Pseudo-crown ether having AIE and PET effects from a TPE-CD conjugate for highly selective detection of mercury ions

A new tetraphenylethylene-cyclodextrin（TPE-CD） conjugate with a linkage composed of long triethylene glycol chain and triazole ring on the CD rim has been designed and synthesized. The TPE-CD conjugate exists in a stretched form in DMSO and enhances its fluorescence after addition of a small amount of water due to aggregation-induced emission（AIE） effect. However, in the presence of a large amount of water, the TPE unit will enter the cyclodextrin cavity to form a folded self-inclusion compound....     

Study on the Conformation of Cyclodecapeptide Loloatin C with Obvious Antibiotic Activity

The conformation of cyclodecapeptide loloatin C with obvious antibiotic activity has been investigated in 2,2,2-trifluoroethanol/sodium acetate buffer solution and then characterized by Fr-IR, CD and NMR spectrum. The results of FT-IR show that there exists β-strand or β-tum secondary structure in the molecule. According to the CD spectrum, the helical turn is dominant but the β-turn structure also exists. Conformation of the whole molecule is probably a helical β-turn.The chemical shifts and coupling constants prove the existence of a β-structure in the regions of Val,Orn2 and Leu3. NOESY data and temperature gradients of amide protons suggest that the molecular conformation is a dumbbell-like structure with the waist located between ornithyl (position 2) and D-phenylalanyl (position 7) and β-turn on both ends.     

Remarkably Decreased CD11b Positive Splenocytes in Aquaporin 3-Null Mice

Aquaporins(AQPs) are molecular water channels that play important physiological roles in fluid transporting organs.The expression and function of AQPs in the immune system are largely unknown.CD11(a―d)/CD18 integrins are adhesion molecules expressed on leukocytes,which play a critical role in leukocyte adhesion,migration and host defense.In the present study,we discovered the expression of aquaporin-3(AQP3) on spleen CD11b positive cells,and the content of CD11b positive splenocytes in aquaporin 3-null mice is significantly decreased.Further analysis suggested remarkably decreased monocyte/macrophage subpopulation and significantly decreased granulocyte subpopulation.It is the first report suggesting an important role of AQP in the development and maturation of immunocytes.     

Molecular modeling and spectroscopic studies on the binding of guaiacol to human immunoglobulin

The fluorogenic property of guaiacol was exploited for the first time to analyze the interaction with target protein as a probe by molecular modeling, fluorescence, circular dichroism (CD) and Fourier transform infrared (FT-IR) spectroscopy. Molecular docking was performed to reveal the possible binding mode or mechanism and suggested that guaiacol can strongly bind to human immu- noglobulin (HIgG). It is considered that guaiacol binds to HIgG mainly by a hydrophobic interaction and there are two hydrogen bond interactions between the drug and the residues LEU 80 and ASP 65, which is in good agreement with the results from the experimental thermodynamic parameters (the enthalpy change △H0 and the entropy change △S0 were calculated to be 65.55 kJ·mol-1 and 132.95 J·mol-1·K-1 according to the Vant’ Hoff equation). Data obtained by the fluorescence spectroscopy indicated that binding of guaiacol with HIgG leads to dramatic enhancement in the fluorescence emission intensity along with significant occurrence of efficient Frster resonance energy transfer (FRET) from the residue of HIgG to the protein bound guaiacol. From the low value of fluorescence anisotropy (r = 0.06), it is argued that the probe molecule is located in the motionally unrestricted environment of the protein. The alterations of protein’s secondary structure in the presence of guaiacol in aqueous solution were quantitatively calculated by the evidences from FT-IR and CD spectroscopes.     

Chemical Reactions and Kinetics of the Carbon Monoxide Coupling in the Presence of Hydrogen

The chemical reactions and kinetics of the catalytic coupling reaction of carbon monoxide to diethyl oxalate were studied in the presence of hydrogen over a supported palladium catalyst in the gaseous phase at the typical coupling reaction conditions. The experiments were performed in a continuous flow fixed-bed reactor. The results indicated that hydrogen only reacts with ethyl nitrite to form ethanol, and kinetic studies revealed that the rate-determining step is the surface reaction of adsorbed hydrogen and the ethoxy radical (EtO-). A kinetic model is proposed and a comparison of the observed and calculated conversions showed that the rate expressions are of rather high confidence.     

Investigation of nitroxoline-human serum albumin interactions by spectroscopic methods

Nitroxoline is a wide spectrum antibacterial and is one of the most important urinary antiseptics.The interaction between nitroxoline and human serum albumin(HSA)has been investigated systematically by fluorescence spectroscopy,synchronous fluorescence,three-dimensional fluorescence,CD spectroscopy and UV-Vis absorption spectroscopy.The results indicated that the quenching of HSA by nitroxoline was static.The corresponding thermodynamic parameters △H,△S and △G calculated according to van’t Hoff equation revealed that the intermolecular forces acting between nitroxoline and HSA were mainly hydrogen bonding and van der Waals forces.The conformational changes in the interaction were studied by synchronous fluorescence,CD spectroscopy and three-dimensional fluorescence spectra which showed changes in the microenvironment and conformation of HSA.     

Electrooxidation Mechanism of Methanol at Pt-Ru Catalyst Modified GC Electrode in Electrolytes with Different pH Using Electrochemical and SERS Techniques

The electrochemical and in-situ surface-enhanced Raman spectroscopy （SERS） techniques were used to investigate the electrooxidation behavior of methanol in acidic, neutral and alkaline media at a Pt-Ru nanoparticle modified glassy carbon （Pt-Ru/GC） electrode. The results showed that methanol could be dissociated spontaneously at the Pt-Ru/GC electrode to produce a strongly adsorbed intermediate, CO. It was found that CO could be oxidized more easily in the alkaline medium than in the acidic and neutral media. The peak potential of methanol oxidation was shifted from 0.663 and 0.708 V in the acidic and neutral media to -0.030 V in the alkaline medium, which is due to that the adsorption strength of CO on the Pt surface in the alkaline medium is weaker than that in the acidic and neutral media. The final product of the methanol oxidation is CO2. However, in the alkaline medium, CO2 produced would form CO3^2- and HCO3^- resulting in the decrease in the alkaline concentration and then in the decrease in the performance of DMFC. Therefore, the performance of the alkaline DMFC is not Stable.     

The Origin of Alligator sinensis

Alligator sinensis and Alligator mississippiensis are put under the Alligator family and Alligator genus as two different species and have been thought that they are closely related in taxonomy. The results of our DNA-DNA hybridization experiments showed that A. sinensis is a relatively young species originated in Asia,whereas A. mississippiensis is the older.It seems that the alligator and crocodilian could evolve from each other.The evolutionary rate of the crocodilian is slower than those of birds and higher vertebrates.The phylogeny of four crocodilians have been obtained and the hypothesis that the ancestor of Crocodylus porosus is a transitional form between A.mississippiensis and A.sinensis is proposed.     

FORMATION AND DEVELOPMENT OF TAIHU LAKE AND RECENT DEPOSITION

Situated in the Taihu plain between the mouth of the Changjiang River and theHangzhou Bay, the Taihu Lake is a large shallow-water lake in China with a surface area of 2427.8 km~2.The lake bottom mainly consists of loess-like sediment. Some buried and silted up channels and residual depressions can be found at the bottom and a lot of Neolithic cultural relics on the loess-like sediment. This indicated that the Taihu Lake was formed on the alluvial plain charaterized by widely deposited loess-like sediment because of siltation and stagnancy of water, instead of by development from lagoons as reported in the past.Recent deposition including influent-effluent current accumulation, wind-driven current and storm deposition in this lake occurred mainly in the south, the west shore and the midst of the lake.The sedimentary rate in the east Taihu Lake is about 1.7-1.8 mm/a, whereas in the west Taihu Lake it is about 0.41 ram/a, only 23％ of that of the former.     

Theoretical Study on the Reaction of Thymine with Iodomehane in the Water Phase

The reaction mechanisms of carcinogenic methylating agent iodomethane (MeI) with keto and enol tautomers of thymine (K- and E-thymine) were studied by using the B3LYP/6-311+G (d, p) method in water phase. The solvent effects were examined using the polarizable continuum model (PCM). Specifically, PCM single-point calculations at the same level of theory were performed in acetone and CCl4 that represent a range in nonpolarity. The calculated results show that the reaction of K-thymine with MeI is a two-step mechanism, whereas that of E-thymine is a one-step mechanism. Our calculations reveal that K-thymine is appreciably more stable than the enol form in the water phase or in the two solvents. The K- and E-form reaction barriers are 135.6 and 222.1 kJ/mol, respectively in water phase. These findings indicate that the reactions mentioned above could not occur efficiently in biological media in the absence of catalyst. Our conclusions are in agreement with the previous studies on the reactions of guanine with methyl chloride and methyl bromide.     

ULTRASTRUCTURE OF THE NUCLEOLUS AND REPLICATION SITES OF RIBOSOMAL DNA IN Allium cepa

Our conventional EM observations indicate that the nucleolus of Allium cepa is composedof the fibrillar centre (FC), fibrillar component (F) and granular region (G). FC is an elec-tron-lucid zone which contains condensed or loosened chromatin. F is a circular, highly elec-tron-dense component which surrounds FC and consists of compact fibrils. EM autoradiographic(EM ARG) studies with ~3H- UdR reveal that the synthesis of ribosomal RNA (rRNA) takesplace in F. G is situated around F and composed of granules about 25 to 30 nm in diameter.EM ARG studies with ~3H- TdR demonstrate that silver grains are predominantly located in Gof the nucleolar periphery and the region of the nucleolus-associated chromatin. In addition,~3H- TdR labels are also present, but with a much lower frequency, in FC. F and G of the nu-cleolar interior. According to the distribution and sphere of silver grains in different compo-nents of the nucleolus, we suggest that the replication sites of ribosomal DNA (rDNA) aremainly located in     

ELECTROCHEMICAL COPOLYMERIZATION OF ANILINE AND AZURE B*

The electrochemical copolymerization of aniline and N,N,N'-trimethylthionin (azure B) in aqueous solutions hasbeen carried out using the potential sweep method, The optimum conditions for the coelectrodeposition are that the pH valueand the temperature of the electrolytic solution are controlled at 5.57 and 30℃, respectively, and the scan potential range isset between - 0.25 and 1.10 V (versus SCE). The copolymerization rate of aniline and azure B is about 3 times larger thanthat of aniline in the absence of azure B. The copolymerization of aniline and azure B was verified from the results of visiblespectra during electrolysis, FTIR spectra and the atomic force microscopy (AFM) images of the polymers. The in situ visiblespectrum for the electrolysis of the solution containing aniline and azure B is different from that of the respective aniline andazure B. The FTIR spectrum of the copolymer is not a superposition of that of polyaniline and poly(azure B). The AFMimage of the copolymer is different from those of polyaniline and poly(azure B) and is not a mixture of individual polymers.The conductivity of thc copolymer synthesized at pH 5.57 is four orders of magnitude higher than that of polyanilinesynthesized under the same conditions, bat in the absence of azure B. The clectrochemical properties of the copolymer aremainly attributed to polyaniline, but the copolymer has a better electrochemical reversibility and a much faster charge transferthan those of polyaniline.     

气相色谱法测定线虫中的脂肪酸含量

ematode is a small organism and the traditional purification method needs a lot of nematodes , but it is difficult for us to foster many nematodes.The fatty acids in nematode were esterified directly in our analytical method,so that,the error is reduced the and sensitivity is improved. The results showed that thisimproved analysis method could be used for rapid and satisfactory determination of the fatty acid change during storagr of this group of nematodes.     

Catalytic reaction mechanism of L-lactate dehydrogenase: an ab initio study

Studies on the catalytic reaction mechanism of L-lactate dehydrogenase have been carried out by using quantum chemical ab initio calculation at HF/6-31G* level. It is found that the interconversion reaction of pyruvate to L-lactate is dominated by the hydride ion HR- transfer, and the transfers of the hydride ion HR and proton HR are a quasi-coupled process, in which the energy barrier of the transition state is about 168.37 kJ/mol. It is shown that the reactant complex is 87.61 kJ/mol lower, in energy, than the product complex. The most striking features in our calculated results are that pyridine ring of the model cofactor is a quasi-boat-like configuration in the transited state, which differs from a planar conformation in some previous semiempirical quantum chemical studies. On the other hand, the similarity in the structure and charge between the HR transfer process and the hydrogen bonding with lower barrier indicates that the HR transfer process occurs by means of an unusual manner. In addition,     

EXPRESSION OF A ZEIN GENE (Z4) INTRODUCED INTO DICOTYLEDONOUS Solanum nigrum

A maize genomic clone containing a zein gene (Z4) is inserted into the T-DNA of the Ti plasmid pTiT37. Agrobacterium tumefaciens strain harboring this modified Ti plasmid is used to infect stem sections of young plants or explants of dicotyledonous Solanum nigrum. Axenic transformed calli active in nopaline synthesis are obtained and transgenic plants are differentiated from them DNA Southern hybridization and RNA dot-hybridization analyses show that the zein gene is really transferred and integrated into the nuclear genome of transformed Solanum nigrum and that the zein gene can be transcribed into mRNA in the transformed calli and shoots. But the presence of the zein protein cannot be detected in either the transformed calli or the transgenic shoots. The results of thte experiments demonstrate that the promoter of a gene from monocotyledonous plants can function normally in transgenic dicots. The possibility of developmentally-regulated expression of the zein gene in transformed dicots is discussed in     

ELECTROCHEMICAL POLYMERIZATION OF ANILINE IN PHOSPHORIC ACID AND THE PROPERTIES OF POLYANILINE

The behavior of the electrochemical polymerization of aniline in a weak acid, phosphoric acid, is very similar to that in strong acids, i.e. its polymerization rate increases quickly with the electrolysis time. The FTIR spectra of polyaniline samples synthesized in phosphoric acid indicate that the counter ion H2PO4^- is present in both the oxidized form and the reduced form of polyaniline. The counter ion plays an important role in adjusting the pH value at the electrode surface of polyaniline during the oxidation and reduction processes. As a result, a pair of redox peaks still appear in cyclic voltammograms of polyaniline in a solution of sodium sulfate of pH 5.5 and in a solution of NaH2PO4 of pH 7.0,respectively, at low potential scan rate; and the color of polyaniline film also changes with applied potential at pH 7.0. Thus,the pH region for the electrochemical activity and the electrochromism of polyaniline is extended to pH 5.5 for a solution of sodium sulfate and to pH 7.0 for a solution of NaH2PO4. The conductivity of polyaniline is 3.3 S cm^-1, depending on the concentration of phosphoric acid used in the stage of polymerization of aniline. The result of elemental analysis of polyaniline is presented here.     

Metal catalyzed ethylene epoxidation:A comparative density functional theory study

Ethylene epoxidation on Ag(111), Pt(111), Rh(111) and Mo(100) has been studied by density functional theory (DFT) calculations. The results show that the adsorption energies of possible adsorbed species involved in the ethylene epoxidation increase in the order: Ag相似文献   

2-取代苯亚胺基噻唑烷类化合物的晶体结构研究

A series of 2-phenyliminothiazolidines has been successfully synthesized; and 2-(2-methylphenyl) iminothiazolidine (I a) and 2-(4-methylphenyl) iminothiazolidine (I b) have been selected to determine their crystal structures by X-ray diffraction technique,from their molecular graph of it is shown that double bond at 2-carbon atom of the heterocycle is all extro-cychc at the crystal state,and there are two main plaines in I a and I b.But in I a ,the angle between the planes is 61.4° and in I b the angle is about 41.4°.And so there is a strong conjugative effect in I b than in I a.So it is thought that the difference in fungicidal activities between 2-substitutedphenyl compounds (I a) and 4-substitutedphenyl compounds(I b) is due to their space factors.     

Preheat Compression Molding for Polyetherketoneketone: Effect of Molecular Mobility

Polyetherketoneketone(PEKK)is a new evolving polymeric material,and is considered as another important member of the polyaryletherketone(PAEK)family in addition to polyetheretherketone(PEEK).Hot compression molding can be used to compact and consolidate the PEKK products,where the temperature and pressure play key roles to affect the molecular mobility,entanglement and crystallization,and thus the mechanical properties of PEKKs.In this study,a preheating treatment was introduced in the compression molding,and it is found that such preheating is very essential to avoid the formation of crystal FormⅡ,based on the increased chain entanglement.Molecular dynamics simulations revealed that the molecular mobility is always suppressed when a compression is applied.Therefore,by increasing the entanglement via the preheating and maintaining such entanglement in the consequent compression molding,strong and tough PEKK materials were obtained,with a negligible fraction of crystal FormⅡ.     

DIFFUSIVITY OF ARRE EARTH ION IN POROUS ION EXCHANGE RESINS

The self-diffusion of Eu^3+ ion in porous resins D72 and D751 was studied by isotope exchange reaction.Applying Kataoka‘s bidisperse pore model,the intraparticle effective diffusivity De were resolved into a solid diffusivity Dg and a macropore diffusivity Dp.The experiments show that De.Dp and Dg all increase with the increase of reaction temperature;the response Dp and Dg of D751 resin is smaller than that of D72 resin;the diffusivity of Eu^3+ ion in solution is larger than Dp,which leads to the conclusion that the diffusion of ion in the pore of resin can not completely be equal to that in solution.