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91.
G. Bruno P. Capezzuto G. Cicala F. Cramarossa 《Plasma Chemistry and Plasma Processing》1986,6(2):109-125
Plasma-chemical reduction of SiCl4 in mixtures with H2 and Ar has been studied by optical emission spectroscopy (OES) and laser interferometry techniques. It has been found that the Ar:H2 ratio strongly affects the plasma composition as well as the deposition (r
D) and etch (r
E) rates of Si: H, Cl films and that the electron impact dissociation is the most important channel for the production of SiClx species, which are the precursors of the film growth. Chemisorption of SiClx and the reactive surface reaction SiClx+H–SiCl(x–1)0+HCl are important steps in the deposition process. The suggested deposition model givesr
D [SiClx][H], in agreement with the experimental data. Etching of Si: H, Cl films occurs at high Ar: H2 ratio when Cl atoms in the gas phase become appreciable and increases with increasing Cl concentration. The etch rate is controlled by the Cl atom chemisorption step. 相似文献
92.
The complexes trans-[PdCl{(ME)=NR'} (PPh3)2] (R=C6H11,p-C6H4OMe; R=p-C6H4OMe, Me) containing a σ-bonded 1,4-diaza-3-menthyl-butadiene-2-yl group with different substituents on the nitrogen atoms have been prepared by two routes. The first involves initial methylation of the mixed isonitrile complex [PdCl2(CNR)(CNR')]by HgMe2, followed by reaction with PPh3 (molar ratio ). The second method involves condensation of primary aliphatic amines with the carbonyl group of the 1-azabut-1-en-3-one-2-yl moiety of the complex trans-[PdCl{(Me) = 0} (PPh3)2]. The 1,4-diaza-3-methylbutadiene-2-yl derivatives act through their imino nitrogen atoms as chelating ligands towards anhydrous metal chlorides MCl2 (M = Co, Ni, Cu, Zn). Magnetic moment measurements and the far-infrared and electronic spectra of these adducts indicate an essentially pseudo-tetrahedral configuration at M in the solid and in solution. With the ZnCl2 adducts, the 1H NMR pattern for the phenyl protons of the p-methoxyphenyl N-substituents dependss upon the position of the substituent i the 1,4-diazabutadiene chain. 相似文献
93.
Bruno Ameduri Bernard Boutevin Fouad Malek 《Journal of polymer science. Part A, Polymer chemistry》1994,32(16):3161-3169
The synthesis of maleimides that have pyrazolic or bipyrazolic pendant groups is described. Their homopolymerization and their copolymerization with 2-chloroethyl vinyl ether (CEVE) is reported. The homopolymerizations of such maleimides were performed under various conditions and led to low molecular-weight polymers. However, alternating copolymers were obtained from CEVE as comonomers whatever the monomers feed compositions. A similar behavior was also observed for maleimides that do not exhibit any spacer, whereas for bulky vinyl ethers, random copolymers were produced. A comparison of the thermal behavior between these copolymers (glass transition temperatures, Tg, and decomposition temperatures) and other copolymers having different spacers between the nitrogenated cycles and the chain are related. Thus, an important decrease of Tg, was observed when C3H6CO2CH2 groups were used as the spacer instead of methylene groups. Moreover, the thermal weakness of these copolymers may come from the substituents of the vinyl ether and is discussed. © 1994 John Wiley & Sons, Inc. 相似文献
94.
Bruno Jean Georges Bokias Lay-Theng Lee Ilias Iliopoulos Bernard Cabane 《Colloid and polymer science》2002,280(10):908-914
The structures of aqueous copolymer solutions have been examined through small angle neutron scattering. The copolymers contained mostly N-isopropylacrylamide (NIPAM) monomers. Poly (NIPAM) solutions have a lower critical solution temperature (LCST), above which the macromolecules separate from water. A small fraction of ionizable N,N-[(dimethylamino) propyl] methacrylamide (MADAP) monomers was introduced into the macromolecules. This had dramatic consequences on the solution behavior at temperatures above the LCST of PNIPAM, where phase separation would have been expected for the homopolymer. When all MADAP monomers were ionized, it was found that the solutions resisted the phase separation. At short spatial scales, the chains were collapsed but at large scales they formed branched aggregates that did not separate out of water. When only half of the MADAP monomers are ionized, the electrical charges were able to redistribute themselves along the chains. In this case, the rise in temperature caused a microphase separation where the electrical charges were relocated on a fraction of the chains that remained in solution.The other chains (or section of chains) formed large nodules of a polymer rich phase. 相似文献
95.
Sequence-specific binding of DNA to liposomes containing di-alkyl peptide nucleic acid (PNA) amphiphiles 总被引:1,自引:0,他引:1
We present a method to covalently attach peptide nucleic acid (PNA) to liposomes by conjugation of PNA peptide to charged amino acids and synthetic di-alkyl lipids ("PNA amphiphile," PNAA) followed by co-extrusion with disteroylphosphatidylcholine (DSPC) and cholesterol. Attachment of four Glu residues and two ethylene oxide spacers to the PNAA was required to confer proper hydration for extrusion and presentation for DNA hybridization. The extent of DNA oligomer binding to 10-mer PNAA liposomes was assessed using capillary zone electrophoresis. Nearly all PNAs on the liposome surface are complexed with a stoichiometric amount of complementary DNA 10-mers after 3-h incubation in pH 8.0 Tris buffer. No binding to PNAA liposomes was observed using DNA 10-mers with a single mismatch. Longer DNA showed a greatly attenuated binding efficiency, likely because of electrostatic repulsion between the PNAA liposome double layer and the DNA backbone. Langmuir isotherms of PNAA:DSPC:chol monolayers indicate miscibility of these components at the compositions used for liposome preparation. PNAA liposomes preserve the high sequence-selectivity of PNAs and emerge as a useful sequence tag for highly sensitive bioanalytical devices. 相似文献
96.
Zhdankin VV Maydanovych O Herschbach J Bruno J Matveeva ED Zefirov NS 《The Journal of organic chemistry》2003,68(3):1018-1023
The preparation and chemistry of novel phosphoranyl-derived lambda(3)-iodanes is reported. The phosphoranyl-derived phenyliodonium sulfonates were prepared in good yields by the reaction of stabilized phosphonium ylides [1-triphenylphosphoranylidene-2-propanone, methyl(triphenylphosphoranylidene)acetate, (triphenylphosphoranylidene)acetaldehyde, and (triphenylphosphoranylidene)acetonitrile] with the pyridinium complex of iodobenzene ditriflate or with [hydroxy(tosyloxy)iodo]benzene under mild conditions. These compounds represent a potentially useful class of reagents that combine in one molecule synthetic advantages of a phosphonium ylide and an iodonium salt. Specifically, phosphorane-derived phenyliodonium tosylates can react with soft nucleophiles, such as iodide, bromide, benzenesulfinate, and thiophenolate anions, with a selective formation of the respective alpha-functionalized phosphonium ylides, which can be further converted to alkenes by the Wittig reaction with benzaldehyde. The phosphoranyl-derived benziodoxoles can be prepared by the reaction of 1-acetoxybenziodoxole with stabilized phosphonium ylides. An unusual ligand exchange on the iodine(III) center resulting in the substitution of a carbon ligand with an oxygen ligand was observed in the reaction of these compounds with strong acids. 相似文献
97.
Alfredo E. Bruno Ronald P. Steer Paul G. Mezey 《Journal of computational chemistry》1983,4(1):104-109
Approximate minimum energy reaction paths have been calculated for two thioketone–enethiol tautomeric systems using an ab initio SCF–MO method. The calculations indicate nearly equal stabil ties of the isolated tautomers in both systems and an energy barrier of ca. 85 kcal/mol for their interconversion. This barrier is expected to be significantly lower in solution as a result of solvent–solute interactions. 相似文献
98.
Calorimetric measurements of molar excess enthalpies, HE, at 298.15 K, of mixtures containing aromatic aldehydes of general formula C6H5(CH2)mCHO (with m = 0, 1 and 2) + n-hexane, n-heptane or benzene are reported, together with the values of HE at equimolar composition compared with the corresponding values of HE for the aromatic ketones in the same solvents. The experimental results clearly indicate that the intermolecular interactions between the carbonyl groups (CHO) are influenced by the intramolecular interactions between the carbonyl and phenyl groups, particularly for the mixtures containing benzaldehyde. 相似文献
99.
The photolysis and thermolysis of the Cyclopropyl silyl ketones 3, 4 , and 5 are described. On n,π* excitation, the silyl ketones 3 and 4 undergo a Norrish-type-II reaction involving γ-H abstraction, cyclopropyl ring cleavage followed by retro-enolization to the acylsilanes 6 and (E/Z)- 12 , respectively. As a common product of 3 and 4 , the dihydrofuran 7 is formed via the alternative C(α)-C(β) cleavage of the cyclopropyl moiety. Compounds 6 , 7 , and (E/Z)- 12 are new types of acylsilane photoproducts. The irradiation of acylsilane 5 gave the analogous dihydrofuran 15 as the only product. On photolysis of 3 and 4 , products 8A + B and 13A + B , derived from a siloxy carbene intermediate, were found as well. On thermolysis of 3 and 4 , the acylsilanes 6 (80%), and (E)- 12 (33%) and (Z)- 12 (34%), respectively, are formed as the only products. Their formation may occur via a [1, 5] sigmatropic H-shift. The thermolysis of 5 gave the diene 16 whose formation can be explained by insertion of a siloxycarbene into the neighboring cyclopropane leading to the cyclobutene 28 as thermally unstable intermediate. 相似文献
100.
E.?DesimoniEmail author B.?Brunetti R.?Cattaneo 《Accreditation and quality assurance》2004,9(8):445-449
Considering the uncertainty of measurement when assessing compliance with reference values given in compositional specifications and statutory limits is still a controversial matter. In theory, assessing compliance requires considering both type I (false positive) and type II (false negative) errors. The more the concentration of the analyte in the sample under investigation is close to the allowed concentration limit, the more critical it is to consider both types of errors. This paper describes how this could be done. The matter is discussed in the light of the most recent literature information. 相似文献