The protection effect of β-CD on DNA damage induced by ultrafine TiO_2

Under the photocatalysis of 365 nm ultraviolet radiation,ultrafine TiO2 caused the oxidative damage of Teasy plasmid DNA. The damage was determined by gel-electrophoresis. Then,a different dose of β-CD was added to the reaction,and the damage was restrained. The rate of damage restraining reached 97% when the mass of β-CD was 4 times as that of TiO2. Through UV scan and IR spectroscopy,it was found that the Ti-O of ultrafine TiO2 was bound with -OH of β-CD cavum and the -OH on the surface of ultrafine TiO2 disappeared,so the formation of ?OH was controlled. The ultrafine TiO2 has been widely used,but it was determined to be carcinogenic by some research. The protection effect of β-CD to DNA in the molecular level takes a new look on the surface modification of nano particles to decrease the toxic effect.     

金属酞菁化合物在TiO2表面的分散研究

Dispersion of copper(Ⅱ) phthalocyanine (CuPc), copper(Ⅱ) phthalocyaninesulfonate (CuPcS) and cobalt(Ⅱ)phthalocyaninetetrasulfonate (CoPcTS) on the surface of titanium dioxide was investigated by XRD, XPS, FT-IR and UV-Vis techniques. Results show that interaction between CuPc and TiO2 was very weak and CuPc was difficult to disperse on the surface of the support. While partly sulfurized CuPcS could be dispersed on the surface of support through sulfo-groups and its dispersion capacity was determined to be 0.085 g CuPcS/g TiO2. Completely sulfurlzed CoPcTS could also be dispersed on the surface of TiO2 as a monolayer and its dispersion capacity was 0.12 g CoPcTS/g TiO2. Interactions of the sulfo-groups as well as the electrons of CoPcTS with the surface of TiO2 could be evidenced by FT-IR characterization. Therefore, it was suggested that CoPcTS molecules be adsorbed on the surface of TiO2 in a flat-lying mode while CuPcS in a slanting one. UV-Vis spectra show that the dispersed CuPcS and CoPcTS molecules exist in both forms of monomers and dimers.     

SYNTHESIS OF POLYMERIC β-CYCLODEXTRIN SUPPORTED BY CROSSLINKED POLY(ACRYLAMIDE-co-VINYLAMINE)AND ITS CATALYSIS OF THE HYDROLYSIS OF p-NITROPHENYL ACETATE

Polymeric β-cyclodextrin (β-CD) supported by crosslinked poly(acrylamide-co-vinylamine) was synthesized as anartificial analog of hydrolytic enzyme and its catalysis of the hydrolysis of p-nitrophenyl acetate (p-NPA) was theninvestigated. The result showed that the polymer-supported β-CD could accelerate the hydrolytic reaction of p-NPA morequickly than β-CD itself and crosslinked poly(acrylamide-co-vinylamine) alone. The acceleration rate of the polymer-supported β-CD was about 10 times as fast as that of free β-CD in 0.01 mol/L phosphate buffer (pH 7.4) containing 32%DMSO at 37±0.1℃ when the molar amount of β-CD units in the polymer was equal to that of free β-CD in the experiments.The enhanced acceleration of thc polymer-supported β-CD should be ascribed to the cooperative contribution of theinclusion effect of β-CD ring and the nucleophilic effect of amino groups on the polymeric support.     

Preparation of a Cyclomaltoheptaose （p—cyclodextrin） Cross—linked Chitosan Derivative via Glyoxal or Glutaraldehyde

A cyclomaltohcptaose-β-cyclodextrin (β-CD) crosslinked chitosan derivative via glyoxal or glutaraldehyde was prepared. The structures of β-CD crosslined chitosan with glyoxal or glutaraldehyde were characterized by IR spectra. The surface morphology of the β-CD crosslinked chitosan particles was examined using a scanning electron microscope. The immobilization capacity of β-CD on chitosan was affected on the weight ratio of β-CD/chitosan,the utilization amount of crosslinking agent, the acidity of the reaction system and the temperature.The adsorption for nicotine indicated that the chitosan-β-CD was a good adsorbent.     

Reason for the loss of hydrophilicity of TiO_2 film and its photocatalytic regeneration

TiO2 film was prepared on soda-lime glass by sol-gel method. The water contact angle (θ) of the fresh TiO2 film is 0°. During storage in air, the surface of TiO2 film is gradually converted to the hydrophobic state. XPS and ITD results reveal that it is due to the adsorption of organic contaminants on TiO2 surface in air ambience. The lost hydrophilicity of TiO2 film can be regenerated by UV illumination.     

Different types of microfibrillated cellulose as filler materials in polysodium acrylate superabsorbents

Three types of microfibrillated cellulose(MFC)with differences in structure and surface charge were used at low concentration as filler materials in polysodium acrylate superabsorbents(SAPs).The swelling of the composite hydrogels was determined in 0.9%NaCl solution as well as in deionized water.The shear modulus of the samples was determined through uniaxial compression analysis after synthesis and after swelling in 0.9%NaCl solution.Furthermore,the ability to retain filler effects after washing was investigated.The results showed that all of the investigated MFCs had a strong reinforcing effect on the shear modulus after synthesis.The filler effect on swelling and on the associated shear modulus of swollen samples showed a more complicated dependence on structure and surface charge.Finally,it was found that the filler effects were reasonably retained after washing and subsequent drying.The results confirm that MFC holds great potential as a filler material in superabsorbent applications.Furthermore,the results provide some insight on how the structural properties and surface charge of MFC will affect gel properties depending on swelling conditions.This information should be useful in evaluating the use of different types of MFC in future applications.     

Using an Inhibitor to Prevent Plasticizer Migration from Polyurethane Matrix to EPDM Based Substrate

The loss of adhesion between the propellant and insulator is one of the most important problems in solid propellant motors due to migration of plasticizer to interface of propellant and insulator. In this work, the polyurethane (PU) binder containing DOP plasticizer was used as a polymeric matrix and β-cyclodextrin (β-CD) was applied as inhibitor agent to prevent plasticizer migration from the PU matrix into the ethylene propylene diene monomer (EPDM) substrate. To increase the compatibility of β-CD and PU matrix, a derivative of β-CD has been synthesized using toluene diisocyanate (β-CD-TDI). The synthesized derivative was characterized by MALDI-MS and FTIR-ATR analyses. FTIR-ATR results confirmed the formation of bonding between β-CD and the polymeric network while the MALDIMS results showed that the synthesized derivative contained two β-CD and 7 TDI molecules bonded to β-CD. Investigation of the mechanical properties of PU modified by β-CD-TDI showed a decrease in tensile strength and an increase in elongation at break with increasing β-CD-TDI content. DMTA results showed a decrement in crosslinking density by increasing the β-CD-TDI content. Also, to investigate plasticizer migration, extraction of the DOP plasticizer from samples was performed using dichloromethane solvent and its concentration was measured by gas chromatography. The results of migration evaluation after four months showed that using β-CD as an inhibitor agent in the PU binder could prevent the migration of plasticizer to EPDM substrate.     

Synthesis and characterization of sulfur-titanium dioxide nanocomposites for photocatalytic oxidation of cyanide using visible light irradiation

A sol-gel method was used to prepare TiO2and sulfur-TiO2(S-TiO2)nanocomposites, which were characterized by N2 adsorption-desorption, X-ray diffraction, X-ray photoelectron spectroscopy, photoluminescene, ultraviolet visible and transmission electron microscopy measurements. The photocatalytic performance of TiO2 and S-TiO2nanocomposites, with respect to the photocatalytic oxidation of cyanide under visible light irradiation, was determined. The results reveal that S is well dispersed on the surface of TiO2 nanoparticles. Additionally, the surface area of the S-TiO2nano-composites was observed to be smaller than that of the TiO2nanoparticles because of blocked pores caused by doping with S. The S-TiO2nanocomposite (0.3 wt% S) exhibited the lowest band gap and the highest photocatalytic activity in the oxidation of cyanide. The photocatalytic performance of S-TiO2(0.3 wt% S) nanocomposites was stable, even after the fifth reuse of the nanoparticles for the oxidation of cyanide.     

纳米结构Ce掺杂PbO2膜电极的电化学沉积和性质

The effect of Ce(Ⅲ) on the morphology and structure of deposited film of lead dioxide was studied by cyclic voltammetry (CV), X-ray diffractometry (XRD) and scanning tunneling microscopy (STM). The results indicated that the Ce-doped PbO2 film consisted of a mixture of α- and β-phase of PbO2. Ce doping changed the size of PbO2 crystal grains and made the crystallite size on the electrode surface in the nanometer range. Owing to the formation of nanometer-structured grains, the specific surface areas and activity sites of the electrode surface were increased, hence the catalytic activity of Ce-doped PbO2 electrode was evidently higher than that of undoped PbO2 electrode.     

Effect of Temperature-responsive Solution Behavior of PNIPAM-bPPEOMA-b-PNIPAM on Its Inclusion Complexation with α-Cyclodextrin

The effect of temperature-responsive solution behavior of PNIPAM-b-PPEOMA-b-PNIPAM on its inclusion complexation with α-cyclodextrin was studied. The triblock polymer was prepared by reversible addition-fragmentation chain transfer(RAFT) polymerization and formed inclusion complexes(ICs) after selective threading of the PEO segment of the triblock polymer through the cavities of α-CD units. For comparison, PPEOMA homopolymer was prepared and the inclusion complexation with α-CD was also studied. The ICs were prepared with α-CD when the polymer was in different conformations by changing the temperature, and the formed ICs were characterized by XRD, 1H-NMR, TGA and DSC. The solutions of the ICs show temperature-responsive clear/turbid transition or fluidic emulsion/gel transition depending on the concentration of the α-CD added, and the stoichiometry determined by 1H-NMR and TGA indicates that the stoichiometry of EO to α-CD of the resulted ICs increases with increasing of temperature.     

Influence of MnO_2 on the photocatalytic activity of P-25 TiO_2 in the degradation of methyl orange

Influences of α-MnO2, β-MnO2, and δ-MnO2 on the photocatalytic activity of Degussa P-25 TiO2 have been investigated through the photocatalytic degradation of methyl orange. The TiO2 photocatalyst, before and after being contaminated by MnO2, was characterized by UV-visible diffuse reflectance spectroscopy (UV-vis DRS), photoluminescence (PL), and X-ray photoelectron spectroscopy (XPS). The results showed that photocatalytic activity of TiO2 could be inhibited significantly or completely deactivated due to the presence of even a small amount of MnO2 particles. It was found that the poisoning effect varied with the crystal phases of MnO2 and the effect was in the order δ-MnO2 >α-MnO2 >β-MnO2. The poisoning effect was attributed to the formation of heterojunctions between MnO2 and TiO2 particles. The heterojunctions changed the chemical state of Ti4 and O2 sites in the crystalline phase of TiO2. MnO2 in contact with TiO2 particles also broadens the band-gap of TiO2, which decreases UV absorption of TiO2. It can also create some deep impurity energy levels serving as photoelec-tron-photohole recombination center, which accelerates the electron-hole recombination.     

XPS study of potassium-promoted molybdenum carbides for mixed alcohols synthesis via CO hydrogenation

The X-ray photoelectron spectroscopy (XPS) was used to investigate the surface characteristic of potassium-promoted or un-promoted both β-Mo_2C and α-MoC_(1-x) pretreated by syngas at different temperatures, and the promotional effect of potassium on the catalytic performance was also studied. XPS results revealed that the content of surface Mo and its valence distribution between β-Mo_2C and α-MoC_(1-x) were quite different. Promoted by potassium, the remarkable changes were observed for surface composition and valence of Mo distribution over β-Mo_2C. Potassium had strong electronic effect on β-Mo_2C, which led to a higher Mo~(4+) content. On the contrary, potassium had little electronic effect on α-MoC_(1-x), and K-Mo interaction was weak. Therefore, Mo~0 and Mo~(2+) became the dominant species on the catalyst surface, and the Mo~(4+) content showed almost no increase as the pretreatment temperature enhanced. In terms of catalytic performance of molybdenum carbides, the increase in Mo~0 most likely explained the increase in hydrocarbon selectivity, yet Mo~(4+) might be responsible for the alcohols synthesis.     

Investigation of radionuclide 60Co(II) binding to TiO2 by batch technique, surface complexation model and DFT calculations

The interaction between radionuclides and solid/water interfaces is important to understand the physicochemical processes of radionuclides in the natural environment.Herein,the interaction of 60Co(Ⅱ) with TiO 2 in aqueous solution as a function of pH and ionic strength was studied by using batch technique combined with surface complexation model and density functional theory(DFT) calculations.The batch experimental results showed that the adsorption of 60Co(Ⅱ) was dependent on pH and independent of ionic strength,indicating the formation of inner-sphere surface complexes on TiO 2 surfaces.The results of surface complexation models and DFT calculations indicated that the surface species of 60Co(Ⅱ) adsorbed on TiO 2 followed the trend:B structure(i.e.,60Co(Ⅱ) was linked to one bridge oxygen site) was the dominant surface species at low pH,and TT structure(i.e.,60Co(Ⅱ) was linked to two terminal oxygen sites) became the important surface complex at neutral and alkaline pH values.These results demonstrated that a multi-technique approach could lead to definitive information on the structures of adsorbed 60Co(Ⅱ) at the molecular level at the TiO 2 /water interfaces,as well as realistic models to rationalize and accurately evaluate the macroscopic manifestations of radionuclide adsorption phenomena.     

超声辅助法合成的石墨烯-TiO2复合材料声催化降解罗丹明B（英文）

A series of graphene-TiO2 composites was fabricated from graphene oxide and titanium n-butoxide(TNB) by an ultrasonic-assisted method.The structure and composition of the nanocomposites were characterized by Raman spectroscopy,BET surface area measurements,X-ray diffraction,transmission electron microscopy,and ultraviolet-visible absorption spectroscopy.The average size of the TiO2 nanoparticles on the graphene nanosheets was controlled at around 10-15 nm without using surfactant,which is attributed to the pyrolysis and condensation of dissolved TNB into TiO2 by ultrasonic irradiation.The catalytic activity of the composites under ultrasonic irradiation was determined using a rhodamine B(RhB) solution.The graphene-TiO2 composites possessed a high specific surface area,which increased the decolorization rate for RhB solution.This is because the graphene and TiO2 nanoparticles in the composites interact strongly,which enhances the photoelectric conversion of TiO2 by reducing the recombination of photogenerated electron-hole pairs.     

β-PHASE CRYSTALLIZATION OF ISOTACTIC POLYPROPYLENE

Effects of cooling rate and crystallization and melt temperatures on the melting curves of predomi-nately β-phase isotactic polypropylene (IPP) were investigated by using DSC instrument. Experimental re-sults indicate that the magnitude of βmelting endctherm increases with decreasing cooling rate and withincreasing crystallization temperature. The temperature of melt has no effect on the β-phase crystallizationof IPP below 300℃, but a further increase of the melt temperature will destroy the β-phase nuclei,then the β-phase crystals will not be produced upon cooling. The linear growth rates of α- and β-phasespherulites were determined as a function of temperature between 123 and 140℃. It was found that thegrowth rate of βspherulites is higher than that of αspherulites below 140℃. Studies of the kinetics ofβ-phase crystallization of IPP were also made using a DSC instrument. The results obtained do not fitthe usual Avrami equation. But it can be described by kinetic theory of imcomplete spher     

Impact and mechanism of TiO_2 nanoparticles on DNA synthesis in vitro

The impact of TiO2 nanoparticles on DNA synthesis in vitro in the dark and the molecular mechanism of such impact were studied. The impact of TiO2 nanoparticles on DNA synthesis was investigated by adding TiO2 nanoparticles in different sizes and at various concentrations into the polymerase chain reaction (PCR) system. TiO2 nanoparticles were premixed with the DNA polymerase, the primer or the template, respectively and then the supernatant and the precipitation of each mixture were added into the PCR system separately to observe the impact on DNA synthesis. Sequentially the interaction be- tween TiO2 nanoparticles and the DNA polymerase, the primer or the template was further analyzed by using UV-visible spectroscopy and polyacrylamide gel electrophoresis (PAGE). The results suggest that TiO2 nanoparticles inhibit DNA synthesis in the PCR system in the dark more severely than mi- croscale TiO2 particles at the equivalent concentration and the inhibition effect of TiO2 nanoparticles is concentration dependent. The molecular mechanism of such inhibition is that in the dark, TiO2 nanoparticles interact with the DNA polymerase through physical adsorption while TiO2 nanoparticles do with the primer or the template in a chemical adsorption manner. The disfunction levels of the bio-molecules under the impact of TiO2 nanoparticles are in the following order: the primer > the tem- plate > the DNA polymerase.     

环糊精与两种有机物的包合物的不同光解特性

The effectiveness of the solubilization and photodegradation of β-cyclodextrin （β-CD） and hydroxypropyl-β- cyclodextrin （HPCD） on two hydrophobic organic compounds （HOC） of methyl parathion and pentachlorophenol was investigated. The results indicate that the solubilization or photodegradation of two HOC were influenced by complexing with β-CD or HPCD. The solubility of pentachlorophenol （PCP） was increased linearly with β-CD concentration. The solubility of methyl parathion （MPT） was increased with the increase of β-CD concentration initially, however, as the β-CD concentration was enhanced above 3 g/L, the solubility was decreased with increase of β-CD concentration. The solubilities of two HOC were increased linearly with the increase of HPCD concentration. Although the photodegradation of MPT was improved, the photodegradation of PCP was restrained by complexation of HOC with β-CD or HPCD. In a word, the effectiveness of photodegradation or solubilization of HPCD was more significant than that of β-CD. One potential application of such a method was the in situ remediation of hydrophobic organic pollutants in contaminated soil and groundwater or industrial waste streams.     

Nickel and potassium co-modified β-Mo2C catalyst for CO conversion

Nickel and potassium co-medified β-Mo2C catalysts were prepared and used for CO hydrogenation reaction. The major products over β-Mo2C were C1-C4 hydrocarbons, only few alcohols were obtained. Addition of potassium resulted in remarkable selectivity shift from hydrocarbons to alcohols at the expense of CO conversion over β-Mo2C. Moreover, it was found that potassium enhanced the ability of chain propagation with a higher C2+OH production. Modified by nickel, β-Mo-2C showed a relatively high CO conversion, however, the products were similar to those of pure β-Mo2C. When co-modified by nickel and potassium,β-Mo2C exhibited high activity and selectivity towards mixed alcohols synthesis, and also the whole chain propagation to produce alcohols especially for the stage of C1OH to C2OH was remarkably enhanced. It was concluded that the Ni and K had, to some extent, synergistic effect on CO conversion.     

Synthesis of SAPO-34 using metakaolin in the presence of β-cyclodextrin

SAPO-34 molecular sieves were synthesized by the addition of β-cyclodextrin(β-CD) as crystal growth inhibitor using metakaolin as silicon and aluminum sources. Properties of the obtained samples were characterized by XRD,SEM,N2adsorption–desorption,FTIR,XRF,EDX,NH293-TPD andSi MAS NMR. When β-CD was added,crystal size of the SAPO-34 crystals decreased. Variation of Si content from the crystal center to surface decreased while total Si content hardly changed.29 Si MAS NMR results showed that β-CD contributed to better Si dispersion and decreased the size of Si(4Si) patches. Moreover,the MTO(methanol-to-olefin) process was conducted to investigate the influence of β-CD on catalytic performance. The synthesized sample with molar ratio of β-CD/Al2O3 equaling 0.055 remained active for 610 min while the sample synthesized without β-CD for only 280 min,which indicates that the lifetime of catalyst synthesized with β-CD is greatly prolonged.     

Room temperature phosphorescence of α-bromonaphthalene induced by β-cyclodextrin in the presence of cyclohexane

β-Cyclodextrin (β-CD) can induce a-bromonaphthalene (BrN) to emit strong room temperature phosphorescence (RTP) in the presence of micro amounts of cyclohexane (c-hexane). Experiments of luminescence spectra, phosphorescence lifetime and fluorescence polarization prove the formation of c-hexane/β-CD/BrN ternary inclusion complex. The apparent formation constant of the ternary inclusion complex was determined and the effect mechanism of c-hexane on the RTP of BrN induced by β-CD is discussed.