Extraction of the polysaccharides from five algae and their potential antioxidant activity in vitro

The sulfated polysaccharides extracted from algae possess excellent antioxidant activities. In this study, we prepared five polysaccharides extracted from five algae including one brown alga Laminaria japonica. one red alga Porphyra haitanensis and three green algae Ulva pertusa, Enteromorpha linza and Bryopsis plumose. And then the antioxidant activities of all the samples were investigated including scavenging effects of superoxide and hydroxyl radicals, and reducing power. The chemical analysis and FT-IR spectrum showed these extracts were polysaccharides. And in addition, we found that certain polysaccharide exhibited stronger antioxidant activity in certain antioxidant activity. Factors effecting and attributing to radical scavenging effect need to be further studied. (C) 2010 Elsevier Ltd. All rights reserved.

The preparation and antioxidant activity of 2-[phenylhydrazine (or hydrazine)-thiosemicarbazone]-chitosan

Chitosan (CS) with two different molecular weight were modified by reacting with methyl hydrazine-dithiocarboxylate and methyl phenylhydrazine-dithiocarboxylate to give 2-(hydrazine-thiosemicarbazone)-chitosan (2-HTCHCS, 2-HTCLCS) and 2-(phenylhydrazine-thiosemicarbazone)chitosan (2-PHTCHCS, 2-PHTCLCS). The structure of the derivatives was characterized by FT-IR spectroscopy and elemental analysis. The antioxidant activities of the derivatives were investigated employing various established systems, such as hydroxyl radical (*OH)/superoxide anion (O-2(center dot-)) scavenging/reducing power and chelating activity. All of the derivatives showed strong scavenging activity on hydroxyl radical than chitosan and ascorbic acid (Vc), and IC50 of 2-HTCHCS, 2-HTCLCS, 2-PHTCHCS and 2-PHTCLCS was 0.362, 0.263, 0.531 and 0.336 mg/mL respectively. The inhibitory activities of the derivatives toward superoxide radical by the PMS-NADH system were strong. The results showed that the superoxide radical scavenging effect of 2-[phenylhydrazine (or hydrazine)-thiosemicarbazone]-chitosan were higher than that of chitosan. The derivatives had obviously reducing power and chelating activity. The data obtained from vitro models clearly establish the antioxidant potency of 2-[phenylhydrazine (or hydrazine)-thiosemicarbazone]-chitosan. (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.

乙酰基二茂铁呋喃甲酰腙与β-环糊精包结物的结构与特性

用饱和溶液法制备了二茂铁酰腙类化合物乙酰基二茂铁呋喃甲酰腙(A FH) 与β-环糊精的包结物。元素分析及溶解常数测定结果证明两者形成了1∶1 包结物.。从溶解度曲线计算得出包合常数为227. 3 L ·mol- 1. 通过UV , FT IR, X 射线粉末衍射研究了包结特性, 并用NMR 技术推断了包结物的结构。

A novel silica-based column packing for reversed-phase HPLC of basic compounds

A novel bonded phase for reversed-phase HPLC was synthesized in two steps. Octylamine was first reacted with beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (beta -ECTS) and then the intermediate product was coupled onto porous silica. The prepared packing was characterized by elemental analysis, solid-state C-13 NMR and Fourier transform infrared (FT-IR). Chromatographic evaluations were carried out by using a mixture of organic compounds including acidic, basic and neutral analytes and methanol-water as binary mobile phase. The results showed that the stationary phase has excellent chromatographic properties and is resistant to hydrolysis between pH = 2 similar to 8. It can be used efficiently for the separation of basic compounds.

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.

Titanium species in titanium silicalite TS-1 prepared by hydrothermal method

The titanium species existing in titanium silicalite TS-1, which is prepared by hydrothermal method, were investigated using chemical analysis, XRD, FT-IR, Si-29 MAS NMR, UV-VIS, ESR. It has been observed that several kinds of titanium species may exist in titanium silicalite. The form that titanium atoms incorporate into the framework of titanium silicalite synthesized using tetrapropylammonium bromide (TPABr) as template differs from that using the classical method. But, the symmetry of titanium silicalite, changes from monoclinic to orthorhombic with the increase of titanium content in both methods. The Ti-O-2(-) originated from framework titanium and H2O2 has the moderate stability and may be active site in oxidation reaction. TS-1 synthesized using TPABr as template does not contain anatase, but contains a kind of partly condensed titanium species with six-fold coordination. The titanium species may correspond to 270-280 mn band in UV-VIS spectra and also can form Ti-O-2(-). But, this kind of Ti-O-2(-) is very stable and cannot be catalytic active site. So, the six-fold coordination titanium species may be inactive in both the oxidation reaction and the decomposition of H2O2. The hypothesis has been further proved by the phenomena that the titanium species is easily washed off using acid, and acid treating will not influence the catalytic performance of TS-1. (C) 2001 Elsevier Science B.V. All rights reserved.

Acid catalyzed synthesis of ordered bifunctionalized mesoporous organosilicas with large pore

Thiol-functionalized mesoporous ethane-silicas with large pore were synthesized by co-condensation of 1,2-bis(trimethoxy-sily)ethane (BTME) with 3-mercaptopropyltrimethoxysilane (MPTMS) using nonionic oligomeric polymer C1H (OCH(2)-CH(2))(10)OH (Brij-76) or poly(alkylene oxide) block copolymer (P123) as surfactant in acidic medium. The results of powder X-ray diffraction (XRD), nitrogen gas adsorption, and transmission electron microscopy (TEM) show that the resultant materials have well-ordered hexagonal mesoscopic structure with uniform pore size distributions. (29)Si MAS NNR, (13)C CP-MAS NMR. FT-IR, and UV Raman spectroscopies confirm the attachment of thiol functionalities in the mesoporous ethane-sificas. The maximum content of the attached thiol group (-SH) in the mesoporous framework is 2.48mmol/g. The ordered mesoporous materials are efficient Hg(2+) adsorbents with almost every -SH site accessible to Hg(2+). In the presence of various kinds of heavy metal ions such as Hg(2+), Cd(2+), Zn(2+), Cu(2+) and Cr(3+), the materials synthesized using poly(alkylene oxide) block cooollxmier (Pluronic 123) g(2+), as surfactant show almost similar affinity to Hg(2+), Cd(2+), and Cr(3+), while the materials synthesized using ofigomeric polymer C(18)H(37)(OCH(2)CH(2))(10)OH (Brij-76) as surfactant exhibit high selectivity to Hg(2+). (C) 2004 Elsevier Inc. All rights reserved.

Highly ordered periodic mesoporous ethanesilica synthesized under neutral conditions

Highly ordered mesoporous ethanesilica (MES) with 2D hexagonal structure was synthesized from 1,2-bis(trimethoxysilyl) ethane under neutral conditions for the first time. Divalent salts, such as NiCl2, MgCl2, ZnCl2, ZnSO4 and Zn(NO3)(2), were used to help the formation of the ordered mesostructure. The MES samples were characterized by powder X-ray diffraction, nitrogen sorption, transmission electron microscopy, FT-IR, C-13 and Si-29 solid-state NMR and thermal gravimetric analysis. A phase transition from a disordered wormhole-like structure to an ordered P6mm structure was observed upon the addition of inorganic salts. The pore size of the MES decreases from 4.7 to 3.9 nm with increasing content of the inorganic salts. Fluoride was also found to be important for the formation of ordered MES under neutral conditions.

Structural relation properties of hydrothermally stable functionalized mesoporous organosilicas and catalysis

The surfactant assistant syntheses of sulfonic acid functionalized periodic mesoporous organosilicas with large pores are reported. A one-step condensation of tetramethoxysilane (TMOS) with 1,2-bis(trimethoxysilyi)ethane (BTME) and 3-mercaptopropyltrimethoxysilane (MPTMS) in highly acidic medium was performed in the presence of triblock copolymer Pluronic P123 and inorganic salt as additive. During the condensation process, thiol (-SH) group was in situ oxidized to sulfonic acid (-SO3H) by hydrogen peroxide (30 wt % H2O2). X-ray diffraction studies along with nitrogen and water sorption analyses reveal the formation of stable, highly hydrophobic, and well-ordered hexagonal mesoscopic structures in a wide range of -CH2CH2-concentrations in the mesoporous framework. The resultant materials were also investigated by Si-29 MAS and C-13 CP MAS NMR, thermogravimetric analyses, UV-Raman spectroscopy, and FT-IR spectroscopy. The role of the bridged organic group on the hydrothermal stability of the mesoporous materials was established, which revealed an enhancement in hydrothermal stability of the materials with incorporation of the bridged organic groups in the network. The catalytic performance of -SO3H functionalized mesoporous materials was investigated in the esterification of ethanol with acetic acid, and the results demonstrate that the ethane groups incorporated in the mesoporous framework have a positive influence on the catalytic behavior of the materials.

Catalytic oxidation of cyclohexane to cyclohexanol and cyclohexanone over Co3O4 nanocrystals with molecular oxygen

Co3O4 nanocrystals with average particle sizes of 30 and 50 run were synthesized using cobalt nitrate as precursor, and were characterized by X-ray diffraction (XRD), nitrogen adsorption, transmission electron microscopy (TEM), and Fourier transform infrared (FT-IR) spectroscopy. Catalytic oxidation of cyclohexane with molecular oxygen was studied over Co3O4 nanocrystals. These catalysts showed obviously higher activities as compared to Co3O4 prepared by the conventional methods, Co3O4/Al2O3, or homogeneous cobalt catalyst under comparable reaction conditions. The 89.1% selectivity to cyclohexanol and cyclohexanone at 7.6% conversion of cyclohexane was realized over 50 nm sized Co3O4 nanocrystals at 393 K for 6 h. (c) 2005 Elsevier B.V. All rights reserved.

Synthesis of FeCoMnAPO-5 molecular sieve and catalytic activity in cyclohexane oxidation by oxygen

A new FeCoMnAPO-5 with AFI structure was synthesized under hydrothermal conditions and characterized by XRD, FT-IR, X-ray fluorescence, nitrogen adsorption and SEM. The oxidation of cyclohexane with molecular oxygen was studied over the catalyst at 403 K. It show d higher activity compared to FeAPO-5, CoAPO-5 and MnAPO-5. The FeCoMnAPO-5 catalyst was recycled twice without loss of activity or selectivity.

Physicochemical properties of silk fibroin after solubilization using calcium chloride with or without ethanol

To elucidate the physicochemical properties of silk protein, we studied the effects of calcium chloride and ethanol on the gelation of fibroin. Fibroin was treated with 5.0 M calcium chloride in water (Ca/W) or 5.0 M calcium chloride in 20% (v/v) ethanol (Ca/Et) and the rheological properties of colloidal fibroin were investigated. The Ca/W-treatment promoted an increased rate of gelation and gave higher gel strength than the Ca/Et-treatment. The maximum gel strengths of Ca/W- and Ca/Et-treated fibroins were obtained at pH 7.0 and pH 5.5, respectively. Scanning electron micrographs showed that the Ca/W-treated fibroin gel had a more developed three-dimensional molecular network than the Ca/Et-treated gel. Further, FT-IR spectra suggested that Ca/W-treated fibroin has more of a beta-structure than Ca/Et-treated one in colloidal conditions. This study indicated that the use of calcium chloride alone was more beneficial to the gelation of fibroin than combined use with ethanol.

Ligand modified real heterogeneous catalysts for fixed-bed hydroformylation of propylene

A novel ligand modified heterogeneous catalyst has been developed for hydroformylation of propylene, which showed excellent activity, selectivity and stability and need not be separated from the product after reaction in a fixed-bed reactor. The coordination bonds between triphenyl phosphine (PPh3) and Rh/SiO2 were confirmed by means of thermogravimetric (TG), solid-state P-31 NMR, XPS and FT-IR. Two types of active species for hydroformylation were formed, which were proved by in situ FT-IR techniques. The problem of metal leaching was greatly reduced by directly fastening Rh particles on the support, and the active Rh species that was responsible for the outstanding performance of propylene hydroformylation was tightly bound by the very strong metal-metal bonds. No sign of deactivation was observed over a period of more than 1000 h on the condition that PPh3 was added at 300-350 h of time on stream. (c) 2005 Elsevier B.V. All rights reserved.

Hydrothermal synthesis of alumina nanotubes templated by anionic surfactant

The alumina nanotubes were prepared by using the anionic surfactant, sodium dodecyl sulfonate (SDS), as structure-directing template for the first time with Al(NO3)(3)center dot 9H(2)O as precursor via a hydrothermal method. Structure and morphology of the nanotubes were characterized by XRD, TEM, FT-IR, TG and N-2 adsorption-desorption. The obtained nanotubes were found having outer diameters from 6 to 8 nm with length up to 200 nm. (C) 2005 Elsevier B.V. All rights reserved.