含氟三元丙烯酸酯乳液共聚物的合成及性能

含氟三元丙烯酸酯乳液共聚物的合成及性能;甲基丙烯酸甲酯;丙烯酸丁酯;含氟甲基丙烯酸酯;β-环糊精     

Ligand-controlled mixed-valence copper rectangular grid-type coordination polymers based on pyridylterpyridine

Six mixed-valence Cu(I)Cu(II) compounds containing 4'-(4-pyridyl)-2,2':6',2' '-terpyridine (L1) or 4'-(2-pyridyl)-2,2':6',2' '-terpyridine (L2) were prepared under the hydrothermal and ambient conditions, and their crystal structures were determined by single-crystal X-ray diffraction. Selection of CuCl(2).2H(2)O or Cu(CH(3)COO)(2).H(2)O with the L1 ligand and NH(4)SCN, KI, or KBr under hydrothermal conditions afforded 1-dimensional mixed-valence Cu(I)Cu(II) compounds [Cu(2)(L1)(mu-1,1-SCN)(mu-Cl)Cl](n) (1), [Cu(2)(L1)(mu-I)(2)Cl](n) (2), [Cu(2)(L1)(mu-Br)(2)Br](n) (3), and [Cu(2)(L1)(mu-1,3-SCN)(2)(SCN)](n)(4), respectively. Compound 5, prepared by layering with CuSCN and L1, is a 2-dimensional bilayer structure. In compounds 1-5, the L1 ligand and X (X = Cl, Br, I, SCN) linked between monovalent and divalent copper atoms resulting in the formation of mixed-valence rectangular grid-type M(4)L(4) or M(6)L(6) building blocks, which were further linked by X (X = Cl, Br, I, SCN) to form 1- or 2-dimensional polymers. The sizes of M(4)L(4) units in 1-4 were fine-tuned by the sizes of X linkers. Reaction of Cu(CH(3)COO)(2).H(2)O with L2 and NH(4)SCN under hydrothermal conditions gave mixed-valence Cu(I)Cu(II) compound [Cu(2)(L2)(mu-1,3-SCN)(3)](n) (6). Unlike those in 1-5, the structure of 6 was constructed from thiocyanate groups and the pendant pyridine of L2 left uncoordinated. The temperature-dependent magnetic susceptibility studies on compounds 1 and 4 showed the presence of mixed-valence electronic structure.     

Morphology-driven surface segregation in a blend of poly(epsilon-caprolactone) and poly(vinyl chloride)

A blend of poly(epsilon-caprolactone) (PCL) and poly(vinyl chloride) (PVC) with 90 wt % PCL was prepared. Two films of this blend, which were grown at 35 and 45 degrees C, showed the absence and presence of banded spherulites, respectively. A detailed examination conducted with time-of-flight secondary ion mass spectrometry (ToF-SIMS) found that the surface composition of the film grown at 45 degrees C was related to its structure, which was shown to contain ridges and valleys. Phase images obtained using atomic force microscopy (AFM) indicated that the ridges and valleys consisted of edge-on and flat-on lamellae, respectively. ToF-SIMS imaging revealed that PVC and PCL were located mainly on the surface of the valleys and ridges, respectively. This morphology-driven surface segregation was caused by the difference in the surface energy between the flat-on and edge-on lamellae.     

Capillary electrophoretic determination of the constituents of Artemisiae Capillaris Herba

Two capillary electrophoretic methods, a micellar electrokinetic electrophoretic (MEKC) one and a capillary zone electrophoretic (CZE) one, were developed for the separation of 12 constituents in Artemisiae Capillaris Herba. Detection at 254 nm with 20 mM sodium dodecyl sulfate and 20 mM sodium borate buffer (pH 9.82) in MEKC or with 25 mM sodium borate and 6.75 mg/ml 2,3,6-tri-O-methyl-beta-cyclodextrin buffer in CZE was found to be the most suitable approach for this analysis. Within 42 min, the MEKC method could successfully separate 12 authentic constituents, whereof chlorogenic acid, however, appeared as a broad and split peak, and capillarisin and chlorogenic acid overlapped partially with other coexisting substances in crude extract of the herb. The CZE method could completely overcome these problems and was used to determine the amounts of capillarisin, chlorogenic acid, scopoletin and caffeic acid in the extract. The effect of buffers on the constituent separation and the validation of the two methods were discussed.     

Sol-gel Preparation of Fluoridated Hydroxyapatite in Ca(NO3)2-PO(OH)3− x (OEt) x -HPF6 System

Fluoridated hydroxyapatite (FHA) has been successfully synthesized via sol-gel method with HPF₆ as the fluorine containing reagent. The chemical reactions induced by HPF₆ addition and the formation process of fluoridated hydroxyapatite (FHA) are investigated. The hydrolysis and alcoholysis of HPF₆ release F ion into the solution which, in turn, reacts with Ca ion to form nanocrystalline CaF₂ (nc-CaF₂). These nc-CaF₂ improves the gelation ability of the system through formation of F‒H hydrogen bonding between F in nc-CaF₂ and H in P precursors. Increasing HPF₆ leads to more nc-CaF₂ thus less Ca(NO₃)₂ in the dried gel, or the presence of nc-CaF₂ in the gel suppresses the formation of Ca(NO₃)₂. At elevated firing temperatures, the P containing groups react with each other to form condensed phosphate. These condensed calcium phosphate, nc-CaF₂/Ca(NO₃)₂, reacts with the rest of the amorphous phase to form FHA phase at above 400°C.     

高温煤气脱硫 Ⅰ.铁基脱硫剂的相态特征和活性

用穆斯堡尔谱考察了氧化铁脱硫剂在高温煤气中还原及硫化时的铁形态变化规律。在反应开始阶段，原脱硫剂中的α-Fe2O3即被迅速还原成Fe3O,Fe3O4可进一步还原转化成α-Fe。反应初期Fe3O4和α-Fe都参与脱硫反应，其中α-Fe具有较高的脱硫活性，对整个脱硫过程而言α-Fe是主要的脱硫活性相。铁化合物与硅铝氧化物载体间存在相互作用，形成磁微 晶颗粒及少量γ-Fe。在高温煤气条件下，FeS是唯一的铁硫化物，θ－Fe3C则是α－Fe转化中的主要产物。适量的θ－F e3C对脱硫有促进作用。     

Two polymorphs of cobalt(II) imidazolate polymers synthesized solvothermally by using one organic template N,N-dimethylacetamide

Two structurally different polymorphs of cobalt(II) imidazolate frameworks are solvothermally synthesized by using N,N-dimethylacetamide as a template: The polymorph 6 (a = 9.797 (4) angstroms, b = 15.301(6) angstroms, c =14.902(6) angstroms, beta = 98.904(6) degrees, monoclinic, P21/n) shows structures of silicate CaAl2Si2O8 with CrB4 topology, while polymorph 7 (a = 15.173(4) angstroms, b = 15.173(4) angstroms, c = 19.089(5) angstroms, Pbca) shows CaGa2O4-related topological structures. In addition, the 7' (a = 15.9712(18) angstroms, b = 15.9253(19) angstroms, c = 18.475(2) angstroms, Pbca), a compound isostructural with 7, is synthesized by using cyclohexanol as a template. Thus, these cobalt(II) imidazolate polymers are reminiscent of the zeolite syntheses in that not only the same topological structure can be synthesized by using the different organic templates, but also different topological structures can be synthesized by using the same organic template.     

Solventless polymerization: spatial migration of a catalyst to form polymeric thin films in microchannels

This paper reports a simple, additive process to generate patterned polymer films without using any solvent. This process involves a highly efficient catalyst, a Grubbs's catalyst, and a volatile monomer, norbornene. The catalyst and monomers have higher local concentrations inside the microchannels, formed by contacting poly(dimethylsiloxane) stamps to a solid surface, and allow the polymeric thin films to be defined by the microchannels. The patterned thin film serves as an excellent resistant to reactive ion etching, which promises that this process is a complementary, useful alternative to spin-coating and plasma polymerization in microfabrication.     

协萃络合物结构的研究——二(1-苯基 -3-甲基-4-三氟乙酰基吡唑啉酮-5)-(1，10菲啰啉)合钴(II)的合成、表征与晶体结构的测定

合成了二(1-苯基-3-甲基-4-三氟乙酰基吡唑啉酮-5)-(1,10菲啰啉)合钴(Ⅱ)混合配体络合物单晶, 由元素分析确定其组成为Co(C_(12)H_3F_3O_2N_2)_2·(C_(12)H_8N_2)。通过溶解性、摩尔电导, 磁性、中红外光谱、远红外光谱、差热、热重分析研究了该化合物的有关性质。用四园单晶衍射仪, 测定了该络合物的分子及晶体结构。晶体属单斜晶系, P2_(l/o)空间群,晶胞参数为:a=1.0422(3) nm, b=1.6462(2) nm, c=2.0678(3) nm, β=75.86(1)°, V=3.4402(1.6) nm, Z=4, F(000)=1580, d_(calc)=1.50 g cm~(-3), d_(exp.)=1.492g cm~(-3)。经最小二乘法修正后, 最终偏差因子R=0.0716。配合物中钴的配位数为六, 分子中有四个氧来自两个双齿配体PMTFP, 两个氮原子由phen所提供。