A facile synthetic method for biphenyltetracarhoxylic dianhydrides

We report a facile and high-yielding procedure for preparing biphenyltetracarboxylic dianhydrides (BPDAs). This method relies on a nickel-catalyzed electroreductive coupling reaction of dimethyl 3-chorophthalate (3-DMCP) and/or dimethyl 4-chorophthalate (4-DMCP) with subsequent hydrolysis of tetra-ester and dehydration of tetra-acid.

Synthesis of neodymium hydroxide nanotubes and nanorods by soft chemical process

A facile soft chemical approach using cetyltrimethylammoniurn bromide (CTAB) as template is successfully designed for synthesis of neodymium hydroxide nanotubes. These nanotubes have an average outer diameter around 20 nm, inner diameter around 2 nm, and length ranging from 100 to 120 nm, high BET surface area of 495.71 m(2) g(-1). We also find that neodymium hydroxide nanorods would be obtained when CTAB absented in reaction system. The Nd(OH)(3) nanorods might act as precursors that are converted into Nd2O3 nanorods through dehydration at 550 degrees C. The nanorods could exhibit upconversion emission characteristic under excitation of 591 nm at room temperature.

Study on the integrated membrane processes of dehumidification of compressed air and vapor permeation processes

Blend modified polyimide (PI) hollow fiber membranes were used in vapor permeation for gas phase dehydration of ethanol. Dry air sweeping operation was used and the dry air was supplied by a dehumidification membrane module of compressed air. An integrated membrane process was composed. The effects of some factors, such as the modification of membrane materials, the humidity and current velocity of sweeping air, the operation temperature, on the efficiency of dehydration were discussed.

TG-DTA properties of new nonlinear optical materials: K(2)Ln(NO3)(5)center dot 2H(2)O (Ln = La, Ce, Pr, Nd, Sm)

Single crystals of K(2)Ln(NO3)(5). 2H(2)O (KLnN) (Ln = La, Ce, Pr, Nd, Sm) were grown from aqueous solution. The thermogravimetric analysis and differential thermal analysis curves of KLnN demonstrate that the processes of dehydration, melting, irreversible phase transformation and decomposition of NO3- take place in sequence in the heating processes (except KCN). There are three stages in the decomposition of NO3- in KLnN (Ln = La, Nd, Sm) while two in KLnN (Ln = Ce, Pr). K(2)Ln(NO3)(5) is formed at about 225 degrees C by the reaction of KNO3 and Ln(NO3)(3). nH(2)O (Ln = La, Ce, Pr, Nd). (C) 2000 Elsevier Science Ltd. All rights reserved.

Crystal growth and TG-DTA properties of K(2)Ln(NO3)(5).2H(2)O (Ln = La, Ce, Pr, Nd, Sm)

Single crystals of KLnN(Ln=La, Ce, Pr, Nd, Sm) can be grown in water solution with pH approximate to 1 similar to 2 at about 40 degrees C. Crystals of KLnN (Ln=La, Ce, Pr, Nd) are orthorhombic with space group Fdd2. KPrN crystal was grwon and its crystal structure was determined for the first time. The KPrN crystal parameters obtained by the direct method are as follows: a=21.411(3) Angstrom, b=11.2210(10)Angstrom, c=12.208(2) Angstrom, Z=6, R=0.0240. The TG-DTA curves of KLnN(Ln=La,Ce, Pr, Nd, Sm) demonstrate that the processes of dehydration, melt, irreversible phase transition and decomposition of NO3- take place in sequence with the temperature increasing(except KCN). There are three steps in the decomposition of NO3- in KLnN(Ln=La, Nd, Sm) while two steps in KLnN (Ln=Ce, Pr). K(2)Ln(NO3)(5). 2H(2)O are formed at about 225 degrees C by the reaction of the starting materials of KNO3 and Ln(NO3)(3). nH(2)O.

Synthesis and properties of optically active aromatic polyimides derived from optically pure 1,1'-bi-2-naphthol

A series of new optically active aromatic polyimides containing axially dissymmetric 1,1'-binaphthalene-2,2-diyl units were prepared from optically pure (R)-(+)-or (S)-(-)-2,2'-bis(3,4-dicarboxyphenoxy)-1,1'-binaphthalene dianhydrides and various aromatic diamines via a conventional two-step procedure that included ring-opening polycondensation and chemical cyclodehydration. The optically pure isomer of dianhydride was prepared by a nucleophilic substitution of optically pure (R)-(+)or (S)-(-)1,1'-bi-2-naphthol with 4-nitrophthalonitrile in aprotic polar solvent and subsequent hydrolysis of the resultant tetranitrile derivatives, followed by the dehydration of the corresponding tetracarboxylic acids to obtain the dianhydrides. These polymers were readily soluble in common organic solvents such as N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and m-cresol, etc., and have glass transition temperatures of 251-296 degrees C, and 5% weight loss occurs not lower than 480 degrees C. The specific rotations of the optically active polyimides ranged from +196 degrees to +263 degrees, and the optical stability and chiroptical properties of them were also studied. (C) 1997 John Wiley & Sons, Inc.

The synthesis of a 1,1'-bi-2-naphthol-based bis(ether anhydride) and aromatic polyimides derived therefrom

2,2'-Bis(3,4-dicarboxyphenoxy)-1,1'-binaphthyl dianhydride was used as a new monomer with various aromatic diamines to obtain polyimides by the usual two-step method. The bis(ether anhydride) was prepared by a nucleophilic substitution of I,1'-bi-2-naphthol with N-phenyl-4-chlorophthalimide, N-methyl-4-nitrophthalimide or 4-nitrophthalonitrile in aprotic polar solvent, and subsequent hydrolysis of the resulting bis(ether imide)s or bis(ether dinitrile), and then dehydration of the corresponding tetracarboxylic acid to afford the dianhydride. Most of the obtained polyimides were soluble in chloroform, pyridine, DMF, etc. The polyimide prepared from p-phenylene diamine was partial crystalline, whereas the others showed amorphous patterns in a WAXD study. These polymers have glass transition temperatures between 255-294 degrees C and 5% weight loss temperatures in the range of 502-541 degrees C in nitrogen and 473-537 degrees C in air. (C) 1997 Elsevier Science Ltd.

Synthesis and thermo-decomposition mechanism of rare earth complexes with phenylacetic acid

Rare earth complexes with phenylacetic acid (LnL(3) . nH(2)O, Ln is Ce, Nd, Pr, Ho, Er, Yb and Y, L is phenylacetate, n = 1-2) were prepared and characterized by elemental analysis, IR spectroscopy, chemical analysis, and X-ray crystal structure. The mechanism of thermal decomposition of the complexes was studied by means of TG-DTG, DTA and DSC. The activation energy and enthalpy change for the dehydration and melting processes were determined.

THE EFFECTS OF LANTHANIDE IONS AND THEIR COMPLEXES ON THE PHASE-TRANSITION PROPERTY OF DIPALMITOYLPHOSPHATIDYLETHANOLAMINE LIPOSOMES

The effects of metal ions and lanthanide complexes on the gel-to-liquid crystal phase transition temperature T-m of dipalmitoylphosphatidylethanolamine liposomes have been studied by differential scanning calorimetry (DSC) method. The results show that the addition of metal ions to the dipalmitoylphosphatidylethanolamine (DPPE) liposomes dispersions increases the main phase transition temperature T-m in the order of monovalent< divalent< trivalent cations. The enhancement of T-m is not large as increasing the lanthanide ions concentration. The enhancement of Pr3+ is larger than that of La3+. Remarkable differences were observed between La-citrate and La-lactate complexes at different pH solutions. At pH 7.0, La-citrate complex has no effect on the T-m, La-lactate complex, however, increases the T-m value, and the increase is larger than that of free lanthanide ions at the same concentration. The decrease of pH of complexes solutions lowers the phase transition temperature. We have preliminarily discussed the mechanism of the enhancements of lanthanide ions and the synergism of lanthanide ion and lactate ligand follow the ion induced dehydration of lipid and the potential effects of ion-lipid interaction.

STUDY ON COMPLEXES OF RARE-EARTH WITH L-PHENYLALANINE BY POTENTIOMETRY WITH CALORIMETRY

The stability constants and thermodynamic functions for complexes of rare earth with L-phenylalanine have been determined by potentiometry and calorimetry at 25-degrees-C and ionic strength of 0.15mol.dm-3(NaCl). Stability of the complexes shows the "Tetrad effect". The entropy change makes a predominant contribution to the stability of these complexes. The ligand is coordinated to rare earth ions through its -CO2- and -NH2 group, and dehydration of ions plays an important role in coordination reaction.

THERMAL DECOMPOSITIONS OF SOME BIOINORGANIC COMPLEXES OF EUROPIUM

Thermogravimetric and derivative thermogravimetric investigations for three kinds of bioinorganic complexes of europium with N-acetyl-DL-alanine, N-acetyl-DL-valine and DL-alanyl-DL-alanine have been performed. It was found that the water molecules in these solid state complexes are not directly coordinated to the europium ion and that there may be three or four steps in the thermal decomposition process of these complexes after dehydration. The possible thermal decomposition reactions of these bioinorganic complexes have been suggested and discussed.

CRYSTAL STRUCTURE AND THERMAL ANALYSIS OF ERBIUM COMPLEX WITH BENZENE ACETIC ACID

The crystal structure of erbium (III) complex of benzene acetic acid is reported. The complex crystallizes in the monoclinic space group P2(1)/a with a = 0,9008(3)nm, b=1.4242(5) nm, c=1.8437(7) nm, beta=98.80(3)degrees, V = 2.337(1) nm(3), Z = 4. The mechanism of thermal decomposition of complex has been studied by TG-DTG-DTA. The activation energy for dehydration reaction has been calculated by Freeman Carroll method. The enthalpy change for dehydration and phase change process has been determined.

TWO SPECIFIC CAUSES OF CELL MORTALITY IN FREEZE-THAW CYCLE OF YOUNG THALLI OF PORPHYRA YEZOENSIS (BANGIALES, RHODOPHYTA)1

Porphyra yezoensis Ueda is an important marine aquaculture crop with single-layered gametophytic thalli. In this work, the influences of thallus dehydration level, cold-preservation (freezing) time, and thawing temperature on the photosynthetic recovery of young P. yezoensis thalli were investigated employing an imaging pulse-amplitude-modulation (PAM) fluorometer. The results showed that after 40 d of frozen storage when performing thallus thawing under 10 degrees C, the water content of the thalli showed obvious effects on the photosynthetic recovery of the frozen thalli. The thalli with absolute water content (AWC) of 10%-40% manifested obvious superiority compared to the thalli with other AWCs, while the thalli thawed at 20 degrees C showed very high survival rate (93.10%) and no obvious correlation between thallus AWCs and thallus viabilities. These results indicated that inappropriate thallus water content contributed to the cell damage during the freeze-thaw cycle and that proper thawing temperature is very crucial. Therefore, AWC between 10% and 40% is the suitable thallus water content range for frozen storage, and the thawing process should be as short as possible. However, it is also shown that for short-term cold storage the Porphyra thallus water content also showed no obvious effect on the photosynthetic recovery of the thalli, and the survival rate was extremely high (100%). These results indicated that freezing time is also a paramount contributor of the cell damage during the freeze-thaw cycle. Therefore, the frozen nets should be used as soon as time permits.

Purification of R-phycoerythrin from Porphyra haitanensis (Bangiales, Rhodophyta) using expanded-bed absorption

R-phycoerythrin (R-PE) was purified from leafy gametophyte of Porphyra haitanensis T. J. Chang et B. F. Zheng (Bangiales, Rhodophyta) by a simple, scaleable procedure. Initially, phycobiliproteins were extracted by repeated freeze-thaw cycles, resulting in release from the algal cells by osmotic shock. Next, R-PE was recovered by applying the crude extract with a high concentration of (NH4)(2)SO4 salt directly to the expanded-bed columns loaded with phenyl-sepharose. An expanded-bed volume twice the settled-bed volume was maintained; then low (NH4)(2)SO4 concentration was used to develop the column. After two rounds of hydrophobic interaction chromatography (HIC), R-PE was purified by anion-exchange column. The method was also successful with free-living conchocelis of P. haitanensis. The purified R-PE was identified with electrophoresis, and absorption and fluorescence emission spectroscopy. The results were in agreement with those previously reported. The yield with a spectroscopic purity (OD565/OD280) higher than 3.2 (the ratio of A(565)/A(620) <= 0.02) was 1.4 mg . g(-1) of leafy gametophyte of P. haitanensis. For the free-living conchocelis of P. haitanensis extract, R-PE could be purified successfully with only one round of HIC. The yield with a spectroscopic purity (OD565/OD280) higher than 3.2 (the ratio of A(565)/A(620) <= 0.02) was 5.0 mg . g(-1) of free-living conchocelis of P. haitanensis. The method described here is a scaleable technology that allows a large quantity of R-PE to be recovered from the unclarified P. haitanensis crude extract. It is also a high protein recovery technology, reducing both processing costs and times, which enhances the value of this endemic Porphyra of China.

Cloning and characterization of beta-carotene ketolase gene promoter in Haematococcus pluvialis

The unicellular green alga Haematococcus pluvialis accumulates a highly valuable ketocarotenoid, astaxanthin, under various environmental stresses. beta-carotene ketolase (BKT) plays a key role in astaxanthin biosynthesis in H. pluvialis. In this paper, an approximate 700 bp 5'-flanking region of the bkt gene containing a putative promoter was cloned through walking upstream. The results of the sequence analysis showed that this bkt 5'-flanking region might have cis-acting elements such as sterol regulatory element (SRE-1)-like motifs, the C-repeat/dehydration responsive element (DRE) and al-3 proximal element (APE)-like motifs, except for typical TATA and CCAAT boxes. The results of the P-galactosidase assay and the transient expression of lacZ driven by a series of sequential deletions revealed that a minimal promoter-like region might exist from -630 to -408 bp, and the highest promoter activity was observed to span the positions from -630 to -308 bp. The results of the site-directed mutagenesis of a C-repeat/DRE and two APE-like motifs in a promoter-like region (-630 to -308 bp) suggested that two APE-like motifs might be essential for transcriptional control of the bkt gene.