GnRH. We further demonstrated dose-dependent inhibition of GnRH-induced Ca(2+) release in Chinese hamster ovary cells that were stably transfected with the human GnRH receptor.