Synthesis and properties of optically active poly(amide-imide)s containing axially dissymmetric 1,1 '-binaphthyl moieties

Novel optically active aromatic poly(amide-imide)s (PAIs) containing 1,1'-binaphthyl-2,2'-diyl units in the main chain were prepared by polycondensation reactions of newly synthesized dianhydride, 2,2'-bis(3,4-dicarboxylzenzamido)-1,1'-binaphthyl dianhydride[(S)-BN-DADA and (+/-)-BNDADA], with diamines, The properties of the resulted PAIs were fully characterized by a combination of investigations on inherent viscosity, thermal properties(DSC and TGA), specific rotation, CD and UV-Vis absorbance. These PAIs showed good solubilities, thermal properties and optical stabilities. Interesting UV-Vis absorption behavior of films casted from these PAIs was observed and analyzed.

Synthesis and characterization of poly(amide imide)s containing cyclohexylidene moieties with bulky substituents

Novel poly(amide imide)s (PAI) containing alkyl-substituted cyclohexylidene moieties were synthesized by conventional polycondensation of trimellitic anhydride chloride with novel aromatic diamines followed by chemical imidization using acetic anhydride and pyridine. The inherent viscosities of the resulting PAIs are relatively high and range from 71 to 112 mt g(-1). The prepared PAIs show excellent thermal stability and good solubility. The glass transition temperatures (T-g) measured by DSC are observed in the range of 312-342 degrees C. Furthermore, all the polymers are readily soluble in less hygroscopic organic solvents like cyclohexanone, gamma-butyrolactone as well as aprotic polar solvents.

Synthesis and characterization of thermotropic copolyesters and copoly(ester-amide)s containing oxyethylene-ether as the spacer

Flexible oxyethylene-ether was introduced into the aromatic copolyesters and copoly (ester-amide)s to reduce the melting point of resulting polymers. The melting point was greatly reduced to 200 degrees C or even lower in some cases, and the molecular weight was satisfactorily high as reflected by inherent viscosity. The polymers exhibited high thermal stability and good mechanical properties as determined by TGA and mechanical tests. The copolyester showed better crystallinity and liquid crystallinity than corresponding copoly (ester-amide)s with similar monomer composition as reflected by POM observation and WAXD study. The melting points for both copolyesters and copoly (ester-amide)s showed great dependence on the p-acetoxybenzoic acid (PAB) content in monomer composition and reached the lowest value when PAB was 29 mol%.

七氟丁酸酐有序超薄膜的制备与结构

在涂敷有聚合物PEI涂层的单晶硅表面上制备了HFBA单层分子膜,接触角测量及XPS结果表明,HFBA在PEI表面产生了化学吸附发生了化学键合(酰胺键),形成了低表面能的HFBA单分子层膜.这一吸附反应的动力学行为可能表现为Langmuir单分子层化学吸附.

Preparation and Tribological Studies of Stearic Acid Self-Assembled Monolayers on Polymer-Coated Silicon Surface

We present a good alternative method to improve the tribological properties of polymer films by chemisorbing a long-chain monolayer on the functional polymer surface. Thus, a novel self-assembled monolayer is successfully prepared on a silicon substrate coated with amino-group-containing polyethyleneimine (PEI) by the chemical adsorption of stearic acid (STA) molecules. The formation and structure of the STA-PEI film are characterized by means of contact-angle measurement and ellipsometric thickness measurement, and of Fourier transformation infrared spectrometric and atomic force microscopic analyses. The micro- and macro-tribological properties of the STA-PEI film are investigated on an atomic force microscope (AFM) and a unidirectional tribometer, respectively. It has been found that the STA monolayer about 2.1-nm thick is produced on the PEI coating by the chemical reaction between the amino groups in the PEI and the carboxyl group in the STA molecules to form a covalent amide bond in the presence of N,N'-dicyclohexylcarbodiimide (DCCD) as a dehydrating regent. By introducing the STA monolayer, the hydrophilic PEI polymer surface becomes hydrophobic with a water contact angle to be about 105degrees. Study of the time dependence of the film formation shows that the adsorption of PEI is fast, whereas at least 24 h is needed to generate the saturated STA monolayer. Whereas the PEI coating has relatively high adhesion, friction, and poor anti-wear ability, the STA-PEI film possesses good adhesive resistance and high load-carrying capacity and anti-wear ability, which could be attributed to the chemical structure of the STA-PEI thin film. It is assumed that the hydrogen bonds between the molecules of the STA-PEI film act to stabilize the film and can be restored after breaking during sliding. Thus, the self-assembled STA-PEI thin film might find promising application in the lubrication of micro-electromechanical systems (MEMS).

Modeling of Ammonothermal Growth of Nitrides

Bulk single crystals of GaN and AlN can be grown from supercritical fluids using the ammonothermal method, which utilizes ammonia as fluid rather than water as in the hydrothermal process. In this process, a mineralizer such as amide, imide or nitride is used to attack a bulk nitride feedstock at temperatures from 200°C to 500°C and pressures from 1 to 4 kbar. Ammonothermal systems have been modeled here using fluid dynamics, thermodynamics and heat transfer models. The nutrient is considered as a porous media bed and the fluid flow is simulated using the Darcy-Brinkman-Forchheimer model. The resulting governing equations are solved using the finite volume method. The effects of particle size on flow pattern and temperature distribution in an autoclave are analyzed.

Effects of Baffle Design on Fluid Flow and Heat Transfer in Ammonothermal Growth System of Nitrides

Efforts have been made in growing bulk single crystals of GaN front supercritical fluids using the ammonothermal method, which utilizes ammonia as fluid rather than water as in the hydrothermal process. Different mineralizers such as amide or azide and temperatures in the range of 200-600degreesC have been used to increase the solubility. The pressure is from 1 to 4 kbar. Modeling of the ammonothermal growth process has been used to identify factors which may affect the temperature distribution, fluid flow and nutrient transport. The GaN charge is considered as a porous media bed and the flow in the charge is simulated using the Darcy-Brinkman-Forchheimer model. The resulting governing equations are solved using the finite volume method. The effects of baffle design and opening on flow pattern and temperature distribution in an autoclave are analyzed. Two cases are considered with baffle openings of 15% and 20% in cross-sectional area, respectively.

Transport Phenomena in Ammonothermal Growth of Gallium Nitride

GaN can be used to fabricate blue/green/UV LEDs and high temperature, high power electronic devices. Ideal substrates are needed for high quality III-nitride epitaxy, which is an essential step for the manufacture of LEDs. GaN substrates are ideal to be lattice matched and isomorphic to nitride-based films. Bulk single crystals of GaN can be grown from supercritical fluids using the ammonothermal method, which utilizes ammonia as fluid rather than water as in the hydrothermal process. In this process, a mineralizer such as amide, imide or azide is used to attack a bulk nitride feedstock at temperatures from 200 - 500癈 and pressures from 1 - 4 kbar. Baffle design is essential for successful growth of GaN crystals. Baffle is used to separate the dissolving zone from the growth zone, and to maintain a temperature difference between the two zones. For solubility curve with a positive coefficient with respect to temperature, the growth zone is maintained at a lower temperature than that in the dissolving zone, thus the nutrient becomes supersaturated in the growth zone. The baffle opening is used to control the mixing of nutrients in the two zones, thus the transfer of nutrient from the lower part to the upper part. Ammonothermal systems have been modeled here using fluid dynamics, thermodynamics and heat transfer models. The nutrient is considered as a porous media bed and the flow is simulated using the Darcy-Brinkman-Forchheimer model. The resulting governing equations are solved using the finite volume method. We investigated the effects of baffle opening and position on the transport phenomena of nutrient from dissolving zone to the growth zone. Simulation data have been compared qualitatively with experimental data.

Cloning of bradykinin precursor cDNAs from skin of Bombina maxima reveals novel bombinakinin M antagonists and a bradykinin potential peptide

Bombinakinin M (DLPKINRKGP-bradykinin) is a bradykinin-related peptide purified from skin secretions of the frog Bombina maxima. As previously reported, its biosynthesis is characterized by a tandem repeats with various copy numbers of the peptide and sometimes co-expressed with other structure-function distinguishable peptides. At present study, two novel cDNAs encoding bombinakinin M and its variants were cloned from a cDNA library from the skin of the frog. The encoded two precursor proteins are common in that each contains three repeats of a novel 16-amino acid peptide unit and one copy of kinestatin at their N- and C-terminal parts, respectively. They differ in that the first precursor contains two copies of bombinakinin M and the second one contains one copy of a novel bombinakinin M variant. Bombinakinin M was found to elicit concentration-dependent contractile effects on guinea pig ileum, with an EC50 value of 4 nM that is four times higher than that of bradykinin (1 nM). Interestingly, the synthetic peptide (DYTIRTRLH-amide), as deduced from the 16-amino acid peptide repeats in the newly cloned cDNAs, possessed weak inhibitory activity on the contractile effects of bombinakinin M, but not on that of bradykinin. Furthermore, the newly identified bombinakinin M variant (DLSKMSFLHG-Ile(1)-bradykinin), did not show contractile activity on guinea pig ileum, but showed potentiation effect on the myotropic activity of bradykinin. In a molar raito of 1:58, it augmented the activity of bradykinin up to two-fold. (C) 2004 Elsevier B.V. All rights reserved.

Purification and characterization of hydrosoluble components from the sap of Chinese lacquer tree Rhus vernicifera

Continuous gradient elution chromatography (CGEC) was employed to purify and separate enzymes and polysaccharides from the sap of Rhus vernicifera Chinese lacquer tree. There are three different molecules with laccase enzyme activity. Two are enzymes of each other (L1, and L2), whereas the third (RL) is an entirely separate entity. Two polysaccharides (GP1 and GP2) were also found. The Rhus laccase (RL), and isoenzymes L1 and L2, have peak molecular masses of 109,100, 120,000, 103,000 respectively; each has four copper atoms per molecule, and the pI values were 8.2, 8.6, and 9.1, respectively. The structure of the laccases was studied by Fourier-transform infrared (FT-IR) and Matrix-assisted laser desorption/ionization time-of flight (MALDI-TOF) mass spectrometry. The typical amide I (1646 cm(-1)) and amide II (1545 cm(-1)) bands were observed. The results from MALDI-TOF were similar to those from CGEC, but the molecular mass from the MALDI-TOF was significantly different from that obtained from sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE). (c) 2006 Elsevier B.V. All rights reserved.

Development of a precolumn derivatization method for the determination of free amines in wastewater by high-performance liquid chromatography via fluorescent detection with 9-(2-hydroxyethyl)acridone

A simple, sensitive, and mild method for the determination of amino compounds based on a condensation reaction with fluorescence detection has been developed. 9-(2-Hydroxyethyl)acridone reacts with coupling agent N,N-carbonyldiimidazole at ambient temperature to form activated amide intermediate 9-(2-acridone)oxyethylcarbonylimidazole (AOCD). The amide intermediate (AOCD) preferably reacts with amino compounds under mild reactions in the presence of 4-(dimethylamino)pyridine (base catalyst) in acetonitrile to give the corresponding sensitively fluorescent derivatives with an excitation maximum lambda(ex) 404 mn and an emission maximum at lambda(em) 440 nm. The labeled derivatives exhibit high stability under reversed-phase conditions. The fluorescence intensities of derivatives in various solvents or at different temperatures were investigated. The method, in conjunction with a gradient elution, offers a baseline resolution of the common amine derivatives on a reversed-phase C-18 column. The LC separation for the derivatized amines shows good reproducibility with acetonitrile-water including 2.5% DMF as mobile phase. The relative standard deviations (n = 6) for each amine derivative are <4.5%. The detection limits (at a signal-to-noise ratio of 3) per injection were 0.16-12.8 ng/mL. Further research for the field of application, based on the AOCD amide intermediate as derivatization reagent, for the determination of free amines in real water samples is achieved.

Rare-Earth Metal Bis(alkyl)s Supported by a Quinolinyl Anilido-Imine Ligand: Synthesis and Catalysis on Living Polymerization of epsilon-Caprolactone

The tridentate ligand N-(2-((2,6-diisopropylphenylimino)methyl)phenyl)quinolin-8-amine (HL) was prepared. Treatment of HL with 1 equiv of Ln(CH2SiMe3)(3)(THF)(2) afforded the corresponding rare-earth metal bis(alkyl) complexes LLn(CH2SiMe3)(2)(THF)(n) (Ln = Sc, n = 0 (1); Y, n = 1 (2); Lu, n = 0 (3)) in high yields. Variable-temperature H-1 NMR spectral analysis showed that these complexes were fluxional at room temperature. Complexes 1 and 3 were THF-free, where the metal center adopted a square-pyramidal geometry, while in 2 the metal center generated a distorted octahedral geometry owing to the coordination of a THF molecule.

Rare-earth metal complexes stabilized by amino-phosphine ligand. Reaction with mesityl azide and catalysis of the cycloaddition of organic azides and aromatic alkynes

Stoichiometric reactions between mesityl azide (MesN(3), Mes = 2,4,6-C6H2Me3) and amino-phosphine ligated rare-earth metal alkyl, LLn(CH2SiMe3) (2)(THF) (L = (2,6-C6H3Me2)NCH2C6H4P(C6H5)(2); Ln = Lu (1a), Sc (1b)), amide, LLu(NH(2,6-(C6H3Pr2)-Pr-i))(2)(THF) (2) and acetylide at room temperature gave the amino-phosphazide ligated rare-earth metal bis(triazenyl) complexes, [L(MesN(3))]Ln[(MesN(3))-(CH2SiMe3)](2) (Ln = Lu (3a); Sc (3b)), bis(amido) complex [L(MesN3)] Lu[NH(2,6-C6H3 Pr-i(2))](2) (4), and bis(alkynyl) complex (5) (L(MesN(3))Lu (C CPh)(2))(2), respectively. The triazenyl group in 3 coordinates to the metal ion in a rare eta(2)-mode via N-beta and N-gamma atoms, generating a triangular metallocycle. The amino-phosphazide ligand, L(MesN(3)), in 3, 4 and 5 chelates to the metal ion in a eta(3)-mode via N-alpha and N-gamma atoms. In the presence of excess phenylacetylene, complex 3a isomerized to 3', where the triazenyl group coordinates to the metal ion in a eta(3) mode via Na and Ng atoms.

Polymerization of 2,2 '-Dimethyltrimethylene Carbonate by Lutetium Complexes Bearing Amino-Phosphine Ligands

A series of lutetium alkyl, amino, and guanidinato complexes based upon an amino-phosphine ligand framework had been prepared. These complexes were applied to initiate ring-opening polymerization of 2,2'-dimethyltrimethylene carbonate (DTC). The type of the initiator significantly influenced the catalytic activity of these complexes in a trend as follows: alkyl approximate to guanidinate > amide, whereas the complexes with flexible backbone between P and N atoms within the ligand exhibited higher activity than those with rigid backbone. The isolated PDTC had bimodal-mode molecular weight distribution. The molecular weights of each fraction increased linearly with the conversion, indicating that there might be two active species. This had been confirmed by analyses of oligomeric DTC living species and oligomer with NMR technique as the metal-alkoxide and the four-membered metallocyclic lactate. Kinetic investigation displayed that the polymerization rate was the first order with the monomer concentration.