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91.
《Electroanalysis》2004,16(10):827-831
An amperometric detector for hydrophobic ions based on a plasticized poly(vinyl) chloride (PVC) membrane incorporated in a flow‐injection system was developed. A four‐electrode potentiostat with ohmic drop compensation was used, while a flow‐through cell incorporated the four electrodes and the membrane, which contained tetrabutylammonium tetraphenylborate. When the influence of the applied potential and of the flow‐injection variables on the determination of tetrabutylammonium was studied, a linear relationship was observed between current peak height and ion concentration over a range of 5×10?6–6×10?5 M tetrabutylammonium. Good repeatability and between‐day reproducibility and high sample frequency were obtained. The effect of other ions was studied. Two different amperometric methods, indirect and direct, were also developed for the determination of dodecylsulfate in the concentration range 3×10?5–9×10?4 M. 相似文献
92.
It is shown that insertion in methacrylic polymers of bulky electron donor/acceptor side-groups with taper-shaped flourinated tails promotes a self-organization of the respective side-chain polymers due to the space demands of the bulky D/A side-groups, leading to a columnar hexagonal mesophase. The presence of an Lc-phase is evidenced by DSC and identified by X-ray analysis. The orientation in the respective copolymers and polymer blends is additionally improved by the CT-interaction between the D/A side-groups. An increased packing effect due to this CT-orientation effect is evidenced in DSC by an increase of the respective transition temperatures. CT-interaction is responsible as well for a preferential polymerization of monomeric D/A-complexes leading to copolymers of alternating structures and for a zip-like arrangement along the main chain of the A/D-complexes between the interacting side-groups in polymer blends. Formation of mesophases is even observed in CT-interacting blends between the Lc-D/A side-chain polymethacrylates and the respective amorphous D/A side-chain polysiloxanes.This revised version was published online in November 2005 with corrections to the Cover Date. 相似文献
93.
V. V. Ozeryanskaya V. E. Guterman I. L. Shukaev V. P. Grigor'ev 《Russian Chemical Bulletin》1998,47(8):1481-1486
Comparative study of the regularities of the reaction and specific features of phase formation during electrochemical incorporation
of lithium from propylene carbonate solutions in intermetallic aluminum-based compounds (CuAl2, Mg2Al3, and NiAl) and pure metals (Al, Cu, Mg, and Ni) was performed. The initial stage of the process was shown to be dissolution
of lithium in the solid phase limited by diffusion for all studied substrates. Trace amounts of lithium-containing by-products,
were detected in NiAl, Ni, and Cu samples. The subsequent change in the limiting stage is related to the beginning of formation
of a new phase: metallic lithium (on Mg2Al3, NiAl, Mg, Ni, and Cu) or LiAl (on Al and CuAl2 cathodes). In the latter case, the solid-phase substitution occurs, which is formally described by the equation: CuAl2+2Li++2e→2LiAl+Cu. Thus, the specific features of phase formation on the CuAl2 electrode correspond to the highest (among three intermetallides studied) concentration of Al atoms in the crystal lattice
of the compound.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8. pp. 1525–1530, August, 1998. 相似文献
94.
95.
《Chemphyschem》2006,7(1):117-130
Ultra‐wideline 27Al NMR experiments are conducted on coordination compounds with 27Al nuclei possessing immense quadrupolar interactions that result from exceptionally nonspherical coordination environments. NMR spectra are acquired using a methodology involving frequency‐stepped, piecewise acquisition of NMR spectra with Hahn‐echo or quadrupolar Carr–Purcell Meiboom–Gill (QCPMG) pulse sequences, which is applicable to any half‐integer quadrupolar nucleus with extremely broad NMR powder patterns. Despite the large breadth of these central transition powder patterns, ranging from 250 to 700 kHz, the total experimental times are an order of magnitude less than previously reported experiments on analogous complexes with smaller quadrupolar interactions. The complexes examined feature three‐ or five‐coordinate aluminum sites: trismesitylaluminum (AlMes3), tris(bis(trimethylsilyl)amino)aluminum (Al(NTMS2)3), bis[dimethyl tetrahydrofurfuryloxide aluminum] ([Me2‐Al(μ‐OTHF)]2), and bis[diethyl tetrahydrofurfuryloxide aluminum] ([Et2‐Al(μ‐OTHF)]2). We report some of the largest 27Al quadrupolar coupling constants measured to date, with values of CQ(27Al) of 48.2(1), 36.3(1), 19.9(1), and 19.6(2) MHz for AlMes3 , Al(NTMS2)3 , [Me2‐Al(μ‐OTHF)]2 , and [Et2‐Al(μ‐OTHF)]2 , respectively. X‐ray crystallographic data and theoretical (Hartree–Fock and DFT) calculations of 27Al electric field gradient (EFG) tensors are utilized to examine the relationships between the quadrupolar interactions and molecular structure; in particular, the origin of the immense quadrupolar interaction in the three‐coordinate species is studied via analyses of molecular orbitals. 相似文献
96.
Shiyang Sun Shouye Sun Yuan Ren Xin Tan Pingping Xu 《Surface and interface analysis : SIA》2020,52(4):167-173
The surface structure and properties of aluminum nitride (AlN) play an important role in many applications. Using the first principle calculations method, we analyzed the surface terminal structure of AlN and its evolution under different conditions by determining the surface energy, adsorption energy, and evaporation energy of the Al and N terminals on the AlN(0001) surface. Our results show that the reason why the N terminal is less stable than the Al terminal is not only because of its high surface energy but also because its adsorption performance is extremely sensitive to the adsorption position. The surface N atoms combine to form N2 molecules that escape during the evaporation process at high temperature. After surface N atoms escape, the AlN surface structure reconstitutes to form a hexagonal closest packing (HCP)–like structure, and the energy barrier for the reconstructing process is 3.2 eV. This shows that the structure and form of the AlN(0001) terminals depend on the environmental conditions. 相似文献
97.
Fang Sun David W. Grainger 《Journal of polymer science. Part A, Polymer chemistry》1993,31(7):1729-1740
Copolymers of 2-hydroxyethyl acrylate and 2-methoxyethyl acrylate with variable compositions were synthesized, fractionated, and characterized by 1H-NMR, IR, GPC, and viscometry. These copolymers were further modified via polymer analog esterification of copolymer hydroxy groups by a series of disulfide-containing carboxylic acids including lipoic acid and (n-pentyldithio) alkyl carboxylic acids (n-C5H11SS(CH2)m? COOH, m = 10, 15, 22) in the presence of 1,3-dicyclohexylcarbodiimide (DCC). Esterification reactions were quantitative for copolymers possessing hydroxy monomer contents ≤ 40% when excess acid and DCC were present for sufficiently long reaction times (2–4 days) at room temperature. Copolymer DSC analysis demonstrates a systematic variation of Tg with copolymer composition in good agreement with ideal mixing theory. These disulfide-bearing copolymers spontaneously yield two-dimensional ultrathin polymer films with side chain-dependent layer thicknesses of 20–45 Å by solution adsorption onto freshly deposited gold surfaces. Such ultrathin polymer films are expected to have diverse applications as bound polymeric surface modification reagents. © 1993 John Wiley & Sons, Inc. 相似文献
98.
99.
Burdick Brent A. Esders Theodore W. Schaeffer James R. Lynn Shirley 《Applied biochemistry and biotechnology》1987,16(1):145-156
Several hydrophilic polymeric thiols were prepared from aminoactivated polymeric supports by reaction with N-acetylhomocysteinethiolactone.
Supports include agaroses, cellulose, Glycophase™ controlled-pore glass, and Matrex™ acrylic beads. Thiol content in these
polymers was 3–72 μmol SH/g dry polymer. Several were effective solid-phase activators of the sulfhydryl-dependent enzyme
creatine phosphokinase at concentrations comparable to that of monomeric thiol required for enzyme activation. The kinetic
activation curves for the polymeric and the monomeric (thioglucose) activators were similar, suggesting unhindered interaction
of the enzyme with the polymeric activator. 相似文献
100.
F. Amat-Guerri J. M. Botija R. Sastre 《Journal of polymer science. Part A, Polymer chemistry》1993,31(10):2609-2615
Thionine ( 1 ) has been covalently bound to linear copoly(styrene-p-vinylbenzyl chloride) and to linear copoly(acrylic acid-2-ethylhexyl acrylate). The resulting polymeric dyes, purified by ultrafiltration, present quantum yields of singlet oxygen generation in dimethylformamide solution lower than their corresponding low-molecular-weight models thionine hydrochloride ( 1.HCl ) and N(3)-acetylthionine ( Ac-1 ), the decrease being more pronounced in the case of the polystyrene-dye photosensitizer. High chromophore concentrations within the volume encompassed by each macromolecule in the solution can explain this fall in efficiency. The free dyes thionine hydrochloride and its hydrolysis products thionoline ( 2 ) and thionol ( 3 ) behave as good singlet oxygen generators, with quantum yields of 0.71, 0.62, and 0.63, respectively. © 1993 John Wiley & Sons, Inc. 相似文献