Calcium/poly(9,9-dioctylfluorene) interaction: a theoretical study

The geometric and electronic structures of poly(9,9-dioctylfluorene) (PFO) oligomer interacting with Ca atoms were studied using M?ller-Plesset perturbation theory. A weak interaction with little charge transfer and with a relatively long Ca-C distance (about 4.0 Angstrom) was found when only one Ca atom was attached to a PFO unit. However, when two Ca atoms were adsorbed at a PFO unit, a strong interaction with a shorter Ca-C distance (about 2.67 Angstrom) took place with considerable charge transfer from the Ca atom to the PFO, resulting in significant deformation in the backbone of the PFO oligomer. In the latter case, the frontier orbitals of the PFO were modified. However, the deformed PFO and its modified frontier orbitals could be recovered when oxygen was added, which is in good agreement with experimental observation.     

A novel three-dimensional pillared-layer hybrid zinc phosphite featuring double-helical channels

A new zinc phosphite (C₂H₈N₂)_0.5(HPO₃)Zn has been hydrothermally synthesized from a mixture of ZnO, H₃PO₃, 4,4’-bipyridine, ethylenediamine, and H₂O. Single-crystal X-ray diffraction analysis reveals that the Zn ions are first interconnected by HPO₃ ²- ligands to produce a neutrally infinite two-dimensional inorganic layer with four- and eight-membered rings, which is further used as the second building units and helically pillared by bridging ethylenediamine molecules to form the scarcely reported three-dimensional pillared-layer hybrid zinc phosphite with double-helical channels due to the flexibility of the ethylenediamine ligands.     

Fabrication of a high-strength hydrogel with an interpenetrating network structure

Hydrogels have potential applications in many fields, but the poor mechanical strength has limited their further development. In this article, we designed a high-strength hydrogel with an interpenetrating network (IPN) structure from polyacrylamide (PAM) and poly(vinyl alcohol) (PVA). Synthesis parameters, such as PVA/AM mass ratio, crosslinker dosage and elongation time were carried out for high tensile strength and elongation. The results showed that chemical crosslinking, physical entanglement and PVA precipitates were the dominant parameters for the improvement of mechanical properties. The PVA structure transferred from crystal to amorphous due to intermolecular and intramolecular interactions (such as hydrogen bond and self-crosslinking). PVA precipitates scatterred in the brittle PAM matrix homogeneously which dispersed the applied stress and improved the hydrogel toughness. The tensile strength and elongation were extremely high, they were 2.4 MPa and 3100%, respectively. The simple method is versatile in synthesizing high-strength IPN hydrogels using many kinds of polymer species.     

Tetraphenylpyrazine-based AIEgens: facile preparation and tunable light emission

Research on aggregation-induced emission (AIE) has been a hot topic. Due to enthusiastic efforts by many researchers, hundreds of AIE luminogens (AIEgens) have been generated which were mainly based on archetypal silole, tetraphenylethene, distyrylanthracene, triphenylethene, and tetraphenyl-1,4-butadiene, etc. To enlarge the family of AIEgens and to enrich their functions, new AIEgens are in high demand. In this work, we report a new kind of AIEgen based on tetraphenylpyrazine (TPP), which could be readily prepared under mild reaction conditions. Furthermore, we show that the TPP derivatives possess a good thermal stability and their emission could be fine-tuned by varying the substituents on their phenyl rings. It is anticipated that TPP derivatives could serve as a new type of widely utilized AIEgen, based on their facile preparation, good thermo-, photo- and chemostabilities, and efficient emission.     

Bioelectrochemical response of a choline biosensor fabricated by using polyaniline

On the basis of the isoelectric point of an enzyme and the doping principle of conducting polymers, choline oxidase was doped in a polyaniline film to form a biosensor. The amperometric detection of choline is based on the oxidation of the H₂O₂ enzymatically produced on the choline biosensor. The response current of the biosensor as a function of temperature was determined from 3 to 40°C. An apparent activation energy of 22.8 kJ·mol⁻¹ was obtained. The biosensor had a wide linear response range from 5 × 10⁻⁷ to 1 × 10⁻⁴ M choline with a correlation coefficient of 0.9999 and a detection limit of 0.2 μM, and had a high sensitivity of 61.9 mA·M⁻¹·cm⁻² at 0.50 V and at pH 8.0. The apparent Michaelis constant and the optimum pH for the immobilized enzyme are 1.4 mM choline and 8.4, respectively, which are very close to those of choline oxidase in solution. The effect of selected organic compounds on the response of the choline biosensor was studied.     

Synthesis of macrocyclic ligands incorporating sulfur and furan subunits

Abstract

Polyammonium macrocycles containing sulfur and furan units in the macrocyclic ring have been synthesized and studied for ATPase activity. The synthetic methodology involved using tosyl protection for the amines and the formation of macrocyclic Lactams, followed by reduction using borane in THF. Deprotection of the tosylated forms of the macrocycle was accomplished using sodium in butanol for the furan macrocycles, and HBr in HOAc for the sulfur containing macrocycle. The macrocycles were found to be poor catalysts for ATP hydrolysis compared to other similar polyammonium macrocycles.     

Salvianolic acid A inhibits PDGF-BB induced vascular smooth muscle cell migration and proliferation while does not constrain endothelial cell proliferation and nitric oxide biosynthesis

Proliferation and migration of vascular smooth muscle cells (VSMCs) are critical events in the initiation and development of restenosis upon percutaneous transluminal coronary angioplasty (PTCA). Polyphenols have been suggested to ameliorate post-angioplasty restenosis. Salvianolic A (SalA) is one of the most abundant polyphenols extracted from salvia. In this study, we investigated the effect of salvianolic A (SalA) on the migration and proliferation of VSMCs. We found a preferential interaction of SalA with cellular systems that rely on the PDGF signal, but not on the EGF and bFGF signal. SalA inhibits PDGF-BB induced VSMC proliferation and migration in the concentration range from 0.01 to 0.1 μM. The inhibition of SalA on VSMC proliferation is associated with cell cycle arrest. We also found that SalA inhibits the PDGFRβ-ERK1/2 signaling cascade activated by PDGF-BB in VSMCs. In addition, SalA does not influence the proliferation of endothelial cells, the synthesis of NO and eNOS protein expression. Our results suggest that SalA inhibits migration and proliferation of VSMCs induced by PDGF-BB via the inhibition of the PDGFRβ-ERK1/2 cascade, but that it does not constrain endothelial cell proliferation and nitric oxide biosynthesis. Thus, the present study suggests a novel adjunct pharmacological strategy to prevent angioplasty-related restenosis.     

Oxovanadium(IV) based hypocrellin B complexes with enhanced photodynamic activity

Hypocrellin B (HB), a naturally occurring photosensitizer, has been extensively and intensively studied as a promising photodynamic therapy (PDT) agent. In this work, three new oxovanadium(IV) complexes were designed and synthesized with HB as a bridging ligand and phen (1,10-phenanthroline, complex 1), tmp (3,4,7,8-tetramethyl-1,10-phenanthroline, complex 2) and dpq (dipyrido[3,2-f:2'3'-h]quinoxaline, complex 3) as terminal ligands. The use of a diimine terminal ligand avoids the formation of polymeric complexes and ensures the three VO(2+)-HB complexes possess a definite molecular formula and molecular weight to meet the single component requirement for an ideal PDT agent. Compared to HB, the VO(2+)-HB complexes exhibit improved water solubility, enhanced absorptivity in the phototherapeutic window, increased binding affinity toward dsDNA, and similar singlet oxygen quantum yield, therefore advanced DNA photocleavage activity. Both the DNA binding constants and photo nuclease activities of the complexes follow the order 2 (tmp) > 3 (dpq) > 1 (phen), demonstrating the importance of the binding affinity to biomolecules, which improves the bioavailability of reactive oxygen species. Our work opens a new avenue for the development of HB-based PDT agents.     

Selective surface reactions for Janus ORMOSIL particles with multiple functional groups using an ordered monolayer film at liquid-liquid interface

Monodispersed, submicron-sized Janus ORMOSIL particles with multiple functional groups were prepared by the selective surface reaction of a monolayer film formed at a hexane-water interface. A well-ordered monolayer film was obtained by self-assembly of ORMOSIL particles with multiple functional groups at hexane-water interface. The photopolymerization of an ordered monolayer containing ORMOSIL particles yields a rigid film strong enough to maintain its integrity for transfer and further chemical reaction. The chemical reaction of this ordered film with organic and inorganic functional groups produced Janus ORMOSIL particles with multiple functional groups. The morphologies, structures, and chemical compositions of monolayer films and Janus ORMOSIL particles were characterized by FT-IR, solid state NMR, X-ray diffraction (XRD), optical microscopy (OM), electron microscopies (SEM and TEM), and confocal laser scanning microscopy.     

An efficient synthesis of unsymmetrical diarylmethanes from the dehydration of arenes with benzyl alcohols using InCl3·4H2O/acetylacetone catalyst system

An efficient and practical synthesis of unsymmetrical diarylmethanes has been achieved from the dehydration of arenes with benzyl alcohols in the presence of catalytic amount of InCl₃·4H₂O/acetylacetone.