Palladium(II) complexes of Y,C,Y‐chelated phosphines: synthesis,structure, and catalytic activity in Suzuki–Miyaura reaction

The phosphines L¹PPh₂ (1) and L²PPh₂ (2) containing different Y,C,Y‐chelating ligands, L¹ = 2,6‐(^tBuOCH₂)₂C₆H₃^? and L² = 2,6‐(Me₂NCH₂)₂C₆H₃^?, were treated with PdCl₂ and di‐µ‐chloro‐bis[2‐[(N,N‐dimethylamino)methyl]phenyl‐C,N]‐dipalladium(II) and yielded complexes trans‐{[2,6‐(^tBuOCH₂)₂C₆H₃]PPh₂}₂PdCl₂ (3), {[2,6‐(Me₂NCH₂)₂C₆H₃]PPh₂} PdCl₂ (4), {[2,6‐(^tBuOCH₂)₂C₆H₃]PPh₂}Pd(Cl)[2‐(Me₂NCH₂)C₆H₄] (5) and {[2,6‐(Me₂NCH₂)₂C₆H₃]PPh₂}Pd(Cl)[2‐(Me₂NCH₂)C₆H₄] (6) as the result of different ability of starting phosphines 1 and 2 to complex PdCl₂. Compounds 3–6 were characterized by ¹H, ¹³C, ³¹P NMR spectroscopy and ESI‐MS. The molecular structures of 3,4 and 6 were also determined by X‐ray diffraction analysis. The catalytic activity of complexes 3–6 was evaluated in the Suzuki‐Miyaura cross‐coupling reaction. Copyright © 2010 John Wiley & Sons, Ltd.     

Simultaneous Separation and Determination of Isosorbide Dinitrate and Isosorbide 5-Mononitrate in Human Plasma by LC–MS–MS

A sensitive, selective, and simple liquid chromatography-tandem mass spectrometry method has been developed for the simultaneous separation and determination of isosorbide dinitrate and its active metabolite, isosorbide 5-mononitrate, in human plasma. Topiramate was used as the internal standard. Sample preparation consisted of a simple one-step liquid–liquid extraction with ethylacetate without pH adjustment. The method was fully validated with respect to linearity, sensitivity, specificity, recovery, accuracy, and precision. Isosorbide dinitrate and isosorbide 5-mononitrate were stable in standard solution and in plasma samples under storage and processing conditions. The assay was successfully applied to the pharmacokinetic study of isosorbide dinitrate and isosorbide 5-mononitrate in human plasma.     

Hydroformylation of Oct‐1‐ene in Novel Ionic Liquid Crystals

Hydroformylation of oct‐1‐ene leading to nonanal (denoted by n) and 2‐methyloctanal (denoted by iso), in a novel series of caprolactam‐based and common imidazolium‐based ionic liquid crystals (ILCs; see Fig. 1) carried out for the first time (caprolactam=hexahydro‐2H‐azepin‐2‐one) (Scheme). Variation of the chain length (n) of the alkyl substituent (C_n) at the caprolactam cation (CP⁺) from n=12 to 18 caused the n/iso ratios to vary from 1.7 to 2.9. Meanwhile, the TOF (turnover frequency) decreased from 148 to 122 mol mol⁻¹ h⁻¹. Hydroformylation in the imidazolium‐based ILCs revealed that [C₁₆MIm]⋅BF₄ (n/iso 5.2, TOF 969 mol mol⁻¹ h⁻¹) was more favorable than [C₁₆MIm]⋅MsO (n/iso 3.7, TOF 969 mol mol⁻¹ h⁻¹) for the formation of the unbranched aldehyde. Although the n/iso ratio in caprolactam‐based ILCs was lower than that in imidazolium‐based ILCs, the conversions are higher in the former ILCs on the whole. It should be noted that the lamellar mesophase has a strong effect on the regioselectivity and TOF of the hydroformylation. Also, it is evident that the influences of different ILCs on the hydroformylation under the various reaction conditions are greatly different. The identification of the reaction products was established by GC and GC/MS analyses.     

Preparation of hierarchical polyaniline nanotubes based on self‐assembly and its electrochemical capacitance

This article reports the preparation and self‐assembly of polyaniline (PANI) nanotubes, which were chemically synthesized by using in situ doping polymerization in the presence of ammonium persulfate (APS; (NH₄)S₂O₈) as the oxidant without the use of an external template. The synthesized hierarchically nanotubes with a shape of a single nanotube with a length of 0.6 to 0.8 µm and an average with of 100 nm assembled from nanoparticles. The effects of the [salicylic acid]/[aniline] ratio on the size and capacitance of PANI nanotubes were studied. The specific capacitance behavior of the PANI nanotubes was also investigated by using cyclic voltammogram and galvanostatic charge–discharge tests. A maximum discharge‐specific capacitance of 422.5 F/g could be achieved, suggesting its potential application in electrode material for electrochemical capacitors. Copyright © 2011 John Wiley & Sons, Ltd.     

Effect of a “Zn Bridge” on the Consecutively Tunable Retention Characteristics of Volatile Random Access Memory Materials

Polyimide memory materials with a donor–acceptor structure based on a charge-transfer mechanism exhibit great potential for next-generation information storage technology due to their outstanding high-temperature resistance and good dimensional and chemical stability. Precisely controlling memory performance by limited chemical decoration is one of core challenges in this field. Most reported work mainly focuses on designing novel and elaborate electron donors or acceptors for the expected memory behavior of polyimides; this takes a lot of time and is not always efficacious. Herein, we report a series of porphyrinated copolyimides coPI−Znx (x=5, 10, 20, 50, 80), where x represents the mole percentage of Zn ion in the central core of the porphyrin. Experimental and theoretical analysis indicate that the Zn ion could play a vital bridge role in promoting the formation and stabilization of a charge-transfer complex by enhancing the hybridization of local and charge transfer (HLCT) excitations of porphyrinated polyimides, endowing coPI−Znx with volatile random access memory performance and continuously tunable retention time. This work could provide one simple strategy to precisely regulate memory performance merely by altering the metal content in porphyrinated polyimides.     

High‐performance holographic polymer‐dispersed liquid crystals by incorporating hyperbranched polymers

A minute amount (0.01–0.3 wt %) of ally isocyanate functionalized hyperbranched 2,2‐bis (hydroxymethyl) propionic acid (bis‐MPA) polyester‐16‐hydroxyl (HBP) was incorporated covalently into polyurethane acrylate‐based holographic polymer dispersed liquid crystals (HPDLCs), and its effects on the compound viscosity, grating kinetics, morphology, diffraction efficiency (DE), and electro‐optical properties of the HPDLC films were examined. HBP at low concentrations (0.01–0.05%) reduced the compound viscosity and domain size of liquid crystal (LC) significantly and augmented the cure rate and saturation DE by up to threefold compared to the HBP‐free compound. At high concentrations (0.10 and 0.30%), HBP increased the compound viscosity and decreased the rate of grating formation, giving rise to distorted LC‐polymer interfaces, which caused a significant decrease in the threshold and operating voltages. The rise and decay time showed a minimum and maximum, respectively, when the compound viscosity was a minimum at 0.03% HBP. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

In vitro and in vivo mineralization and osseointegration of nanostructured Ti6Al4V

Surface characteristics of the orthopedic implants remarkably affect the corresponding biological responses. In this study, Ti6Al4V alloy was subjected to the surface mechanical attrition treatment (SMAT) in order to achieve favorable surface properties. The SMAT substrates exhibited a highly hydrophilic surface with nanograins about 20–40 nm. Then, the in vitro and in vivo mineralizations were evaluated on the untreated and SMAT processed substrates. The in vitro experimental results showed a significant increase in the deposition of calcium-containing minerals on the SMAT surface both with and without osteoblasts. The in vivo experiments also revealed a higher bone mineral apposition on the SMAT processed implants after 8 and 12 weeks post operation. The well-organized bone formation on the SMAT substrates indicated an enhanced osseointegration on the bone-implant interface. Therefore, it was suggested that the obvious improvements of biomineralization and osseointegration were attributed to the nanostructure features on the SMAT surface, as well as the higher surface hydrophilicity.