SAPO-5分子筛骨架结构研究

SAPO-5分子筛的骨架是由PO_4~-、AlO_4~-和SiO_4四面体构成.可以看作是硅同晶置换AlPO_4-5分子筛骨架上的磷或铝而得到,其取代方式可以通过三种可能的途径实观;(1)Si 取代Al;(2)Si 取代P;(3)两个Si 等同取代一个P 和一个Al.由于取代方式的不同,将导致骨架TO_4(T=P、Al,Si)的连接方式的不同,因此Si 在SAPO-5分子筛骨架中的存在状态是人们十分关注的问题.目前这方面的研究工作都采用固体核磁共振的方法,并且认为合成条件的不同其取代机理也不相同.本工作用~(31)P 和~(29)Si 固体高分辨核磁共振技术结合电子探针和光电子能谱方法对HF 参与下得到的SAPO-5分子筛骨架构成进行了系统的研究.     

Microwave assisted hydrothermal synthesis of tin niobates nanosheets with high cycle stability as lithium-ion battery anodes

SnNb₂O₆ and Sn₂Nb₂O₇ nanosheets were synthetized via microwave assisted hydrothermal method, and innovatively employed as anode materials for lithium-ion battery. Compared with Sn₂Nb₂O₇ and the previously reported pure Sn-based anode materials, the SnNb₂O₆ electrode exhibited outstanding cycling performance.     

Synthesis and Characterization of p—[Perfluoro—1—（2—fluorosulfonylethoxy）]ethylated Polystyrene

A new fluorinated polystyrene bearing a p-sulbstiuted perfluoro[1-(2-fluorosulfonylethoxy)]ethyl group was synthesized via one-electron oxidation of polystyrene by perfluoro[2-(2-fluorosulfonylethoxy)]propionyl peroxide at different peroxide to polystyrene molar ratios.The yield of perfluoroalkylation decreases with the increase of the reactant molar ratio.The modified polymer has been characterized by various techniques:the ring pefluoro[1-(2-fluorosulfonylethoxy)]ethylation has been proved by FT-IR and ^19FNMR;the X-ray photoelectron spectra(XPS) show the maximum binding energy of F18,O18,C18(two kinds of carbon atoms,namely C-H and C-F)and S2p,respectively; desulfonylation of the fluorinated polystyrene appearing at 217℃ has been found by its thermogravimetric analysis (TGA).The determinations of contact angle,refractive index and glass transition temperature of the modified polymer have disclosed that when the contact angle increases with the increase of the molar ratio,the refractive index and glass transition temperature decrease.The polydispersity values indicate that the degradation of the polymer chains did not occur during the reaction.     

Novel fragmentation of N-diisopropyloxyphosphoryl dipeptides and tripeptides by fast atom bombardment mass spectrometry

Positive ion fast atom bombardment mass spectrometry of N-diisopropyloxyphosphoryl dipeptides and tripeptides showed a novel cleavage pattern in that only the N-phosphoryl fragment ions gave intense peaks while the C-terminal series of ions was suppressed. The base peak was the N-phosphoryl imino ion responding to the N-terminal residue. These advantages are superior to those of other types of N-protecting groups.     

2]Catenane assembly from calix[4]arene crown ethers [In Process Citation

A variety of novel calix[4]arene-incorporating crown ethers with or without intramolecular hydrogen bonding have been prepared by two efficient methods and utilized as donor rings to assemble calix[4]arene [2]catenanes based on pi-stacking interaction between hydroquinone and bipyridinium units. Treatment of calix[4]arene crown ethers 4, 10a, or 10b, whose cone conformation was fixed by intramolecular hydrogen bonding within the calix[4]arene moiety, with dicationic salt 15 x 2PF6 and dibromide 16 afforded the corresponding [2]catenanes 17a x 4PF6, 17b x 4PF6, and 17c x 4PF6 in 20%, 53%, and 55% yields, respectively, whereas from the reactions of 15 x 2PF6 and dibromide 16 in the presence of conformationally flexible 11 or 12 with a cone conformation kept by two propyl groups, [2]catenanes 18 x 4PF6 and 19 x 4PF6 were obtained in 12% and 6% yields. [2]Catenanes 21a x 4Cl, 21b x 4Cl, and 21c x 4Cl, incorporating calix[4]arene in both the donor and acceptor rings, were also successfully assembled from 10a or 10b, 16, and dicationic salts 20a x 2PF6 or 20b x 2PF6. The dynamic 1H NMR and absorption spectra of the [2]catenanes have been investigated, which revealed a strongest donor-acceptor interaction in 17a x 4PF6 and that the cone [2]catenanes 17a-c x 4PF6 can isomerize to the partial cone isomer at high temperature. The difference of the dynamic properties of these catenanes was discussed. The results demonstrate that catenation is one new general method to change the conformational distributions of calix[4]arenes.     

Fe(bpb)(CN)2]- as a versatile building block for the design of novel low-dimensional heterobimetallic systems: synthesis, crystal structures, and magnetic properties of cyano-bridged Fe(III)-Ni(II) complexes [(bpb)(2-) = 1,2-bis(pyridine-2-carboxamido)benzenate

A dicyano-containing [Fe(bpb)(CN)2]- building block has been employed for the synthesis of cyano-bridged heterometallic Ni(II)-Fe(III) complexes. The presence of steric bpb(2-) ligand around the iron ion results in the formation of low-dimensional species: five are neutral NiFe2 trimers and three are one-dimensional (1D). The structure of the 1D complexes consists of alternating [NiL]2+ and [Fe(bpb)(CN)2]- generating a cyano-bridged cationic polymeric chain and the perchlorate as the counteranion. In all complexes, the coordination geometry of the nickel ions is approximately octahedral with the cyano nitrogen atoms at the trans positions. Magnetic studies of seven complexes show the presence of ferromagnetic interaction between the metal ions through the cyano bridges. Variable temperature magnetic susceptibility investigations of the trimeric complexes yield the following J(NiFe) values (based on the spin exchange Hamiltonian H = -2J(NiFe) S(Ni) (S(Fe(1)) + S(Fe(2))): J(NiFe) = 6.40(5), 7.8(1), 8.9(2), and 6.03(4) cm(-1), respectively. The study of the magneto-structural correlation reveals that the cyanide-bridging bond angle is related to the strength of magnetic exchange coupling: the larger the Ni-N[triple bond]C bond angle, the stronger the Ni- - -Fe magnetic interaction. One 1D complex exhibits long-range antiferromagnetic ordering with T(N) = 3.5 K. Below T(N) (1.82 K), a metamagnetic behavior was observed with the critical field of approximately 6 kOe. The present research shows that the [Fe(bpb)(CN)2]- building block is a good candidate for the construction of low-dimensional magnetic materials.     

SCATTERING FUNCTION OF POLYMER BLENDS

For a system of flexible polymer molecules, the concepts of two concentrations, namely the segmental and the molecular concentrations, have been proposed in this paper. The former is equivalent to the volume fraction. The latter can be defined as the number of the gravity centers of macromolecules in a unit volume. The two concentrations should be correlated with each other by the conformational function of the polymer chain and should be discussed in different thermodynamic equations. On the basis of these concepts it has been proved that the Flory-Huggins entropy of mixing should be the result of the mixing “ideal gases of the gravity centers of macromolecules“. The general correlation between the free energy of mixing and the scattering function (structural factor) of polymer blends has been studied based on the general fluctuation theory. When the Flory-Huggins free energy of mixing is adopted, the de Gennes scattering function of a polymer blend can be derived.     

Comparison of Methionine α,γ‐Lyase and Homocysteine α,γ‐Lyase for Electrochemical Determination of Homocysteine

Recently, a novel enzymatic method was developed for determination of homocysteine. This method utilizes the electrochemical hydrogen sulfide sensor along with methionine α,γ‐lyase to accomplish the fast, accurate, sensitive and selective measurements. As a continuation of this work, another enzyme, homocysteine α,γ‐lyase, was used and the parallel experiments of using both enzymes were carried out against the effect of pH, sensitivity, linearity, and interferences, in an intended comparison between these two enzymes. The excellent linearity of amperometric currents against homocysteine concentrations, high sensitivities and low detection limits for both enzymes reconfirmed that the electrochemical method is superior over other analytical means. The high enzymatic activity of methionine α,γ‐lyase surpassing homocysteine α,γ‐lyase endowed the former higher sensitivity, lower detection limit and faster response than the latter, suggesting methionine α,γ‐lyase a better candidate for homocysteine measurement by electrochemical method. The differences between these two enzymes on the trends of response time and sensitivity at different pH environments, reactivity toward several forms of homocysteine as well as on the interference from several agents were also addressed and discussed.     

RESONANCE-ENHANCED CARS SPECTROSCOPY OF BILIPROTEINS. INFLUENCE OF AGGREGATION and LINKER PROTEINS ON CHROMOPHORE STRUCTURE IN ALLOPHYCOCYANIN (Mastigocladus laminosus)

Abstract— Resonance-enhanced coherent anti-Stokes Raman spectra (CARS) are reported for monomers and for trimers with and without linker proteins of allophycocyanin isolated from Mastigocladus laminosus. The CARS spectrum of the monomer is independent of the presence of linker proteins and is very similar to that of phycocyanin monomers indicating that the equivalent chromophores exhibit like structures in both biliproteins. Large differences are, however, observed between the spectra of phycocyanin trimers and those of allophycocyanin trimers with or without linker proteins (L_c^8,9). The observed differences between monomer and trimer spectra are consistent with a change of the α-chromophore-protein arrangement upon aggregation without linker. If linker proteins are present in the trimer, then additional geometry changes of the β-chromophores are induced; these could relate to a transition from the 15Z- anti to 15Z- syn conformation.     

Determination of chlorogenic acid and rutin in cigarettes by an improved capillary electrophoresis indirect chemiluminescence system

An improved capillary electrophoresis indirect chemiluminescence system was employed for the determination of chlorogenic acid and rutin in cigarette samples. After being separated by capillary electrophoresis, the analyte zones were determined by indirect chemiluminescence of luminol-potassium hexacyanoferrate. In this system, luminol was added into running buffer solution and introduced at the head of separation capillary, and potassium hexacyanoferrate was introduced at the end of the capillary. A high potential buffer reservoir was constructed from a running buffer cell and an electrode buffer one, which were jointed with a frit, in order to avoid luminol electrolysis in high potential reservoir and the excursion of chemiluminescence baseline. A low potential flow reservoir was used to prevent electrode buffer solution from the contamination of chemiluminescence waste. Therefore, the proposed capillary electrophoresis-chemiluminescence system can avoid the electrolysis of chemiluminescence reagent, retain the stability of chemiluminescence baseline and prolong the working time of running and electrode buffer solutions. In addition, the matrix of cigarette sample solutions has also an inhibitory effect on the chemiluminescence intensity in the indirect detection, whereas the influence was not observed in the separation of standard solutions. After the correction of matrix inhibition and the calibration with standard addition method, chlorogenic acid and rutin were determined in four cigarette samples by the improved capillary electrophoresis-chemiluminescence system.