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101.
The treatment of octafluorocyclopentene with organolithium reagents gave the corresponding symmetrical disubstituted perfluorocyclopentenes in good to high yields. The reaction with Grignard reagents led to the monosubstituted perfluorocyclopentenes, which were subjected to the further nucleophilic substitution reaction using another Grignard or aryllithium reagents, unsymmetrical disubstituted perfluorocyclopentenes being obtained in high yields. 相似文献
102.
Double Pore Silica Gel Monolith Applied to Liquid Chromatography 总被引:2,自引:0,他引:2
K. Nakanishi H. Minakuchi N. Soga N. Tanaka 《Journal of Sol-Gel Science and Technology》1997,8(1-3):547-552
Silica gels retaining double pore structure in the size ranges of micrometer and nanometer have been applied to the rod-shaped
monolithic column for liquid chromatography. The macropore structure was designed by controlling the phase separation process
induced by the hydrolysis and polycondensation of alkoxysilane, whereas the mesopore structure was tailored by the solvent
exchange treatments on wet gels. The size exclusion chromatograms on polystyrene standards exhibited almost similar features
for octadecyl-modified rod and conventional packed beads columns. The dependence of plate height on the velocity of mobile
phase determined for amylbenzene was by far weaker in the rod column than in the packed beads column, suggesting that additional
geometrical factors should be considered in describing the separation mechanism in the rod column. 相似文献
103.
Ana I. Olives Emiliano E. Romero-Ale M. Antonia Martín Benito del Castillo Pilar López-Alvarado J. Carlos Menéndez 《Journal of inclusion phenomena and macrocyclic chemistry》2007,57(1-4):553-559
Carbazole-9-carbonyl chloride (C9CC) and 9-carbazolylacetic acid (9CAA) were selected as model fluorescent reagents. The effect
of different chemically modified cyclodextrins (CDs) added to the aqueous solutions of these reagents was studied in water
and in buffered aqueous solutions at pH 4.5 and 8.8. The CDs employed were 2-hydroxypropyl-β-cyclodextrin (HP-βCD), 2,3-di-O-methyl-β-cyclodextrin (DM-βCD) and 2,3,6-tri-O-methyl-β-cyclodextrin (TM-βCD). The inclusion of these reagents inside the cavities of the CDs was verified and this process
can affect the derivatization reaction because CDs can modify the reactivity of the guest molecules. The basic conditions
necessary for the derivatization reaction between C9CC and amines lead to the formation of carbazole anion through hydrolysis
followed by decarboxylation. In the presence of CDs, the hydrolysis-decarboxylation of carbazole-9-carbonyl chloride is faster
than in buffered aqueous homogeneous solutions. The behaviour observed for these reagents in aqueous solutions of CDs was
compared to the one observed in basic ethanolic solutions. These changes are particularly noticeable in the case of 2,3-di-O-methyl-β-CD and 2-hydroxypropyl-β-CD. The characteristics of the fluorescent reagents are compared to carbazole and 9-methylcarbazole
as model compounds.
This paper was presented at XIIIth International Cyclodextrin Symposium. Torino, Italy, May 14–17, 2006. 相似文献
104.
A. D. Dilman D. E. Arkhipov P. A. Belyakov M. I. Struchkova V. A. Tartakovsky 《Russian Chemical Bulletin》2006,55(3):517-522
Reactions of tris(pentafluorophenyl)silanes RSi(C6F5)3 with salicylaldehyde and secondary amines were studied. The reactions afforded α-pentafluorophenyl-substituted amines. Silanes
RSi(C6F5)3 (R = Me, Ph, C6F5, CH2CH=CH2, and CH=CH2) were found to be efficient reagents for transfer of the C6F5 group to the iminium cation generated from salicylaldehyde and amine. However, tris(pentafluorophenyl)phenylethynyl-and tris(pentafluorophenyl)silanes
were not able to serve as a source of a fluorinated substituent because of competitive transfer of acetylenide fragment or
hydride.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 498–503, March, 2006. 相似文献
105.
106.
Shimpei Sugiyama 《Tetrahedron letters》2006,47(49):8771-8775
The treatment of γ-lactones having a sulfinyl group at the γ-position, which were synthesized from 1-chlorovinyl p-tolyl sulfoxides with lithium enolate of carboxylic esters, with isopropyl magnesium chloride in THF at −78 °C gave γ-chloromagnesio γ-lactones by the sulfoxide-magnesium exchange reaction in high yields. The generated γ-chloromagnesio γ-lactones were found to be stable at below −50 °C for at least 2 h. The reaction of these γ-chloromagnesio γ-lactones with electrophiles and the stereochemistry of the reactions were investigated. 相似文献
107.
失效原子力显微镜硅针尖再生 总被引:2,自引:0,他引:2
原子力显微镜的传统商品硅针尖在使用过程中极易因磨损而失效,本文研究了一种在实验室条件下简易可行的回收利用失效硅针尖的方法。在原子力显微镜的敲击模式下使用曲率半径大于100 nm的失效硅针尖对生长单壁碳纳米管的样品表面进行扫描,把样品表面的单壁碳纳米管管束粘接到硅针尖上,可制得直径在5~20 nm的碳纳米管针尖。实验对碳纳米管针尖和新的商品硅针尖进行了成像对比,所制备的碳纳米管针尖不仅在成像分辨率而且在成像稳定性上都优于新的商品硅针尖。 相似文献
108.
Nitrogen ion implantation (24 keV, 4.6 × 1017 cm?2) into (100) a p‐type silicon wafer material and a subsequent electron beam annealing at 1100 °C for 15 s under high vacuum conditions leads to the formation of an uneven surface in the implanted region caused by nitrogen bubbles beneath the surface. Annealing at 1200 °C for 300 s results in surface cavities with a mean diameter of 350 nm and a surface coverage of 3–4% and an average depth of ~60 nm. Nuclear reaction analysis reveals that the nitrogen concentration in the as‐implanted state exceeds 57 at%, the value of stoichiometric Si3N4. Annealing at 1100 °C for 15 s slightly reduces the nitrogen peak concentration, whereas annealing at 1200 °C for 300 s induces a significant alteration to the shape of the nitrogen depth profile coupled with the lowering of the concentration close to the stoichiometry of Si3N4. The results present a new method of producing sub‐micrometre cavities embedded in a thin silicon nitride film on wafer silicon which may lead to novel micro‐electronic and biotechnology applications. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
109.
110.
Traditionally, the application of supercritical fluid chromatography has been limited to compounds of relatively low polarity.
Thus, we report here that one secondary amine and two quaternary amine salts were successfully eluted from a Deltabond Cyano-bonded
silica column with the addition of sodium alkylsulfonate to the methanol-modified, carbon dioxide-based mobile phase. A possible
ion-pairing interaction between the positively charged analytes and the anionic part of the sulfonate additive has been proposed.
In another set of experiments, the three amine salts readily eluted from both Ethyl-pyridine-bonded silica and Amino-bonded
silica phases without the need of additive although the peak shapes were less than desirable. The addition of sulfonate salt
to the mobile phase again sharpened the peaks. In the presence of a mixture of methanol and CO2, we suggest that these stationary phases are positively charged. We describe here also for the first time the employment
of a strong silica-based anion exchange (SAX) column for supercritical fluid separation of cationic species. Two elution mechanisms
were proposed for the three amine salts depending upon whether the ionic additive was incorporated into the mobile phase.
Separation as the ion-pair was proposed with an ionic additive in the mobile phase; whereas separation of the intact amine
salt from the positively charged basic stationary phases was suggested to be operational without the ionic additive. 相似文献