Ester-functionalized poly(3-alkylthiophene) copolymers: Synthesis,physicochemical characterization and performance in bulk heterojunction organic solar cells

The introduction of functional moieties in the donor polymer (side chains) offers a potential pathway toward selective modification of the nanomorphology of conjugated polymer:fullerene active layer blends applied in bulk heterojunction organic photovoltaics, pursuing morphology control and solar cell stability. For this purpose, two types of poly(3-alkylthiophene) random copolymers, incorporating different amounts (10/30/50%) of ester-functionalized side chains, were efficiently synthesized using the Rieke method. The solar cell performance of the functionalized copolymers was evaluated and compared to the pristine P3HT:PCBM system. It was observed that the physicochemical and opto-electronic characteristics of the polythiophene donor material can be modified to a certain extent via copolymerization without (too much) jeopardizing the OPV efficiency, as far as the functionalized side chains are introduced in a moderate ratio (<30%) and that preference is given to side chains with a small molar volume. A range of complementary techniques – UV–Vis spectroscopy, (modulated temperature) differential scanning calorimetry, transmission electron microscopy and X-ray diffraction analysis – indicated that variations in polymer crystallinity, while maintaining a high level of regioregularity, are probably the main factor responsible for the observed differences.     

Inversion of Aromaticity of NH-Tautomers of Free-Base Corroles in the Lowest Triplet T1-State

Journal of Applied Spectroscopy - The aromaticity in the lowest triplet T1-state of NH-tautomers of corrole free bases with different peripheral substitution architecture was investigated using...     

An Organoid for Woven Bone

Bone formation (osteogenesis) is a complex process in which cellular differentiation and the generation of a mineralized organic matrix are synchronized to produce a hybrid hierarchical architecture. To study the mechanisms of osteogenesis in health and disease, there is a great need for functional model systems that capture in parallel, both cellular and matrix formation processes. Stem cell-based organoids are promising as functional, self-organizing 3D in vitro models for studying the physiology and pathology of various tissues. However, for human bone, no such functional model system is yet available. This study reports the in vitro differentiation of human bone marrow stromal cells into a functional 3D self-organizing co-culture of osteoblasts and osteocytes, creating an organoid for early stage bone (woven bone) formation. It demonstrates the formation of an organoid where osteocytes are embedded within the collagen matrix that is produced by the osteoblasts and mineralized under biological control. Alike in in vivo osteocytes, the embedded osteocytes show network formation and communication via expression of sclerostin. The current system forms the most complete 3D living in vitro model system to investigate osteogenesis, both in physiological and pathological situations, as well as under the influence of external triggers (mechanical stimulation, drug administration).     

Oxidative Addition of Haloheteroarenes to Palladium(0): Concerted versus SNAr‐Type Mechanism

The kinetics of the oxidative additions of haloheteroarenes HetX (X=I, Br, Cl) to [Pd⁰(PPh₃)₂] (generated from [Pd⁰(PPh₃)₄]) have been investigated in THF and DMF and the rate constants have been determined. In contrast to the generally accepted concerted mechanism, Hammett plots obtained for substituted 2‐halopyridines and solvent effects reveal a reaction mechanism dependent on the halide X of HetX: an unprecedented S_NAr‐type mechanism for X=Br or Cl and a classical concerted mechanism for X=I. These results are supported by DFT studies.     

Detection challenges in quantitative polymer analysis by liquid chromatography

Accurate quantification of polymer distributions is one of the main challenges in polymer analysis by liquid chromatography. The response of contemporary detectors is typically influenced by compositional features such as molecular weight, chain composition, end groups, and branching. This renders the accurate quantification of complex polymers of which there are no standards available, extremely challenging. Moreover, any (programmed) change in mobile‐phase composition may further limit the applicability of detection techniques. Current methods often rely on refractive index detection, which is not accurate when dealing with complex samples as the refractive‐index increment is often unknown. We review current and emerging detection methods in liquid chromatography with the aim of identifying detectors, which can be applied to the quantitative analysis of complex polymers.     

Matrix Isolation Infrared Spectra of Methylacetate III. UV-Induced Z→E photorotamerisation of Methylacetate in Argon Matrices

Abstract

Broadband UV-irradiation of methylacetate isolated in argon matrices causes rather strong modifications to appear in the IR spectrum. Evidence was obtained for a photochemical interconversion of the stable Z-conformer into the less stable E-conformer followed by photolytic decomposition of the latter into stable products. Most of these products could be identified from their IR absorptions. The reverse E→Z interconversion is a thermal process with an activation energy of about 10 kJmole^?1. A normal coordinate analysis based on a transferable valence force field obtained from the literature allowed to assign approximate IR frequencies of E-methylacetate.     

Comments on the Implementation of a Simple Peak Capacity Optimization Procedure and Comparison of Poly(styrene–divinylbenzene) and RP-18 Silica Monolithic Capillary Columns of 5-cm for the Analysis of Protein Digests

For the analysis of protein digests, the peak capacity in reversed-phase liquid chromatography is of paramount importance. A univariate method to maximize the peak capacity as developed by Wang et al. (Anal Chem 78:3406–3416, 20) has been applied and tested for a monolithic RP-18 silica capillary column. In their method, using model peptides representing a bovine serum albumin digest, the gradient time and temperature are kept constant while the flow rate and eluent strength are varied. Despite our criticism on the fixed starting conditions, a long gradient time leading to an unnecessary long analysis time and a high temperature leading to possible degradation products in the chromatogram, and the peak capacity as the only optimization parameter this fast and simple optimization strategy turns out to be applicable to capillary monolithic columns. Furthermore, the influence of the peak capacity on a second optimization parameter, the MS protein identification score, is examined. The procedure is also used to enhance the performance of two popular types of monolithic capillary LC columns (silica-C18 and poly(styrene–divinylbenzene)) of the same length for the analysis of protein digests. Comparison of both columns show that the calculated chromatographic parameters, like productivity and peak capacity, and identification score for both columns are about the same. For a more complicated nine-protein digest the performance of the silica monolith is slightly better.     

Lewis Acid Mediated Vinyl‐Transfer Reaction of Alkynes to N‐Alkylimines by Using the N‐Alkyl Residue as a Sacrificial Hydrogen Donor

A variety of N‐alkyl‐α,α‐dichloroaldimines were vinylated by terminal acetylenes in the presence of Lewis acids such as In(OTf)₃ or BF₃ ? OEt₂ and hexafluoroisopropanol (HFIP) as an additive. The reaction proceeds at ambient temperature and leads to geometrically pure allylic β,β‐dichloroamines. This approach is complementary to previously reported transition‐metal‐catalyzed vinyl‐transfer methods, which are not applicable to aliphatic imines and are restricted to imines that contain an electron‐withdrawing nitrogen substituent. In the present approach, terminal alkynes were used as a source of the vinyl residue, and the N‐alkyl moiety of the imine acts as a sacrificial hydrogen donor. The additional advantage of this methodology is the fact that no external toxic or hazardous reducing agents or molecular hydrogen has to be used. This new methodology nicely combines a C(sp²)? C(sp) bond formation, hydride transfer, and an unusual cleavage of an unactivated C? N bond, thereby giving rise to functionalized primary allylic amines. A detailed experimental study supported by DFT calculations of the mechanism has been done.     

Development of Novel Isoindolone-Based Compounds against Trypanosoma brucei rhodesiense

This study identified the isoindolone ring as a scaffold for novel agents against Trypanosoma brucei rhodesiense and explored the structure-activity relationships of various aromatic ring substitutions. The compounds were evaluated in an integrated in vitro screen. Eight compounds exhibited selective activity against T. b. rhodesiense (IC₅₀<2.2 μm ) with no detectable side activity against T. cruzi and Leishmania infantum. Compound 20 showed low nanomolar potency against T. b. rhodesiense (IC₅₀=40 nm ) and no toxicity against MRC-5 and PMM cell lines and may be regarded as a new lead template for agents against T. b. rhodesiense. The isoindolone-based compounds have the potential to progress into lead optimization in view of their highly selective in vitro potency, absence of cytotoxicity and acceptable metabolic stability. However, the solubility of the compounds represents a limiting factor that should be addressed to improve the physicochemical properties that are required to proceed further in the development of in vivo-active derivatives.     

Sustainable Three‐Component Synthesis of Isothioureas from Isocyanides,Thiosulfonates, and Amines

Multiple applications of isothioureas as fine chemicals (or their precursors) are known, but a general sustainable method for their synthesis was hitherto unavailable. We report a novel general approach towards S‐alkyl and S‐aryl isothioureas through a copper(I)‐catalyzed three‐component reaction between amines, isocyanides, and thiosulfonates. The formal synthesis of a superpotent sweetener further illustrates the applicability of our method.