Research of Inclusion Complexation of 4,4'-Thiodiphenol Effected by β-Cyclodextrin in Aqueous Solutions and the Effect on Photodegradation

The inclusion behavior of 4,4′ -Thiodiphenol (TDP),a typical bisphenol and endocrine disruptor,reacts with β-cyclodextrin (β-CD) in aqueous solutions has been investigated by means of UV absorption spectrum and quantum-chemical calculation with Gaussian 98 software. The results show that the inclusion behavior of TDP is quite different in acidic solutions (pH 5.9) from that in alkaline solutions (pH 10.0). This behavior difference is attributed to the different formula structures in aqueous solutions at acidic and alkaline pH values that are demonstrated by quantumchemical modeling and calculation. TDP forms a 1∶1 β-CD inclusion complex in aqueous solutions. The equilibrium constant K was calculated to be 553.49 L/mol at pH 5.9 and 1 318.20 L/mol at pH 10.0 respectively for the inclusion complex reaction by using the modified Benesi-Heldbrand equation. After inclusion TDP's structure is changed especially at the inclusion part with the bond order becoming larger,which results in inhibitive photodegradation during direct photooxidation and H2O2 assisted photooxidation.     

Formation of the Inclusion Complex of Orange II with β-Cyclodextrin and Its Photostability

Inclusion complex of Orange II with β-Cyclodextrin (β-CD) and the anti-photolysis effect under UV-light were investigated. The molar ratio of inclusion complex of β-Cyclodextrin and Orange Ⅱ is 1∶1. The formation constant K=1.236×103 L/mol was determined by the UV and Fluorescence spectra respectively, which was quite in accordance with the calculation with a modified Benesi-Hildbrand equation. The inclusion complex was characterized by the IR spectra and the molar ratio of inclusion complex is 1∶1 too. The formation constant K=1.266×103 L/mol was determined by 1 H NMR analysis and was nearly the same by UV and fluorescence spectra. The photocatalytic decolorization rate of Orange Ⅱ solutions containing β-CD and TiO2 was smaller by 51.9% than that of the Orange Ⅱ solutions only containing TiO2, while in the case of direct photolysis of Orange Ⅱ solutions, β-CD can lower the photolysis rate by 48.1% under UV-light. This result indicates β-CD can inhibit the photolysis and photocatalytic decolorization of Orange Ⅱ under UV-light. The β-CD inclusion complex was found to be persistent to UV-light photolysis.     

Molecular self-assembly behavior of mono[6-O-6-(4-carboxyl-phenyl)]-β-CD in solution and solid state

A novel modified cyclodextrin, mono[6-O-6-(4-carboxyl-phenyl)]-]-β-CD (1), has been synthesized by the reaction of mono[6-(p-toluenesulfonyl)]-β-CD with 4-hydroxybenzoate, and its molecular self-assembly behavior in both solution and solid state was studied by means of crystallography, NMR spectroscopy and microcalorimetry. The results indicate that the bezoic acid groups are successively penetrated intermolecularly into the adjacent β-CD cavities to form helical columnar supramolecules in the solid state. As compared with crystal, the similar self-assembly behavior of 1 in aqueous solution has also been confirmed by the ^1H ROESY spectroscopy. Thermodynamically, the formation of polymeric supramolecules by modified CD in aqueous solution is mainly driven by entropy changes.     

Fabrication and characterization of novel tentacle-type adsorbent for resolution of chiral drugs

Novel tentacle-type chiral adsorbent based on silica gels modified with β-cyclodextrin (β-CD) and polyvinyl alcohol(PVA) is synthesized by surface grafting technique. The adsorption behavior of chiral pharmaceuticals using the resulting adsorbents is investigated. In the study, FT-IR and thermogravimetric analysis (TGA) are employed to characterize the chemical and physical properties of the adsorbent; mandelic acid (MA) serves as model solute to evaluate the sorption capacity and selectivity of the adsorbent. The experimental results show that the novel tentacle-type adsorbent is possessed of larger equilibrium adsorption capacity and better selectivity over the conventional one and could be as potential chiral stationary phase (CSPs).     

Preparation,Characterization and Antioxidant Activity of Inclusion Complex of Bakuchiol with Hydroxypropyl-β-cyclodextrin

Bakuchiol isolated from Psoralea corylifolia is a naturally occurring prenylated phenolic monoterpene with a variety of bioactivities. The aim of this study was to improve the water solubility and thermal stability of bakuchiol through complexing it with hydroxypropyl-β-cyclodextrin(HP-β-CD). The bakuchiol/HP-β-CD inclusion complex's behavior and characterization were investigated by ultraviolet-visible(UV-vis) spectroscopy, Fourier transform infrared spectroscopy(FT-IR), thermogravimetric analysis(TGA),X-ray diffraction(XRD),~1H nuclear magnetic resonance(NMR), and two-dimensional(2 D) NMR. The obtained results indicated the formation of 1∶1 inclusion complex for bakuchiol with HP-β-CD. Water solubility of bakuchiol was significantly improved by complexation with HP-β-CD as demonstrated by phase solubility studies. The encapsulation of bakuchiol was confirmed by UV-vis, FT-IR, and XRD. The thermal stability was effectively enhanced by TGA and derivative thermogravimetry(DTG) analysis. In vitro antioxidant activity showed that bakuchiol/HP-β-CD inclusion complex had a little higher antioxidant ability than free bakuchiol. Moreover, we got the possible inclusion mode for the bakuchiol/HP-β-CD inclusion complex through NMR analysis. These results suggest that the inclusion complex can be a potentially useful approach in the design of novel formulations of bakuchiol for medical applications.     

Research of Inclusion Complexation of 4,4＇-Thiodiphenol Effected by β-Cyclodextrin in Aqueous Solutions and the Effect on Photodegradation

The inclusion behavior of 4, 4＇ -Thiodiphenol （TDP）, a typical bisphenol and endocrine disruptor, reacts with β-cyclodextrin （β-CD） in aqueous solutions has been investigated by means of UV absorption spectrum and quantum-chemical calculation with Gaussian 98 software. The results show that the inclusion behavior of TDP is quite different in acidic solutions （pH 5.9） from that in alkaline solutions （pH 10.0）. This behavior difference is attributed to the different formula structures in aqueous solutions at acidic and alkaline pH values that are demonstrated by quantum- chemical modeling and calculation. TDP forms a 1 ： 1 fl-CD inclusion complex in aqueous solutions. The equiiibrium constant K was calculated to be 553.49 L/mol at pH 5.9 and 1 318.20 L/mol at pH 10.0 respectively for the inclusion complex reaction by using the modified Benesi-Heldbrand equation. After inclusion TDP＇s structure is changed especially at the inclusion part with the bond order becoming larger, which results in inhibitive photodegradation during direct photooxidation and H2O2 assisted photooxidation.     

Purification and Partial Characterization of a Collagenolytic Enzyme Produced by Pseudomonas aeraginosa SCU Screened from Rotten Hides

Strain Pseudomonas Aeraginosa SCU isolated from rotten hides is shown to produce various gelatinolytic enzymes with molecular masses ranging from - 50 to - 200 kD. A gelatinolytic enzyme called PAC exhibiting collagenolytic activity is purified by SP sepharose fast flow, Sephadex G-200 gel filtration and native PAGE cutting method. The purified enzyme has an apparent molecular weight of about 110 kD by SDS PAGE without β-mercaptoethanol. Treatment withtβ-Me suggests that PAC is dissociated into three subunits approximately 33 kD, 25 kD and 20 kD with a ratio of 2:1:1, named sub A, sub B and sub C repectively. EDFA and EGTA display a significant inhibitory effect on the enzyme activity while PMSF, leupeptin and pepstain do not appreciably inhibit it. The first 15 amino acid residues of the major subunit (subA) are determined and the sequence is Ala-Glu-Ala-Gly-Gly-Pro-Gly-Gly-Asn-Gln-Lys-Ile-Gly -Lys-Tyr. This sequence is identical to that of elastase of P. aeruginosa. The fragment of encoding mature sub A is cloned and its sequence is determined, which has a high homology with the gene of elastase. These results indicate that PAC is a novel collagenolytic metalloprotease composed of three kinds of subunits, of which elastase is the major one.     

Density functional theory calculation on the C―H bond insertion reaction of dibromocarbene with acetaldehyde

The insertion reaction mechanism of CBr_2 with CH_3CH_O has been studied by using the B3LYP/6-31G(d) method. The geometries of reactions, transition state and products were completely optimized. All the energy of the species was obtained at the CCSD(T)/6-31G(d) level. All the transition state is verified by the vibrational analysis and the internal reaction coordinate (IRC) calculations. The results show that the propionaldehyde (~HP1) is the main product of CH_2 insertion with CH_3CH_O. The calculated results indicated that all the major pathways of the reaction were obtained on the singlet potential energy surface. The singlet CBr_2 not only can insert the C_α-H [reaction I(1)]) but also can react with C_β-H [reaction II(1)]. The statistical thermodynamics and Eyring transition state theory with Wigner correc- tion are used to study the thermodynamic and kinetic characters of I(1) and II(1) in temperature range from 100 to 2200 K. The results show that the appropriate reaction temperature rang is 250 to 1750 K and 250 to 1600 K at 1.0 atm for I(1) and II(1) respectively. The rate constant and equilibrium constant are distinct in the range from 250 to 1000 K so that I(1) more easily occurs, while the reactions are not selected in the temperature range of 1000-1600 K     

New approach for screening anti—tumor compounds

A new screening approach for anticancer active compounds is presented.In this method,a target enzyme is incubated with a mixture of compounds,and then the com-plex formed by the target and small molecules is separated from the rest of the mixture by ultra-filtration.The complex that is retained on the membrane is subsequently washed with acid and small molecules that are specifically bound to the target are released and collected,then analyzed by high-performance liquid chromatograph combined with electrospray ionization mass spectrometry (HPLC/ESI-MS) analysis.We have successfully applied this method to screen anti-cancer compounds.DNA topoisomerase Ⅱ is used as a target to capture anti-tumor candidates from a mixture of combinatorial compounds,such as doxorubicin,daunorubi-cin and pravastain.     

Syntheses of New Functionalized Monomers for π-Conjugated Polymers

1 Results Tailored monomers based on the activated esters of 2,5-dibromobenzoic (sulfonic) acid derivatives, the 3-substituted 2,5-dibromothiophenes, the 9-substituted 2,7-dibromocarbazoles, and on the brominated 1,10-phenanthrolines suitable for Suzuki, Yamamoto or Grignard metathesis (GRIM) coupling reactions were synthesized and characterized by melting point, elemental analysis, 1H NMR, FTIR and TLC. The Horner-Wadsworth-Emmons reaction mechanism was utilized for the preparation of the 3-[2-(pyren-1-yl)vinyl]- or 3-[2-(quinolin-1-yl)vinyl]-2,5-dibromothiophenes. 4-Nitrophenol or N-hydroxysuccinimide were used for the preparation of activated esters. The Cadogan ring closure was utilized for the synthesis of 2,7-dibromocarbazole derivatives. A monomer with β-diketone structure was prepared and characterized as well. 1,10-Phenanthroline (phen) is a typical β-deficient aromatic compound and experience (and literature) advises that simple bromination is poor and nonselective. Of course, bromo derivatives can be obtained by the Skraup synthesis, but the low-yield and multi-step procedure is tedious. There are two main reasonable procedures available at present for the synthesis of 3,8-dibromo-1,10-phenanthroline. The methods utilize either phen monohydrochloride monohydrate for bromination or phen with addition of pyridine and sulfur chloride S2Cl2. We have found in our laboratory that the replacement of sulfur chloride by sulfur dichloride SCl2 and the use of phen monohydrate gives the possibility to prepare 3-bromo-, 3,8-dibromo-, 3,5,8-tribromo- and 3,5,6,8-tetrabromo-1,10-phenanthrolines in reasonable yields, and these derivatives can be separated by crystallization or by column chromatography.     

Correlation of coral fluorescence with nearshore rainfall and runoff in Hainan Island, South China Sea

Under UV-laser excitation, the Porites coral from Longwan bay waters. Hainan Island, could emit yellow-green fluorescence. After fitting the data of the fluorescent intensity (FI) of the coral with the rainfall (RF) in nearshore area of Qionghai. a good relationship between FI and RF was found with a linear formula of RF = 889 — 4.54 FI and a correlation coefficient of 0.78. Based on this formula, the rainfall sequence from 1982 to 1997 has been reconstructed. The peak annual rainfall is usually related to global El nino events. By fitting the data of the fluorescent intensity and the runoff (RO). a quadric formula was obtained as RO = — 0.0279FI —18.59 FI - 950.9 with a correlation coefficient of 0.74. The reconstructed runoff sequence from 1982 to 1997 coincided with the rainfall occurrence. The results indicate that flood and drought incidents in coastal areas of the south China are affected by global change to a great extent.     

2,5-二苯基1,3,4-二噁唑和2,5-二苯基1,3-噁唑与β-环糊精作用机理的研究

用核磁共振和稳态荧光等方法研究了2,5-二苯基1,3,4-二噁唑(PPD)和2,5-二苯基1,3-噁唑(PPO)分子与β-环糊精(β-CD)的相互作用,测定了包合物的组成和结合常数.发现疏水作用是形成PPD(或PPO)-β-CD包合物的主要作用力.直链脂肪醇(正丙醇～正戊醇)的加入使得PPD(或PPO)分子从β-CD内腔排斥到水相中.实验结果表明:唑类分子能否与环糊精形成纳米管聚合物,立体选择性是关键因素.     

Inhibitory effect of a modified adenovirus type 5 E1A gene on the NF-kB activity in porcine aortic endothelial cells induced by TNF-α

During the DXR process of xenotransplantation, the endothelial cells (EC) are activated, and the expression of NF-kB is immediately up-regulated[1]. NF-kB consisting of p65/p50 heterodimers or homodimers are retained in the cytoplasm by association with IkB (inhibitor of NF-kB) proteins. After stimulation, IkB is degraded, re-leasing NF-kB from these trimeric complexes, and allow-ing NF-kB translocation to the nucleus to play its biology function[2,5]. The promoter and enhancer region…     

Influences of 2.5wt% Mn addition on the microstructure and mechanical properties of Cu-Al-Ni shape memory alloys

The influences of 2.5wt% Mn addition on the microstructure and mechanical properties of the Cu-11.9wt%Al-3.8wt%Ni shape memory alloy (SMA) were studied by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), and differential scanning calorimeter (DSC). The experimental results show that Mn addition influences considerably the austenite-martensite transformation temperatures and the kind of martensite in the Cu-Al-Ni alloy. The martensitic transformation changes from a mixed xed β₁→β'₁+γ'₁ transformation to a single β₁→β'₁ martensite transformation together with a decrease in transformation temperatures. In addition, the observations reveal that the grain size of the Cu-Al-Ni alloy can be controlled with the addition of 2.5wt% Mn and thus its mechanical properties can be enhanced. The Cu-Al-Ni-Mn alloy exhibits better mechanical properties with the high ultimate compression strength and ductility of 952 MPa and 15%, respectively. These improvements are attributed to a decrease in grain size. However, the hardness decreases from Hv 230 to Hv 140 with the Mn addition.     

Ab initio research on DNA base alkylation by theβ-position me-tabolite of methylethylnitrosamine

Ab initio calculation is carried out to study the different supposed mechanisms of DNA base alkylation by [β-sulphate-nitrosamines at RHF/6-31G(d) and MP2/6-31G(d) levels. Full geometric structure optimization is done for all reactants, intermediates, products and transition states. The activation energy and IRC are obtained. The results show that the anchimeric assistant effect promotes the alkylation of DNA base by β-sulphate-nitrosamines. Solvent calculation is carried out with Onsager model of SCRF method at the same level. The results indicate that the activation energy is decreased obviously in water.     

Seasonal and inter-annual variations of length of day and polar motion observed by SLR in 1993―2006

A time series of length of the day (LOD) and polar motion (PM) were estimated from the range data measured by the satellite laser ranging technique (SLR) to LAGEOS 1/2 through 1993 to 2006. Compared with EOPC04 released by the International Earth Rotation and Reference Systems Service (IERS), the root mean squares errors for LOD, X and Y of PM are 0.0067 milliseconds (ms), 0.18 milli-arc-sec- onds (mas) and 0.20 mas, respectively. Then the time series are analyzed with the wavelet transformation and least squares method. Wavelet analysis shows that there are the obvious seasonal and inter- annual variations of LOD and PM, but the annual variation cannot be distinguished from the Chandler variation because these two frequencies are very close. The trends and periodic variations of LOD and PM are given in the least squares sense. LOD changes with the annual and semiannual periods. The annual and Chandler variations for PM are also detected, but the semiannual motion for PM is not found. The trend rate of the LOD change in 1993―2006 is ?0.18 ms per year, and the difference from the well- known 1.7 ms per century showed that the trend rate is diverse in different periods possibly. The trend rates of PM in the X and Y directions are 2.25 and 1.67 mas per year respectively, and the North Pole moves to 36.5°E relative to the crust, which is different from the direction of Greenland.     

The effect of antibody surface packing density on its antigen binding capacity

Following our recent study of the binding of antigen hCG (human chorionic gonadotropin) onto a mouse monoclonal antibody anti-β-hCG immobilized onto the support surface, we report a more recent study of the site-specific recognition of another surface immobilized mouse monoclonal antibody anti-α-hCG by hCG. The two antibodies have similar structures and molecular weights but different site-specific recognition from hCG. They both are used in the fabrication of fertility test immunoassays. Previous study by neutron reflection has indicated the “flat-on” orientation of anti-β-hCG with its Fc and two Fabs lying flat on the support surface. The aim of this work is to determine if there is any measurable difference in hCG binding between the two antibodies that could be attributed to the steric hindrance associated with specific binding sites. The adsorption and hCG binding for anti-α-hCG were made under the surface and in solutions as for anti-β-hCG so that the outcome could be directly compared. The results show that the two antibodies are bound by hCG in an almost identical fashion, suggesting that apart from the site-specific recognition there is no measurable difference in the steric hindrance between the α and β sites.     

Monitoring the binding of metal cations and histones to DNA in real time using fluorescence assays

The binding of cations (Na +,K +,Mg 2+,Ca 2+,Mn 2+) and histones to DNA can be studied using fluorescence assays.Here,we measured the fluorescence intensity and fluorescence anisotropy of DNA and DNA-histone complexes in the presence of cations.We demonstrate that when different cations are added into a DNA solution,the fluorescence intensities of the stained DNA are reduced by different amounts.Compared with divalent cations,monovalent cations had a weaker effect on fluorescence intensity and fluorescence anisotropy.Divalent (Mn 2+,Mg 2+,Ca 2+) cations markedly enhanced the fluorescence anisotropy of DNA.The binding modes of monovalent and divalent cations to DNA may be different.Divalent cations can change the structure of DNA molecules,or promote the assembly of DNA strands.The addition of histones causes DNA condensation,which mostly occurs during the first few seconds.Cation binding to DNA is abrupt,and is much faster than that of histones.