Liquid crystalline hexa-amides and side chain polysiloxanes of azacrown [18]-N6

The hexa-4-dodecyloxybenzoyl derivative 1 of azacrown [18]-N₆ was originally reported to have a 'tubular' mesophase on the basis of its large central ring and 6-fold symmetry. Starting in the mesophase, annealing of 1 under a cover slip results in formation of a new crystalline phase that melts directly to an isotropic liquid at the temperature previously observed for the mesophase to isotropic transition. Thus the phase behaviour of 1 is kinetically controlled. The analogous hexa-3,4-bisdodecyloxybenzoyl derivative 2 of azacrown [18]-N₆ has no kinetic limitations to its phase changes and has an enantiotropic columnar liquid crystalline phase. We have synthesized side chain copolysiloxanes with a (CH₂)₁₁ spacer and 75-84 per cent by weight of the same 4-dodecyloxybenzoyl-[18]-N₆ mesogen. The polysiloxanes also display a liquid crystalline phase.     

Synthesis and characterization of novel thermoresponsive‐co‐biodegradable hydrogels composed of N‐isopropylacrylamide,poly(L‐lactic acid), and dextran

A series of novel multifunctional hydrogels that combined the merits of both thermoresponsive and biodegradable polymeric materials were designed, synthesized, and characterized. The hydrogels were copolymeric networks composed of N‐isopropylacrylamide (NIPAAM) as a thermoresponsive component, poly(L‐lactic acid) (PLLA) as a hydrolytically degradable and hydrophobic component, and dextran as an enzymatically degradable and hydrophilic component. The chemical structures of the hydrogels were characterized by an attenuated total reflection–Fourier transform infrared spectroscopy (ATR–FTIR) technique. The hydrogels were thermoresponsive, showing a lower critical solution temperature (LCST) at approximately 32 °C, and their swelling properties strongly depended on temperature changes, the balance of the hydrophilic/hydrophobic components, and the degradation of the PLLA component. The degradation of the hydrogels caused by hydrolytic cleavage of ester bonds in the PLLA component was faster at 25 °C below the LCST than at 37 °C above the LCST, determined by the ATR–FTIR technique. Due to their multifunctional properties, the designed hydrogels show great potential for biomedical applications, including drug delivery and tissue engineering. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5054–5066, 2004     

Analysis of Paeoniae Radix by high-performance liquid chromatography-electrospray ionization-mass spectrometry.

A method has been developed for the qualitative analysis of paeonol, paeoniflorin and their derivatives in Paeoniae Radix by high-performance liquid chromatography-electrospray ionization-mass spectrometry (HPLC-ESI-MS). Gradient elution with acetonitrile-water solvent system was employed in an HPLC-ESI-MS study. The negative-ion ESI mode was suitable for these compounds. The peaks were identified by their mass spectra, UV spectra and fragments of their MS2 spectra. The structures of three unknown compounds are inferred in this paper.     

Formation of β‐iPP in isotactic polypropylene/ethylene–propylene rubber blends: Effects of preparation method,composition, and thermal condition

The effects of preparation method, composition, and thermal condition on formation of β‐iPP in isotactic polypropylene/ethylene–propylene rubber (iPP/EPR) blends were studied using modulated differential scanning calorimeter (MDSC), wide angle X‐ray diffraction (WAXD), and phase contrast microscopy (PCM). It was found that the α‐iPP and β‐iPP can simultaneity form in the melt‐blended samples, whereas only α‐iPP exists in the solution‐blended samples. The results show that the formation of β‐iPP in the melt‐blended samples is related to the crystallization temperature and the β‐iPP generally diminishes and finally vanishes when the crystallization temperature moves far from 125 °C. The phenomena that the lower critical temperature of β‐iPP in iPP/EPR obviously increases to 114 °C and the upper critical temperature decreases to 134 °C indicate the narrowing of temperature interval, facilitating the formation of β‐iPP in iPP/EPR. Furthermore, it was found that the amount of β‐iPP in melt‐blended iPP/EPR samples is dependent on the composition and the maximum amount of β‐iPP formed when the composition of iPP/EPR blends is 85:15 in weight. The results through examining the effect of annealing for iPP/EPR samples at melt state indicate that this annealing may eliminate the susceptibility to β‐crystallization of iPP. However, only α‐iPP can be observed in solution‐blended samples subjected to annealing for different time. The PCM images demonstrate that an obvious phase‐separation happens in both melt‐blended and solution‐blended iPP/EPR samples, implying that compared with the disperse degree of EPR in iPP, the preparation method plays a dominant role in formation of β‐iPP. It is suggested that the origin of formation of β‐iPP results from the thermomechanical history of the EPR component in iPP/EPR. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1704–1712, 2007     

Metallothionein as a biomarker for mercury in tissues of rat fed orally with cinnabar

Cinnabar, as one of the most widely used mineral drugs in traditional Chinese medicines, has been proven to have prominent curative effects in clinical use for more than 2000 years. But the safety and toxicity of the drug has been under constant debate in clinic usage. Metallothionein (MT) contains about 30% of cysteine in the molecule, and plays an important detoxification role against heavy metals. In this study, it was used as a biomarker to assess mercurial accumulation in rats fed orally with cinnabar. After feeding rats with cinnabar by gastric gavage at different dosages and at different times, the distribution of heavy metals (including mercury, copper and zinc) and MT was investigated among rat tissues, including liver, kidney, heart, brain, testis and blood. Metals and MT determinations were carried out using inductively coupled plasma mass spectrometry (ICP‐MS) and a modified mercury saturation assay technique respectively. The results indicated that mercury was easily accumulated in the tissues of rats exposed to cinnabar, especially in kidney. For example: at a feeding dosage of 5 g kg^?1 (bw) for 4 weeks, the mercury concentrations in kidney were 13, 8.7, 21.6 and 26 times those in liver, testis, brain and heart respectively; and at 2.5 g kg^?1 (bw) for 2 weeks, the mercury concentrations in kidney were 21, 2.1, 3 and 21 times those in liver, testis, brain and heart respectively. In addition, mercury in kidney and liver of all cinnabar groups was significantly higher than that of the control group (P < 0.01). A high positive correlation observed between MT concentrations and mercury levels in both liver and kidney (R² = 0.9299, P < 0.02 for liver; R² = 0.9923, P < 0.0008 for kidney) indicated that MT could be used as a biomarker for mercury in tissues. Copyright © 2004 John Wiley & Sons, Ltd.     

Synthesis of some chiral liquid crystals and study of the effect of intramolecular hydrogen bonding on the phase behaviour

The synthesis of three new series of chiral Schiff's bases containing benzilideneaniline and 2-hydroxybenzilideneaniline moieties as mesogenic cores is presented. Differential scanning calorimetry, optical polarizing microscopy and X-ray diffraction measurements were used to study the phase transition temperatures and behaviour. The results reveal that most of these materials show chiral smectic mesomorphism.     

Synthesis of optically active poly(N‐propargylsulfamides) with helical conformation

A novel chiral N‐propargylsulfamide monomer ( 1a ) and its enantiomer ( 1b ) were synthesized and polymerized with (nbd)Rh⁺B^?(C₆H₅)₄ as a catalyst providing poly(1) (poly( 1a ) and poly( 1b )) in high yields (≥99%). Poly(1) could take stable helices in less polar solvents (chloroform and THF), demonstrated by strong circular dichroism signals and UV–vis absorption peaks at about 415 nm and the large specific rotations; but in more polar solvents including DMF and DMSO, poly(1) failed to form helix. Quantitative evaluation with anisotropy factor showed that the helical screw sense had a relatively high thermal stability. These results together with the IR spectra measured in solvents showed that hydrogen bonding between the neighboring sulfamide groups is one of the main driving forces for poly(1) to adopt stable helices. In addition, copolymerization of monomer 1a and monomer 2 was conducted, the solubility of poly(1) was improved drastically. However, the copolymerization had adverse effects on the formation of stable helices in the copolymers. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 500–508, 2007     

Synthesis of grafted poly(p‐phenyleneethynylene) with energy donor–acceptor architecture via atom transfer radical polymerization: Towards nonaggregating and hole‐facilitating light‐emitting material

In this contribution, we demonstrate a new effective methodology for constructing highly efficient and durable poly(p‐phenyleneethynylene) (PPE) containing emissive material with nonaggregating and hole‐facilitating properties through the introduction of hole‐transporting blocks into the PPE system as the grafting coils as well as building the energy donor–acceptor architecture between the grafting coils and the PPE backbone. Poly(2‐(carbazol‐9‐yl)ethyl methacrylate) (PCzEMA), herein, is chosen as the hole‐transporting blocks, and incorporated into the PPE system as the grafting coils via atom transfer radical polymerization. The chemical structure of the resultant copolymer, PPE‐g‐PCzEMA, was characterized by NMR and gel permeation chromatography, showing that the desirable copolymer was obtained with the narrow polydispersity. The increased thermal stability of PPE‐g‐PCzEMA was confirmed by thermogravimetric analysis and differential scanning calorimetry along with its macroinitiator. The optoelectronic properties of this copolymer were studied in detail by ultraviolet‐visible absorption, photoluminescence emission and excitation spectra, and cyclic voltammogram (CV). The results indicate that PPE‐g‐PCzEMA exhibits the solid‐state luminescent property dominated by individual lumophores, and also the energy transfer process from the PCzEMA blocks to the PPE backbone with a relatively higher energy transfer efficiency in the solid‐state compared to that of the solution state. Additionally, the hole‐injection property is greatly facilitated due to the presence of PCzEMA, as confirmed by CV profiles. All these data indicate that PPE‐g‐PCzEMA is a good candidate for use in optoelectronic devices. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3776–3787, 2007