Synthesis of lanthanide-alkylaluminium bimetallic complexes and studies on their catalytic activities for polymerization of some polar monomers

Three new lanthanide (Ln)-alkylaluminium (Al) bimetallic complexes with the formula [(mu-CF3CO2)(2)Ln(mu-CF3CHO2)AIR(2) . 2THF](2) (Ln = Nd, Y, R=i-C4H9 (i-Bu); Ln=Eu, R=C2H5(Et); THF=tetrahydrofuran) were synthesized by the reaction of Ln(CF,CO,), (Ln=Nd, Y) with HAI (i-Bu)(2) and of Eu(CF3CO2)(3) with AlEt(3), respectively. Their crystal structures were determined by X-ray diffraction at 233 K. [(mu-CF3CO2)(2)Nd (mu-CF3CHO2)Al(i-Bu)(2) . 2THF](2) (Nd-Al) and [(mu-CF3CO2)(2)Y(mu-CF3CHO2)Al(i-Bu)(2) . 2THF](2) (Y-Al) are isomorphous and crystallize in space group with a=12.441(3) Angstrom [12.347(5) Angstrom for Y-Al], b=12.832(3) Angstrom [12.832(4) Angstrom], c=11.334(3) Angstrom [11.292(8) Angstrom], alpha=104.93 (2)degrees [104.45(4)degrees], beta=98.47(2)degrees [98.81(4)degrees], gamma=64.60(2)degrees [64.30(3)degrees], R=0.519 [0.113], R(w)=0.0532 [0.110], Z=1 and [(mu-CF3CO2)(2)Eu(CF3CHO2)AlEt(2) . 2THF](2)(Eu-Al) in space group P2(1)/n with a=11.913(6) Angstrom, b=14.051(9) Angstrom, c=17.920(9) Angstrom, alpha=101.88(11)degrees, beta=gamma=90 degrees, R=0.0509, R(w)=0.0471 and Z=2. The six CF3CO2- (including CF3CHO2-) of each complex, among which pairs are equivalent, coordinated to Ln and Al in three patterns: (A) the two oxygen atoms in one of the three CF3CO2- type coordinated to two different Ln; (B) the two oxygen atoms in the second of CF3CO2- type coordinated to Ln and Al, respectively; (C) one of the two oxygen atoms in the third CF3CO2- type bidentately coordinated to two Ln and another oxygen coordinated to Al and one of the two Ln, respectively. Unlike types A and B, in type C the carboxyl carbon with a hydrogen atom bonded to it was found to appear as an sp(3)-hybridized configuration rather than an sp(2)-one. 1D and 2D NMR results further confirmed the existence of such a disproportionated CF3CHO2- ligand. Methyl methacrylate (MMA) and epichlorohydrin (ECH) could be polymerized by Y-Al or Eu-Al as a single-component catalyst and highly syndiotactic poly(MMA) was obtained. THF could also be polymerized by Y-Al in the presence of a small amount of ECH.

Studies on three-dimensional quantitative structure-activity relationships between the structures of N-nitroso compounds and their carcinogenic activities

Comparative molecular fiels analysis (CoMFA) has been applied to the studies of the correlation of the N-nitroso compounds and their carcinogenic activities, The comparison of CoMFA results with different lattice spacing and different atom probes was investigated, CoMFA resulted in a quantitative description of the major steric and electrostatic field effects and gave significant new insights to factors governing potency.

Influence of intraperitoneal injection of rare earth compounds on the activities of antioxidant enzymes and the level of lipid peroxidation in mice livers

Following intraperitoneal injection of lanthanum and terbium chloride and their complexes of diethyltriaminopentagacetic acid (DTPA) to adult mice with a dose of 0.28 mmol/kg body weight/day for three days. The activities of superoxide dismutase (SOD) and glutathione peroxidase (GSH-Px) and the content of lipid end product, malonaldehyde (MDA) in the mice livers have been assayed respectively. The results show that the activity of SOD was increased and the content of MDA was reduced for LaCl3 treated mice and the two targets were not changed for TbCl3, but the activity of GSH-Px was reduced markedly for both LaCl3 and TbCl3 while the above three targets were not changed for La-DTPA and Tb-DTPA complexes.

RELATIONSHIP BETWEEN CONFORMATION OF TASTE COMPOUNDS AND THEIR ACTIVITIES

The conformation analysis and study on structure-taste relation-ships of 4 taste compounds have been performed, the results reveal that the sweetnees will decrease with the increase of the specific dihedral angle O-1-C-2-C-3-C-4, and the mechanism was intepreted.

SYNTHESES AND CHARACTERIZATION OF [(MU-CF3CO2)(2)LN(MU-CF3CHO2)ALR(2)CENTER-DOT-2THF](2) AND THEIR CATALYTIC ACTIVITIES FOR POLYMERIZATION OF SOME POLAR MONOMERS

Three new bimetallic complexes were synthesized and crystalized by reactions of (CF3CO2)(3)Ln With R(1) AlR(2)(Ln=Nd and Y, R(1)=H, R=i-C4H9; Ln=Eu, R=R(1)=C2H5) in tetrahydrofuran solution, and their crystal structures were determined using a X-ray diffraction method. The structures and the questions on valence state and noncoplanarity in the structures were confirmed and cracked by means of H-1 NMR and C-13 NMR spectra, especially by C-13-H-1 COSY 2D NMR technique. A general formula of molecules of the three rare earth complexes was defined as follows: [(mu-CF3CO2)(2)Ln(mu-CF3CHO2)AlR(2) . 2THF](2) A mechanism on the formation of the new complexes was also proposed through the following five steps: alkylating, beta-elimination (or hydrogenation), hydrogen transfer, linkage and association. Both Y-Al and Eu-Al complexes function as a catalyst in polymerization of MMA and ECH. The polymer obtained from the first monomer is mainly syndiotactic chain structure and the polymerization of the last monomer shows higher catalytic activity. The Y-Al complex also capable of ring-opening polymerization of THF in case of adding-vary small amount of ECH and a oxonium ion mechanism of THF polymerization was suggested from the analysis of THF polymer terminal.

Synthesis, structures and antitumor activities of beta-phenolester propyl germanium sesquioxides

Eight new compounds of (GeCH2CH (CH3) COOAr)(2)O-3 type were synthesized. Four of them were tested for antitumor activities against Hela cells in vitro, showing considerable tumor inhibitory activities.

In vitro antioxidative activities of extract and semi-purified fractions of the marine red alga, Rhodomela confervoides (Rhodomelaceae)

The methanol-chloroform extract of the marine red alga, Rhodomela confervoides, was measured for antioxidant activity, using the alpha,alpha-diphenyl-beta-picrylhydrazyl radical-scavenging assay and the beta-carotene-linoleate bleaching assay systems, and compared with those of the positive Controls of butylated hydroxytoluene, gallic acid and ascorbic acid, The active extract was further purified by liquid-liquid partition to afford four fractions, of which the ethyl acetate-soluble (EA) fraction exhibited the strongest antioxidant activity in both assay systems. This fraction was further divided into seven subfractions, designated as EA1-EA7, by silica gel vacuum liquid chromatography. in most cases, EA1 and EM Were found to possess the strongest activity. The total phenolic contents and reducing powers of the extract, fractions, and subfractions were also determined. Significant associations between the antioxidant potency and the total phenolic content, as well as between the antioxidant potency and the reducing power, were found for the tested fractions and subfractions. (c) 2008 Elsevier Ltd. All rights reserved.

Algal biotechnology industries and research activities in China

In old China there were very few people engaged in the study of the algae, but in new China, freshwater and marine algae are studied by over one hundred old and new phycologists. There is now an algal biotechnology industry consisting of an aquaculture industry, producing large amounts of the seaweeds Laminaria, Porphyra, Undaria, Gracilaria, eucheumoids, and the microalgae Dunaliella and Spirulina. There is also a phycocolloid industry, producing algin, agar and carrageenan; an industry producing chemicals and drugs, such as iodine, mannitol, phycocyanin, beta -carotene, PSS (propylene glycol alginate sulfate) and FPS (fucose-containing sulfated polysaccharides) and an industry producing food, feed and fertilizer. The Laminaria cultivation industry produces about 900,000 t dry Laminaria, probably the largest producer in the world and 13,000 t algin, undoubtedly one of the largest algin producer in the world.

Optimization of conditions for tetraspore release and assessment of photosynthetic activities for different generation branches of Gracilaria lemaneiformis Bory

Gracilaria lemaneiformis Bory is an economically important alga that is primarily used for agar production. Although tetraspores are ideal seeds for the cultivation of G. lemaneiformis, the most popular culture method is currently based on vegetative fragments, which is labor-intensive and time-consuming. In this study, we optimized the conditions for tetraspore release and evaluated the photosynthetic activities of different colonies formed from the branches of G. lemaneiformis using a PAM (pulse-amplitude-modulated) measuring system. The results showed that variations in temperature and salinityhad significant effects on tetraspore yield. However, variations in the photon flux density (from 15 mu mol m(-2) s(-1) to 480 mu mol m(-2) s(-1)) had no apparent effect on tetraspore yield. Moreover, the PAM-parameters Y(I), Y(II), ETR(I), ETR(II) and F (v)/F (m) of colonies formed from different branches showed the same trend: parameter values of first generation branches > second generation branches > third generation branches. These results suggest that the photosynthetic activities of different colonies of branches changed with the same trend. Furthermore, photosynthesis in G. lemaneiformis was found to be involved in vegetative reproduction and tetraspore formation. Finally, the first generation branches grew slowly, but accumulated organic compounds to form large numbers of tetraspores. Taken together, these results showed that the first generation branches are ideal materials for the release of tetraspores.

Simple, mild and convenient synthesis of two novel N-dichloroacetyl oxazolidines and their biological activities

Two N-dichloroacetyl oxazolidines were synthesized with a simple, mild and convenient method. All the compounds were characterized by IR, (HNMR)-H-1 and elemental analysis. The preliminary biological test showed that the compounds protected maize against injury by some herbicides to some extent.

Study on impact of dinoflagellate Alexandrium tamarense on life activities of marine bivalves

The effects of a PSP producing dinoflagellate Alexandrium tamarense on marine bivalves at their several important life,stages: egg, D - shape larva, eyespot larva, juvenile and adult, were studied! The results show that the hitching survival, activity, filtration and! growth were adversely affected by the alga and the impact was significantly increased with the increase of algal density. The inhibitory effect on egg hatching was most significant, which the hatching rate was only 30% of the control when exposed to the alga at 100 cell/cm(3) after 36 h. Further experiments show that the algal culture, re-suspended cells and cell fragments had the inhibitory effect, while no such effect was from the cell-free medium, cell contents and standard STX. The results indicate that the alga could produce unknown toxins, rather than PSP, associated with the cell surface.

Summer feeding activities of zooplankton in Prydz Bay, Antarctica

Grazing of dominant zooplankton copepods (Calanoides acutus. and Metridia gerlachei), salps (Salpa thompsoni) and microzooplankton was determined during the austral summer of 1998/1999 at the seasonal ice zone of the Prydz Bay region. The objective was to measure the ingestion rates of zooplankton at the seasonal ice zone, so as to evaluate the importance of different groups of zooplankton in their grazing impact on phytoplankton standing stock and primary production. Grazing by copepods was low, and accounted for less than or equal to 1% of phytoplankton standing stocks and 3.8-12.5% of primary production for both species during this study, even the ingestion rates of individuals were at a high level compared with previous reports. S. thompsoni exhibited a relatively high grazing impact on primary production (72%) in the north of our investigation area. The highest grazing impact on phytoplankton was exerted by microzooplankton during this investigation, and accounted for 10-65% of the standing stock of phytoplankton and 34-100% of potential daily primary production. We concluded that microzooplankton was the dominant phytoplankton consumer in this study area. Salps also played an important role in control of phytoplankton where swarming occurred. The grazing of copepods had a relatively small effect on phytoplankton biomass development.

Feeding activities of zooplankton in the Bohai Sea

The Bohai Sea was the site of the Chinese national GLOBEC programme. During the June 1997 cruises of R/V Science No.1, observations and experiments on zooplankton feeding were conducted. At five 48 h time-series stations the following observations and measurements on zooplankton were carried out: (1) diurnal vertical migration, by collecting samples at different layers every 3 h with a closing net; (2) diurnal feeding rhythms, by gut pigment analysis; and (3) ingestion rate, by both gut pigment analysis and the dilution method. A classification by body size was used to deal with the diversity of species and developmental stages of zooplankton assemblages. Samples were separated into three size groups: small (200-500 mu m), medium (500-1000 mu m) and large (> 1000 mu m). The results showed that the copepods (Calanus sinicus, Paracalanus parvus, Acartia bifilosa and Centropages mcmurrichi) performed clear diurnal vertical migrations. However, their behaviour was different at different stations. The variation in gut pigment content over the 24 h cycle showed strong diurnal feeding rhythms, particularly for the large size group. Gut pigment contents reached their daily maximum during the time from dusk to midnight (18:00-24:00). The peak value was about 10 times the minimum observed in the daytime. The in situ daily grazing rate, based on gut pigment contents and evacuation experiments, was 4.00-12.65 ng chla ind(-1) day(-1) for the small size group, 5.99-66.58 ng chla ind(-1) day(-1) for the medium size group and 31.31-237.13 ng chla ind(-1) day(-1) for the large size group. The copepods consumed only a small part (2.90-13.52%) of the phytoplankton biomass hut about 77% of the daily production. The grazing mortality rate of phytoplankton by microzooplankton (<200 mu m) measured by the dilution method ranged from 0.43 to 0.69 day(-1) The calculated daily consumption of phytoplankton biomass was 35-50%, and 85-319% of the potential production.

In vitro antioxidant activities of acetylated, phosphorylated and benzoylated derivatives of porphyran extracted from Porphyra haitanensis

Porphyran extracted from red algae Porphyra haitanensis is a sulfated polysaccharide, which possesses excellent antioxidant activities. In this study, we prepared the acetylated, phosphorylated and benzoylated derivatives of porphyran. And then the antioxidant activities of all the samples were investigated including scavenging effects of superoxide and hydroxyl radicals and reducing power. The results of chemical analysis and FT-IR spectrum showed the modifications of porphyran were successful. And in addition, we found that certain derivative exhibited stronger antioxidant activity than raw material. And the mechanism of the structure-function relationship of these derivatives needs to be attended to. (C) 2009 Elsevier Ltd. All rights reserved.

Preparation of the different derivatives of the low-molecular-weight porphyran from Porphyra haitanensis and their antioxidant activities in vitro

Porphyran extracted from Porphyra haitanensis is a sulfated polysaccharide, which possesses excellent antioxidant activities. In this study, we prepared one low-molecular-weight porphyran and its sulfated, acetylated, phosphorylated and benzoylated derivatives. Their antioxidant activities were investigated including scavenging effect of superoxide, hydroxyl and 1,1-diphenyl-2-picrylhydrazyl radicals. The results of chemical analysis and FT-IR spectrums showed the modification was successful. And in addition, we found that certain derivative exhibited stronger antioxidant activity than low-molecular-weight porphyran. The benzoylated derivative showed the most excellent antioxidant activity in three assays, so this derivative needs to be attended to. (C) 2009 Elsevier B.V. All rights reserved.