Liquid-phase hydrogenation of furfural to tetrahydrofurfuryl alcohol catalyzed by polymer resin supported palladium catalysts

Three kinds of polymer resin supported Pd catalysts were prepared by mixing PdCl2, with alkaline styrene anion exchange resins[D392 -NH2, D382, -NHCH3, D301R, -NH(CH3)(2)], strongly alkaline styrene anion exchanged resin [201 X 7DVB, -NH+ (CH3)(3)] and alkaline epoxy exchange resin (701, -NH2), and hydrogenating in liquid phase at 1.013 X 10(5) Pa. The hydrogenation of furfural was studied under the reaction conditions such as solvent, temperature. Pd content in the supported catalyst and the amount of the catalyst. The yield of hydrogenation reaction of furfural markedly increased to 100% and the selectivity to tetrahydrofurfuryl alcohol increased to over 98% by polymer (alkaline styrene anion exchange resins D392, -NH2, D382, -NHCH3) supported palladium catalysts comparing with the yield over 70% and selectivity over 97% by palladium catalyst, in 50% alcohol-50% water or pure water solution at 1.013 X 10(5) Pa. The relationship between hydrogenation and the structures of functional group in the supporting resin was examined by XPS method.

Synthesis and catalytic properties of layered double hydroxides pillared by heteropolyoxometalate

Layered double hydroxides (LDHs) pillared with heteropolyoxometalate have been synthesized via both restructuring of hydrotalcite-like compounds and direct anion exchange under microwave field. LDHs and their derivatives are both found to be efficient for alkylation of isobutane with butene with a higher butene conversion and selectivity towards C-8(0).

Alrylation Over Layered Double Hydrotalcites Pillared by Heteropolyoxometalate Catalysts

Layered double hydroxides (LDHs) pillared with heteropolyoxo-metalate have been synthesized via both restructuring of hydrotalcite-like compounds and direct anion exchange under microwave field. LDHs and their derivatives are both found to be efficiency f

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.

Characterization of the main light-harvesting chlorophyll a/b-protein complex of green alga, Bryopsis corticulans

The main light-harvesting chlorophyll a/b -protein complex (LHC II) has been isolated directly from thylakoid membranes of shiphonous green alga, Bryopsis corticulans Setch. by using two consecutive runs of anion exchange and gel-filtration chromatography. Monomeric and trimeric subcomplexes of LHC 11 were obtained by using sucrose gradient ultracentrifugation. Pigment analysis by reversed-phase high performance liquid chromatography showed that chlorophyll a (Chl a), chlorophyll b (Chl b), neoxanthin, violaxanthin and siphonaxanthin were involved in LHC 11 from B. corticulans. The properties of electronic transition of monomeric LHC II showed similarities to those of trimeric LHC II. Circular dichroism spectroscopy showed that strong intramolecular interaction of excitonic dipoles between Chl a and between Chl b exist in one LHC II apoprotein, while the intermolecular interaction of these dipoles can be intensified in the trimeric structure. The monomer has high efficient energy transfer from Chl b and siphonaxanthin to Chl a similarly to that of the trimer. Our results suggest that in B. corticulans, LHC II monomer has high ordered pigment organization that play effective physiological function as the trimer, and thus it might be also a functional organization existing in thylakoid membrane of B. corticulans.

Isolation of the main light-harvesting chlorophyll a/b-protein complex from thylakoid membranes of marine alga, Bryopsis corticulans by a direct method

The main chlorophyll a/b light-harvesting complex (LHC 11) has been isolated directly from thylakoid membranes of marine green alga (Bryopsis corticulans Setch.) by two consecutive runs of anion exchange and gel-filtration chromatography. LHC 11 proteins in the membrane extracts treated with 3% n-Octyl-b-D-glucopyranoside (OG) obtained specific binding ability on Q Sepharose column, and thus were isolated from the thylakoid membranes in a highly selective fraction. The monomeric, trimeric and oligomeric subcomplexes of LHC 11 have been obtained by fractionation of the LHC 11 mixes with sucrose density gradient ultracentrifugation. The SDS-PAGE analysis of peptide composition and absorption spectrum showed that LHC 11 monomers, trimers and oligomers prepared through this work were intact and in high purity. Our report is the first to show that it is possible to purify LHC If directly from thylakoid membranes without extensively biochemical purification.

Large-scale recovery of C-phycocyanin from Spirulina platensis using expanded bed adsorption chromatography

C-phycocyanin was purified on a large scale by a combination of expanded bed adsorption, anion-exchange chromatography and hydroxyapatite chromatography from inferior Spirulina platensis that cannot be used for human consumption. First, phycobiliproteins were extracted by a simple, scaleable method and then were recovered by Phenyl-Sepharose chromatography in an expanded bed column. The purity (the A(620)/A(280) ratio) of C-phycocyanin isolated with STREAMLINE (TM) Column was up to 2.87, and the yield was as high as 31 mg/g of dried S. platensis. After the first step, we used conventional anion-exchange chromatography for the purification steps, with a yield of 7.7 mg/g of dried S. platensis at a purity greater than 3.2 and with an A(620)/A(650) index higher than 5.0. The fractions from anion-exchange chromatography with a level of purity that did not conform to the above standard were subjected to hydroxyapatite chromatography, with a C-PC yield of 4.45 mg/g of dried S. platensis with a purity greater than 3.2. The protein from both purification methods showed one absolute absorption peak at 620 nm and a fluorescence maximum at 650 nm, which is consistent with the typical spectrum of C-phycocyanin. SDS-PAGE gave two bands corresponding to 21 and 18 kDa. In-gel digestion and LC-ESI-MS showed that the protein is C-phycocyanin. (c) 2006 Elsevier B.V. All rights reserved.

Spectral changes of C-phycocyanin with different molar ratios of SPDP

Pure C-phycocyanin was prepared from Spirulina platensis using one-step anion-exchange chromatography. The C-PC obtained was with an absorption maximum at 620 nm and a fluorescence emission maximum at 640 nm when excited by 580 nm. SPDP is an excellent heterobifunctional crosslinker for thiolating amines. Different molar ratios of SPDP have remarkable influence on the absorption and fluorescence spectra of C-phycocyanin. The absorption maximum and fluorescence emission maximum both decreased and blue-shifted from 640 run to 630 nm as the molar ratios of SPDP increased. It was found that the molar ratios of SPDP to C-phycocyanin was not more than 100 was appropriate to being conjugated with other biomolecules from the absorption and fluorescence spectra of C-phycocyanin.

Antioxidant activities of sulfated polysaccharide fractions from Porphyra haitanesis

Three sulfated polysaccharide fractions (F1, F2, and F3) were isolated from Porphyra haitanesis, an important economic alga in China, through anion-exchange column chromatography and their in vitro antioxidant activities were investigated in this study. Galactose was the main sugar unit of the three fractions. The analytical results indicated that polysaccharide fractions from P. haitanesis had similar chemical components to porphyran from other species, but differed in their high sulfate content. The sulfate content of F1, F2 and F3 was 17.4%, 20.5% and 33.5% respectively. All three polysaccharide fractions showed antioxidant activities. They had strong scavenging effect on superoxide radical, and much weaker effect on hydroxyl free radical. Lipid peroxide in rat liver microsome was significantly inhibited, and H2O2 induced hemolysis of rat erythrocyte was partly inhibited by F1, F2 and F3. Among them, F3 showed strongest scavenging effect on superoxide radical; F2 had strongest effect on hydroxyl radical and lipid peroxide.

Antioxidant activity of sulfated polysaccharide fractions extracted from Laminaria japonica

Fucoidan, a group of sulfated heteropolysaccharide, was extracted from Laminaria japonica, an important economic alga species in China. Three sulfated polysaccharide fractions (F1, F2, and F3) were successfully isolated through anion-exchange column chromatography and had their antioxidant activities investigated employing various established in vitro systems, including superoxide and hydroxyl radical scavenging activity, chelating ability, and reducing power. Chemical analysis suggested that F1 and F3 were heteropolysaccharide in which galactose was the major component, while F2 was a typical fucoidan. All fractions possessed considerable antioxidant activity, and F1, F2 and F3 had stronger antioxidant ability than fucoidan in certain tests. The correlation between the sulfate content and scavenging superoxide radical ability was positive. Available data obtained with in vitro models suggested that the ratio of sulfate content/fucose was an effective indicator to antioxidant activity of the samples. (C) 2007 Elsevier B.V. All rights reserved.

利用MC-ICP-MS测定硼同位素及其在西藏地热和盐湖中的初步应用

Based on previous studies, boron can be separated from aqueous samples with Amberlite IRA-743 resin. Experiments on the elute temperature, elute volume and the dynamic resin exchange capacity have been performed in this study. Results show that the dynamic exchange capacity of the resin is 4.2mg B/g and at room temperature, boron fixed on the resin within this capacity level can be extracted quantitatively by using 5ml 2%HNO3. A new procedure has been developed for the measurement of boron isotope ratios in water samples using a Neptune MC-ICP-MS, after resolving the memory effect, which is a key problem, and investigating the impacts of mass bias and Si matrix effect. Using this method, it usually takes 20 min to perform one measurement on 0.1ppm boron solution with a precision of 0.23‰ (SD). If the relative deviation between a sample and the standard is large, the washout time needs to be doubled to achieve a higher precision. δ11B values of water samples from Yangbajing geothermal field vary from -10.53 to -9.13‰. Owing to the large difference B concentration and the small B isotope difference between deep geothermal water and surface water, B isotope ratios of the shallow geothermal fluids are dominated by the deep end member rather than the shallower one in the mixing process. As a consequence, δ11B-B relation is indicative basically of a dilution process. Vapor-liquid separation and calcite scaling also greatly influence B isotope fractionation. δ11B values of water samples from Dagejia geothermal field are from -15.98‰ to -11.67‰. Boron in Changma River near the field has two sources, freshwater lakes (Dajiamang Lake and Canke Lake) and geothermal waters. Finally, a preliminary discussion is included on boron geochemical characteristics of the salt lakes in Shuanghu area and other geothermal fields, to provide information for future studies on boron isotope geochemistry of geothermal systems and salt lakes in Tibet.

Lu-Hf同位素的MC-ICP-MS实验方法及其在华北克拉通典型火山岩研究中的应用

Over past ten years, a great development has been made in the Lu-Hf isotopic system with the advent of MC-ICP-MS. Based on a comprehensive review of available references in the related field, a novel analytical protocol of three exchange chromatographies after one mixed acid attacking geological samples was developed in this work, which not only avoids common multiple sample treatments for natural inhomegeneous samples, but also is useful for Rb-Sr, Sm-Nd and Lu-Hf isotopic system simultaneously, especially for the garnet- and apatite-bearing rocks for the Sm-Nd and Lu-Hf geochronology. An analytical procedure for the Lu and Hf concentration in geological samples determined by by ID-MC-ICP-MS was detailedly investigated. The Hf yield is > 90 % and total procedural blank is less than. 50 pg for Hf and 10 pg for Lu, respectively. The developed method was successfully applied to the determination of Lu and Hf concentrations for USGS geological materials. A one-column procedure for Hf purification in geological samples using common anion exchange chromatography and its isotopic analyses by MC-ICP-MS were also established. Multiple analyses of Standard Reference Materials demonstrate that this method was simple, time-saving, cheap and efficient, especially suitable for the Hf isotopic compositions of young samples. Finally, the measurements of Sr and Nd isotopic compositions using Neptune MC-ICP-MS were described briefly, which indicates that Neptune MC-ICP-MS can precisely measure Sr and Nd isotopic compositions as the TIMS does, even more efficient and less time-consuming than the TIMS method. The Hf isotopic characteristics of typical volcanic rocks (Cenozoic Changle-Linqu basalts, Mesozoic Fangcheng basalts, Mesozoic Jianguo basalts, Mesozoic Wulahada high-Mg andesite, Cenozoic Fanshi, Zuoquan and Xiyang-Pingding basalts of the Taihang Mountains, Paleozoic diamondiferous Menyin and Fuxian Kimblites) from the North China Craton were firstly studied in this work. Coupled with Nd isotopic compositions, it shows that the Hf isotopes could be a better tracer for mantle sources than the Nd isotopes. Individual kimberlite fields from both the Mengyin and Fuxian regions have quite uniform Hf isotopic compositions, similar to the situation for the Nd isotopes.

Hydrodynamics in an expanded bed of large size ion-exchange resin, and natural product adsorption

Successful applications of expanded bed adsorption (EBA) technology have been widely reported in the literature for protein purification. Little has been reported on the recovery of natural products and active components of Chinese herbal preparations using EBA technology. In this study, the hydrodynamic behavior in an expanded bed of cation resin, 001 x 7 Styrene-DVB, was investigated. Ephedrine hydrochloride (EH) was used as a model natural product to test the dynamic binding capacity (DBC) in the expanded bed. EBA of EH directly from a feedstock containing powdered herbs has also been investigated. These particles are different from commercially available expanded bed adsorbents by virtue of their large size (20S to 1030 gm). When the adsorbent bed is expanded to approximately 1.3 to 1.5 times its settled bed height, the axial liquid-phase dispersion coefficient was found to be of the order 10(-5) m(2) s(-1), which falls into the range 1.0 x 10(-6) to 1.0 X 10(-5) m(2) s(-1) observed previously in protein purification. Because of the favorable column efficiency (low axial dispersion coefficient), the recovery yield and purification factor values of EH directly from a feedstock reached 86.5% and 18, respectively. The results suggest that EBA technology holds promise for the recovery of natural products and active components of Chinese herbal preparations.

Counterion exchange at the surface of polyelectrolyte multilayer film for wettability modulation

Counterions present at the surface of polyelectrolyte multilayers (PEMs) were utilized for modulation of surface wettability via ion exchange. The PEM film was dipped in aqueous solutions of different anions, respectively, and the water contact angle of the surface varied from about 10 degrees to 120 degrees, depending on the hydration characteristics of the anion. The ion exchange mechanism was verified by X-ray photoelectron spectroscopy. The process was rapid and reversible. Ionic strength of the polyelectrolyte solution used for preparing the PEMs was found to be crucial to the surface wetting properties and the reversibility and kinetics of the process, and the effects were correlated to the surface density of the excess charge and counterion. This work provides a general, facile and rapid approach of surface property modulation.

Direct synthesis of ordered N-methylimidazolium functionalized mesoporous silica as highly efficient anion exchanger of Cr(VI)

Ordered N-methylimidazolium functionalized mesoporous silica (SBA-15) anion exchangers were directly synthesized by co-condensation of tetraethoxysilane with 1-methyl-3(triethoxysilylpropyl)imidazolium chloride. The prepared samples with rod-like morphology showed high surface areas (> 400 m(2) g(-1)), well-ordered pores (> 58 angstrom), and excellent thermal stability up to 387 degrees C. The adsorption behaviors of Cr(VI) from aqueous solution on the anion exchangers were studied using the batch method. The anion exchangers had high adsorption capacity ranging from 50.8 to 90.5 mg g(-1), over a wider pH range (1-8) than amino functionalized mesoporous silica. The adsorption rate was fast, and the maximum adsorption was obtained at pH 4.6. The adsorption data for the anion exchangers were consistent with the Langmuir isotherm equation. Most active sites of the anion exchangers were easily accessible. The mixed solution of 0.1 mol L-1 NH3 center dot H2O and 0.5 mol L-1 NH4Cl was effective desorption solution, and 95% of Cr(VI) could be desorbed.