An acidic polysaccharide with xylose branches from Porphyra yezoensis

An acidic polysaccharide (PY3) was isolated from the hot water extract of the red algae Porphyra yezoensis by successive column chromatographies over DEAE-cellulose and Sephadex G-200. PY3 with an average molecular weight of 1.8x10(5) was demonstrated to be composed of galactose (Gal), 3,6-anhydrogalactose (3,6-AnGal), 6-OSO3-galactose (6-OSO3-Gal) and xylose (Xyl) in an approximate molar ratio of 25 : 15, 10, 1. In view of Smith degradation and methylation and on the basis of spectral evidence including those of IR, GC, GC-MS, and H-1 and C-13 NMR, the most probable repeating unit of PY3 could be proposed as [(1-->3)beta -D-Gal(1 --> 4)alpha -L-3,6-AnGal](3)-[(1 --> 3)beta -D-Gal(1 --> 4)alpha -L-6-OSO3-Gal](2) with a xylose moiety at the C-6 of one of every twenty-five beta -D-Gal residues. To our knowledge, PY3 was shown to be the first porphyran possessing occasional xylose branches.

Molecular cloning and expression of a novel Kazal-type serine proteinase inhibitor gene from Zhikong scallop Chlamys farreri, and the inhibitory activity of its recombinant domain

Serine proteinase inhibitors (SPIs) play important roles in host physiological and immunological processes in all multicellular organisms. A novel Kazal-type SPI gene was cloned from the Zhikong scallop Chlamys farreri (designated as CfKZSPI) by expressed sequence tag (EST) and rapid amplification of cDNA ends (RACE) approaches. The full-length cDNA of CfKZSPI was of 1788 nucleotides with a canonical polyadenylation signal sequence AATAAA and a polyA tail, and an open reading frame (ORF) encoding a polypeptide of 509 amino acids with a putative signal peptide of 22 amino acids. The deduced amino acid sequence of CfKZSPI contained 12 tandem Kazal domains with high similarity to other Kazal-type SPIs. The temporal expression of CfKZSPI in hemocytes after Vibrio anguillorum challenge was recorded by quantitative real-time RT-PCR. The relative mRNA expression level of CfKZSPI was up-regulated and reached 43.6-fold at 3 h post-challenge. After a decrease at 6 h, the expression Level increased again and reached 207.8-fold at 12 h post-challenge. The 12th Kazal domain of CfKZSPI was recombined into pET-32a(+) and expressed in Escherichia coli Rosetta-gami (DE3) to investigate its inhibitory activity. The purified recombinant protein (rCf KZSPI-1 2) showed significant inhibitory activity against trypsin but no activity against thrombin. When the molar ratio of inhibitor to trypsin reached 1:1, almost 90% of the enzyme activity could be inhibited, which suggested that one molecule of rCfKZSPI-12 was able to inhibit one molecule of trypsin. Kinetics analysis with Dixon plot showed that the inhibition constant (K-i) of rCfKZSPI-12 to trypsin was 173 nmol L-1. These results indicated that CfKZSPI was a novel Kazal-type SPI with significant inhibitory activity against trypsin, and was suspected to be involved in scallop immune response. (c) 2008 Elsevier Ltd. All rights reserved.

Nutrients in the Changjiang River

N, P and SiO3-Si in the Changjiang mainstream and its major tributaries and lakes were investigated in the dry season from November to December, 1997, and in the flood season in August and October, 1998. An even distribution of SiO3-Si was found along the Changjiang River. However, the concentrations of total nitrogen, total dissolved nitrogen, dissolved inorganic nitrogen, nitrate and total phosphorus, total particulate phosphorus increased notably in the upper reaches, which reflected an increasing impact from human activities. Those concentrations in the middle and lower reaches of the Changjiang River were relatively constant. Dissolved N was the major form of N and the particulate P was the major form of P in the Changjiang River. The molar ratio of dissolved N to dissolved P was extremely high (192.5-317.5), while that of the particulate form was low (5.6-37.7). High N/P ratio reflected a significant input of anthropogenic N such as N from precipitation and N lost from water and soil etc. Dissolved N and P was in a quasi-equilibrium state in the process from precipitate to the river. In the turbid river water, light limitation, rather than P limitation, seemed more likely to be a controlling factor for the growth of phytoplankton. A positive linear correlationship between the concentration of dissolved N and the river's runoff was found, mainly in the upper reaches, which was related to the non-point sources of N. Over the past decades, N concentration has greatly increased, but the change of P concentration was not as significant as N. The nutrient fluxes of the Changjiang mainstream and tributaries were estimated, and the result showed that the nutrient fluxes were mainly controlled by the runoff, of which more than a half came from the tributaries. These investigations carried out before water storage of the Three Gorges Dam will supply a scientific base for studying the influences of the Three Gorges Dam on the ecology and environment of the Changjiang River and its estuary.

Nutrient compositions of cultured Thalassiosira rotula and Skeletonema costatum from the Jiaozhou Bay in China

Carbon, nitrogen, phosphorus, silicon composition of cultured two different sized phytoplankton common species of Thalassiosira rotula and Skeletonema costatum from the Jiaozhou Bay were measured. Carbon, nitrogen, phosphorus, silicon contents in cell were. obvious higher in T. rotula than in S. costatum, but the percents of nitrogen, phosphorus, silicon contents in cell dry mass in T. rotula were lower than those in S. costatum. The dry mass concentrations of nitrogen,phosphorus,silicon in S. costatum were much higher than those in T. rotula, particularly silicon, the former was 6.4 times of the latter, showing that S. costatum could more assimilate these elements. Especially, S. costatum had competitive dominance for assimilating silicon, which is beneficial to its becoming a major dominant species in relative short silicon of the Jiaozhou Bay. There were some differences in numerical value of nutrient ratios both laboratory-cultured phytoplankton and different sized suspended particulates (mainly phytoplankton) in the Jiaozhou Bay, which was caused by the changes of environment. High contents of carbon, nitrogon and relative low phosporus,silicon, high molar ratio of nitrogen to phosphorus (far higher than Redfield value) and low ratio of silicon to phosphorus and silicon to nitrogen (far lower than Redfield values) in the two diatoms and different sized suspended particulates were consistent with those in the seawater. Relative short silicon in the seawater and phytoplankton showed that silicon was possibly affectting phytoplankton growth in the Jiaozhou Bay.

The preparation and antioxidant activity of the sulfanilamide derivatives of chitosan and chitosan sulfates

Chitosan (CS) and chitosan sulfates (CSS) with different molecular weight (Mw) were reacted with 4-acetamidobenzene sulfonyl chloride to obtain sulfanilamide derivatives of chitosan and chitosan sulfates (LSACS, HSACS, LSACSS, HSACSS). The preparation conditions such as different reaction time, temperature, solvent, and the molar ratio of reaction materials are discussed in this paper. Their structures were characterized by FTIR spectroscopy and elemental analyses. The antioxidant activities of the derivatives were investigated employing various established in vitro systems, such as hydroxyl-radical (OH) superoxide anion (O-2(center dot-)) scavenging and reducing power. All kinds of the compounds (HCS, LCS, HCSS, LCSS, HSACS, LSACS, HSACSS, LSACSS) showed stronger scavenging activity on hydroxyl radical than ascorbic acid (Vc). The inhibitory activities of the derivatives toward superoxide radical by the PMS-NADH system were obvious. The experiment showed that the superoxide radical scavenging effect of sulfanilamide derivatives of chitosan and chitosan sulfates was stronger than that of original CS and CSS. All of the derivatives were efficient in the reducing power. The results indicated that the sulfanilamide group were grafted on CS and CSS increased the reducing power of them obviously. (c) 2007 Elsevier Ltd. All rights reserved.

Structural studies on a novel fucogalactan sulfate extracted from the brown seaweed Laminaria japonica

A low molecular weight fucogalactan, obtained from the brown seaweed Laminaria japonica, was separated into three fractions (LF1, LF2 and LF3) by DEAE-Sepharose FF column chromatography. All three fractions contained predominantly fucose, sulfate group and galactose. The results showed that the main fraction LF2 consisted of L-fucose, D-galactose and sulfate at a molar ratio 6:1:9. Structural study on the LF2 was carried out by NMR spectroscopy. The backbone of LF2 was primarily (1 -> 3)-linked alpha-L-fucopyranose residues (75%) and a few (1 -> 4)-alpha-L-fucopyranose linkages (25%). The branch points were at C-4 of 3-linked alpha-L-fucopyranose residues by beta-D-galactopyranose unites (35%, molar ratio) or at C-2 of 3-linked alpha-L-fucopyranose residues by non-reducing terminal fucose unites (65%, molar ratio). Sulfate groups occupied at position C-4 or C-2, sometimes C-2, 4 to fucose residues, and C-3 and/or C-4 to galactose residues. The structure of LF2 was supposed as following: [GRAPHICS] (C) 2010 Elsevier B.V. All rights reserved.

Degradation of porphyran from Porphyra haitanensis and the antioxidant activities of the degraded porphyrans with different molecular weight

In the present paper, ascorbate and hydrogen peroxide (H2O2) were used to degrade porphyran. It was found that porphyran could be degraded by free radical that was generated by ascorbate and H2O2 in combination. It was possible to prepare desired porphyran products with different molecular weight by adjusting ascorbate to H,02 proportions and their concentrations. The molar ratio of I was demonstrated more effective than in other ratios. Higher concentrations accelerated the degradation. Moreover, results of chemical analysis and FT-IR spectra suggested that the main structure of degraded products still remained although some changes happened. The degraded and natural porphyrans possessed scavenging 1,1-diphenyl-2-picrylhydrazyl (DPPH)-radical activity and reducing power. Higher antioxidant activities were found in both systems when the molecular weight was reduced. The results indicated that the antioxidant activities were closely related to the molecular weight. The degraded porphyrans are potential antioxidant in vitro. (c) 2006 Elsevier B.V. All rights reserved.

中国北方中新世风尘物质来源及古气候的地球化学指示

The most prominent tectonic and environmental events during the Cenozoic in Asia are the uplift of the Himalaya-Tibetan plateau, aridification in the Asian interior, and onset of the Asian monsoons. These caused more humid conditions in southeastern China and the formation of inland deserts in northwestern China. The 22 Ma eolian deposits in northern China provide an excellent terrestrial record relative to the above environmental events. Up to date, many studies have focused on the geochemical characters of the late Mio-Pleistocene eolian deposits, however, the geochemical characteristics of the Miocene loess and soils is still much less known. In this study, the elemental and Sr-Nd isotopic compositions of the eolian deposits from the Qinan (from 22.0 to 6.2 Ma) and the Xifeng (from 3.5 Ma until now) loess-soil sections were analyzed to examine the grain size effects on the element concentrations and the implications about the dust origin and climate. The main results are as follows: 1. The contents of Si, Na, Zr and Sr are higher in the coarser fractions while Ti and Nb have the highest contents in the 2-8 μm fractions. Al, Fe, Mg, K, Mn, Rb, Cu, Ga, Zn, V, Cr, Ni, LOI have clear relationships with grain-size, more abundant in the fine fraction while non significant relationship is observed for Y. Based on these features, we suggest that K2O/Al2O3 ratio can be used to address the dust provenance, and that VR (Vogt ratio = (Al2O3+K2O)/(MgO+CaO+Na2O)) can be used as a chemical weathering proxy for the Miocene eolian deposits because of their relative independence on the grain size. Meanwhile, SiO2/Al2O3 molar ratio is a best geochemical indicator of original eolian grain size, as suggested in earlier studies. 2. Analyses on the Sr and Nd isotope composition of the last glacial loess samples (L1) and comparison with the data from the deserts in northern China suggest that that Taklimakan desert is unlikely to be the main source region of the eolian dust. In contrast, these data suggest greater contributions of the Tengger, Badain Jaran and Qaidam deserts to the eolian dust during the last glacial cycle. Since the geochemical compositions (major, trace, REE and Sr, Nd isotope) of loess samples for the past 22 Ma are broadly similar with the samples from L1, these data trend to suggest relatively stable and insignificant changes of dust sources over the past 22 Ma. 3. Chemical weathering is stronger for Miocene paleosol samples than for the Plio-Pleistocene ones, showing warmer/more humid climatic conditions with a stronger summer monsoon in the Miocene. However, chemical weathering is typical of Ca-Na removal stage, suggesting a climate range from semiarid to subhumid conditions. These support the notion about the formation of a semi-arid to semi-humid monsoonal regime by the early Miocene, as is consistent with earlier studies.

Direct synthesis and characterization of titanium-substituted mesoporous molecular sieve SBA-15

Ti-substituted mesoporous SBA-15 (Ti-SBA-15) materials have been synthesized by using a new approach in which the hydrolysis of the silicon precursor (tetramethoxysilane, TMOS) is accelerated by fluoride. These materials were characterized by powder X-ray diffraction patterns (XRD), X-ray fluorescence spectroscopy (Y-RF), N-2 sorption isotherms, diffuse-reflectance UV-visible (UV-vis) and UV-Raman spectroscopy, Si-29 MAS NMR, and the catalytic epoxidation reaction of styrene. Experiments show that Ti-SBA-15 samples of high quality can be obtained under the following conditions: F/Si greater than or equal to 0.03 (molar ratio), pH less than or equal to 1.0, aging temperature less than or equal to 80 degreesC, and Ti/Si less than or equal to 0.01. It was found that the hydrolysis rate of TMOS was remarkably accelerated by fluoride, which was suggested to play the main role in the formation of Ti-SBA-15 materials of high quality. There is no stoichiometric incorporation of Ti, and the Ti contents that are obtained are quite low in the case of the approach that is proposed. The calcined Ti-SBA-15 materials show highly catalytic activity in the epoxidation of styrene.

Thioreduction of cyclopentanone and hydrodesulfurization of dibenzothiophene over sulfided nickel or cobalt-promoted molybdenum on alumina catalysts

Two series of sulfided Ni or Co promoted Mo/alumina catalysts, having different Ni or Co loadings, were characterized by their activities for the transformation of cyclopentanone into cyclopentanethiol (flow reactor, 220 degrees C, atmospheric pressure) and for the hydrodesulfurization of dibenzothiophene (flow reactor, 340 degrees C, 3 MPa hydrogen pressure). The addition of the promoter increased significantly the activity of the Mo/alumina catalyst for both reactions, up to a maximum obtained with the catalysts having a (promoter)/(promoter+Mo) molar ratio equal to 0.3-0.4. This increase in activity was due in part to an increase in the hydrogenating properties of the Mo/alumina catalyst. However, an additional modification of the catalyst (basic and nucleophilic properties) must be considered to account for the spectacular effect of the promoter on the rate of the dibenzothiophene direct desulfurization reaction. (C) 1999 Elsevier Science B.V. All rights reserved.

Preparation of titania-based catalysts for formaldehyde photocatalytic oxidation from TiCl4 by the sol-gel method

Titania sols were prepared by acid hydrolysis of a TiCl4 precursor instead of titanium alkoxides. The effect of acid concentration on the particle size and stability of sol was investigated. Stable titania sols with mean particle size of 14 nm could be obtained when the H+/Ti molar ratio was 0.5. The titania sols were modified with Pt, SiO2, ZrO2, WO3 and MoO3 to prepare a series of modified catalysts, which were used for the photocatalytic oxidation of formaldehyde at 37 degreesC. They showed different photocatalytic activities due to the influence of the additives. Comparing with pure TiO2, the addition of silica or zirconia increased the photocatalytic activity, while the addition of Pt and MoO3 decreased the activity, and the addition Of WO3 had little effect on the activity. It is of great significance that the conversion of formaldehyde was increased up to 94% over the SiO2-TiO2 catalyst. The increased activity was partly due to higher surface area and porosity or smaller crystallite size. A comparison of our catalyst compositions with the literature in this field suggested that the difference in activity due to the addition of a second metal oxide maybe caused by the surface chemistry of the catalysts, particularly the acidity. (C) 2001 Elsevier Science B.V. All rights reserved.

Structure and base properties of calcined hydrotalcites

Five hydrotalcites with Mg/Al molar ratio range of 3-15 were prepared. The structure and basicity of Mg-Al mixed oxides (Mg(Al)O) transformed from hydrotalcites were investigated by TPD, XPS, XRD, FT-IR and NMR techniques. The results of elemental analysis and XPS indicate that Al is enriched in the surface regions of Mg(Al)O, and its amount increases with the Mg/Al molar ratio and, the calcination temperature. Al-27-MAS-NMR results show that Al exists in two chemical environments: tetrahedral aluminium (Al(t)) and octahedral aluminium (Al(o)) in Mg(AI)O. The amount of Al(t) increases with the Mg/Al molar ratio and the calcination temperature. It is assumed that Al(t) may be mainly from the surface Al. Temperature-programmed desorption (TPD) of CO2 shows that the number of basic sites of Mg(Al)O samples increases with the Mg/Al molar ratio, and the maximum number of basic sites is obtained for hydrotalcite calcined at 773 K. Infrared spectra of adsorbed CO2 and B(OCH3)(3) reveal that there are two kinds of basic sites: weak basic OH- sites and strong basic O2- sites on the Mg(AI)O samples, the base strength depends on the Mg/Al molar ratio and calcination temperature.

Phenylurea herbicides-selective polymer prepared by molecular imprinting using N-(4-isopropylphenyl)-N'-butyleneurea as dummy template

A phenylurea herbicides-selective molecularly imprinted polymer (MIP) was prepared using N-(4-isopropylphenyl)-N'-butyleneurea as a dummy template and toluene as a porogen. The experimental results showed that the optimum molar ratio of template, functional monomer (MAA) and cross-linker (EDMA) was 1:8:20. Scatchard analysis showed that two classes of binding sites were formed in the imprinted polymer with dissociation constants of 26.81 mu L mol l(-1) and 1.428 mmol l(-1). The affinity and selectivity of MIP for phenylurea herbicides were studied. Among the 14 phenylurea herbicides tested, the MIP prepared showed obviously high affinity and selectivity for 10 chemicals (monuron, diuron, isoproturon, fenuron, chlortoluron, difenoxuron, metoxuron, neburon, buturon and fluometuron) with dichloromethane containing 10% hexane as mobile phase while non-imprinted polymer showed very low affinity for all the phenylurea herbicides tested. The experimental and calculated results also indicated that the size and property of the group at the N' position of phenylurea molecules have great influence on the affinity of MIP for them and the recognition site is mainly located at the N' position of phenylurea herbicides. (c) 2005 Elsevier B.V. All rights reserved.

Autothermal reforming of n-octane on Ru-based catalysts

In an attempt to effectively integrate catalytic partial oxidation (CPO) and steam reforming (SR) reactions on the same catalyst, autothermal reforming (ATR) of n-octane was addressed based on thermodynamic analysis and carried out on a non-pyrophoric catalyst 0.3 wt.% Ru/K2O-CeO2/gamma-Al2O3. The ATR of n-octane was more efficient at the molar ratio Of O-2/C 0.35-0.45 and H2O/C 1.6-2.2 (independent parameters), respectively, and reforming temperature of 750-800 degrees C (dependent parameter). Among the sophisticated reaction network, the main reaction thread was deducted as: long-chain hydrocarbon -> CH4, short-chain hydrocarbon -> CO2, CO and H-2 formation by steam reforming, although the parallel CPO, decomposition and reverse water gas shift reaction took place on the same catalyst. Low temperature and high steam partial pressure had more positive effect on CH4 SR to produce CO2 other than CO. This was verified by the tendency of the outlet reformate to the equilibrium at different operation conditions. Furthermore, the loss of active components and the formation of stable but less active components in the catalyst in the harsh ATR atmosphere firstly make the CO inhibition capability suffer, then eventually aggravated the ATR performance, which was verified by the characterizations of X-ray fluorescence, BET specific surface areas and temperature programmed reduction. (c) 2005 Elsevier B.V. All rights reserved.

Study of Mn-based catalysts for oxidative dehydrogenation of cyclohexane to cyclohexene

The gas-phase oxidative dehydrogenation (ODH) of cyclohexane to cyclohexene in the presence of molecular oxygen has been studied over various Mn-based catalysts. It is found that LiCl/MnOx/PC (Portland cement) catalyst exhibits the highest catalytic performance, and a 42.8% cyclohexane conversion, 58.8% cyclohexene selectivity and 25.2% cyclohexene yield can be achieved under 600 degrees C, 20,000 h(-1) and C6H12/O-2/N-2= 14/7/79. There are good correlations between the selectivities to cyclohexene and the electrical conductivities of Li doped Mn-based catalysts, from which it is deduced that the non-fully reduced oxygen species (O-2(-), O-2(2-), O-) involved in a new phase of LiMn2O4 might be responsible for the high selectivity toward cyclohexene, whereas the Mn2O3 crystal phase results in the COx formation. The selectivity to cyclohexene increases with increasing molar ratio of Li to Mn in LiCl/ MnOx/PC.