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131.
Josef Janča 《Mikrochimica acta》1994,112(5-6):197-215
The primary field forces can generate spatially oriented gradient of the effective property of a continuum or pseudo-continuum fluid (carrier liquid). When this gradient is coupled with the action of a secondary field of identical or different nature the isoperichoric focused zones of the dispersed species can appear. Consequently, they can be separated according to differences responding to the property gradient of the carrier liquid. This concept can be applied under static (non-flow) conditions in thin layer focusing as well as under dynamic conditions with the elution due to the carrier liquid flow in focusing field-flow fractionation. The gradient established by the action of the primary field and the concentration distribution of the isoperichoric focused zone formed by the coupled effect of the gradient and of the primary or secondary field are described theoretically. The rigorous relationship describing the shape of the focused zone is compared with the approximate solutions. The performances of the proposed principle were evaluated by model calculations. Potential experimental configurations considering the implementation of the static and dynamic conditions are discussed. The generalized isoperichoric focusing theory can be applied to describe the particular processes operating in analytical and preparative focusing separations of the particles of various, but especially of biological origin. 相似文献
132.
甲烷在SrO-La2O3/CaO催化剂上的氧化偶联Ⅱ.反应动力学的研究 总被引:1,自引:0,他引:1
在20%La2O3/CaO(LC)催化剂中添加SrO(添加SrO的LC以SLC表示)明显地提高了反应活性和C2选择性。反应动力学研究表明,LC和SLC催化剂在甲烷氧化偶联反应中,在表观活化能和表观反应级数上存在很大的差异。LC催化剂在CH4转化以及C2和COx形成过程中,表观活化能大于SLC催化剂,而SLC催化剂的指前因子小于LC体系,两者存在着补偿形象。SLC催化剂的反应速率常数比kc2/kCH 相似文献
133.
超声波作用下羰基化合物的还原偶联反应 总被引:5,自引:0,他引:5
超声波在一些有机反应中有明显的促进作用「“,Luche等认为超声波的作用有两种主要类型[’j.一类是涉及电子转移的自由基或离子一自由基型反应,由于超声波的空化作用所产生的局部高温高压可以促进电子转移,从而明显地加快反应速度;对大多数离子型反应,超声波只能起到机械的物理作用.我们曾报道偕二卤化合物在Li、Na、Mg等金属作用下产生卡宾的反应是单电子转移过程,该反应可由于超声辐射而大大加速[‘];而在芳基叔脚的断裂反应中,超声波可以促进三苯基俄与金属馊反应生成二苯基脚负离子,但对它进一步的亲核取代反应却没有明… 相似文献
134.
Dieter Seebach 《Angewandte Chemie (International ed. in English)》1988,27(12):1624-1654
The chemistry of lithium enolates is used to demonstrate that complex structures held together by noncovalent bonds (“supramolecules”) may dramatically influence the result of seemingly simple standard reactions of organic synthesis. Detailed structural data have been obtained by crystallographic investigations of numerous Li enolates and analogous derivatives. The most remarkable features of these structures are aggregation to give dimers, tetramers, and higher oligomers, complexation of the metal centers by solvent molecules and chelating ligands, and hydrogen-bond formation of weak acids such as secondary amines with the anionoid part of the enolates. The presence in nonpolar solvents of the same supramolecules has been established by NMR-spectroscopic, by osmometric, and by calorimetric measurements. The structures and the order of magnitude of the interactions have also been reproduced by ab-initio calculations. Most importantly, supramolecules may be product-forming species in synthetic reactions of Li enolates. A knowledge of the complex structures of Li enolates also improves our understanding of their reactivity. Thus, simple procedures have been developed to avoid complications caused by secondary amines, formed concomitantly with Li enolates by the common methods. Mixtures of achiral Li enolates and chiral Li amides can give rise to enantioselective reactions. Solubilization by LiX is observed, especially of multiply lithiated compounds. This effect is exploited for alkylations of N-methylglycine (sarcosine) CH2 groups in open-chain oligopeptides. Thus, the cyclic undecapeptide cyclosporine, a potent immunosuppressant, is converted into a THF-soluble hexalithio derivative (without epimerization of stereogenic centers) and alkylated by a variety of electrophiles in the presence of either excess lithiumdiisopropyl amide or of up to 30 equivalents of lithium chloride. Depending on the nature of the LiX additive, a new stereogenic center of (R) or (S) configuration is created in the peptide chain by this process. A structure-activity correlation in the series of cyclosporine derivatives thus available is discussed. 相似文献
135.
Li—Ni—La—O系复合氧化物催化剂上甲烷氧化偶联的研究 总被引:2,自引:0,他引:2
考察了Li-Ni-La-O系催化剂的组成、结构及反应条件对甲烷氧化偶联反应活性的影响。在780℃、CH4:O2:N2=2:1:7、空速15000h^-1时,C2烃收率可达25.8%。XRD、IR、XPS及SEM等的结构分析表明,在LiLa1-xNixO2催化剂中,当0.1≤x≤0.9时,该催化剂由LiNiO2和La2Ni1-yLiyO4-λ两相组成,x<0.3时出现了LiLaO2相,La2Ni1- 相似文献
136.
Anthony P. Panarello 《Tetrahedron letters》2005,46(8):1353-1356
Chiral ansa-ethylene-bis(indenyl)-metal complexes, EBI-MX2, are useful pre-catalysts for a wide variety of reactions, including hydrogenations, hydrosilylations, and polymerization reactions. In order to immobilize these complexes onto heterogeneous supports, a new methodology was developed to introduce functional anchors to the ethylene-bis(indenyl) ligand, EBI. This was accomplished by selective alkylation of indene to form toluene-4-sulfonic acid 2-(3H-inden-1-yl)-ethyl ester, which was then used to alkylate 6-bromoindene. The selective introduction of an aryl bromide then undergoes coupling reactions with aryl borates via the Suzuki coupling to efficiently introduce an alkenyl or alcohol, functional anchor in a simple four step synthesis. 相似文献
137.
Toshimi Anzo 《Tetrahedron letters》2007,48(48):8442-8448
A formal synthesis of the antimicrobial tricyclic macrolides, tubelactomicins A and E, featured by a transannular Diels-Alder (TADA) approach, has been explored. The key issue for the transannular cyclization was the synthesis of a 24-membered macrolactone equipped with all the requisite functionalities, which has been achieved using an intramolecular Hiyama cross-coupling strategy. The Hiyama coupling reaction spontaneously triggered off the TADA reaction. From the endo-TADA adduct, formal syntheses of tubelactomicins A and E were achieved. The 24-membered macrolactone formation was also achieved via an intramolecular ring-closing metathesis approach. 相似文献
138.
The coupling of two or four mono-6-amino β-cyclodextrin (amino-CD) units, (unprotected or permethylated hydroxyls), to diisopropoxycalix[4]arene crown-6 (CAL) was realised using the N,N′-succinyldiamide linker. The resulting molecules in two series were characterised with the help of mass and NMR spectroscopies. The yields of all coupling products were improved for permethylated sugar series compared to the hydroxylated CD series or to our previous studies. The two β-cyclodextrin (β-CD) residues coupled to disubstituted CAL were orientated from the same side of the crown ether. 相似文献
139.
Natural rubber is reinforced with a novel type of grass fiber (Cyperus Tegetum Rox b). The effects of fiber loading of different mesh sizes on curing characteristics and mechanical properties of grass fiber filled natural rubber composite are studied. Since 400 mesh grass fiber loaded natural rubber composite shows superior mechanical properties, therefore the effect of silane coupling agent was studied for this particular composite. Here composites were prepared by using water leached grass fiber. Optimum cure time increases with the increase in fiber loading but the change in scorch time is less. The same trend of increase in optimum cure time is observed in the presence of Si69. But the value is higher compared to that of rubber composite without Si69. With increase in the fiber loading, modulus and hardness of the composite increases but tensile strength decreases. The mechanical properties of the composite, namely moduli at 200 and 300% elongation and hardness increase in the presence of Si69 but tensile strength is less compared to that of the composite without Si69. Elongation at break is not much affected due to the presence of Si69. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
140.