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991.
Memboeuf A Vékey K Lendvay G 《European journal of mass spectrometry (Chichester, England)》2011,17(1):33-46
Density functional theoretical methods, including several basis sets and two functional, were used to collect information on the structure and energetic parameters of poly(ethylene glycol) (PEG), also referred to as poly(ethylene oxide) (PEO), coordinated by alkali metal ions. The oligomer chain is found to form a spiral around the alkali cation, which grows to roughly two helical turns when the oligomer size increases to about the decamer for each alkali ion. Above this size, the additional monomer units do not build the spiral further for Li(+) and Na(+); instead, they form less organized segments outside or next to the initial spiral. The distance of the first layer of co-ordinating O atoms from the alkali cation is 1.9-2.15 ? for Li(+), 2.3-2.5 ? for Na(+), 2.75-3.2 ? for K(+) and 3.5-3.8 ? for Cs(+) complexes. The number of O atoms in the innermost shell is five, six, seven and eleven for Li(+), Na(+), K(+) and Cs(+). The collision cross sections with He increase linearly with the oligomer to a very good approximation. No sign of leaning towards the 2/3 power dependence characterizing spherical particles is observed. The binding energy of the cation to the oligomer increases up to polymerization degree of about 10, where it levels off for each alkali-metal ion, indicating that this is approximately the limit of the oligomer size that can be influenced by the alkali cation. The binding energy-degree of polymerization curves are remarkably parallel for the four cations. The limiting binding energy at large polymerization degrees is about 544 kJ mol(-1), 460 kJ mol(-1), 356 kJ mol(-1) and 314 kJ mol(-1) for Li, Na, K and Cs, respectively. The geometrical features are compared with the X-ray and neutron diffraction data on crystalline and amorphous phases of conducting polymers formed by alkali-metal salts and PEG. The implications of the observations concerning collision cross sections and binding energies to ion mobility spectroscopy and mass spectrometry are discussed. 相似文献
992.
Forced ideal carbocationic copolymerization of isobutylene/styrene systems has been achieved by continuous addition of mixed monomer feeds to 2-chloro-2,4,4-trimethylpentane/TiCl4 in n-hexane/methylene chloride charge by keeping the input rate equal to the overall rate of copolymerization. The composition of the copolymers was identical to that of the feeds over the entire monomer concentration range. The number-average molecular weight of the copolymers increased almost linearly with the amount of consumed monomers at higher isobutylene concentrations in the feed. The molecular weight increase was less pronounced at higher styrene concentration because more methylene chloride had to be used in the solvent system to keep the copolymer in solution. The micro-structure of the copolymers is uniform as determined by gel permeation chromatography (UV plus RI) and 13C-NMR spectroscopy According to these studies, true copolymers have formed. The probability of triads in the copolymer has been determined. 相似文献
993.
The double Kabachnik–Fields condensation of primary amines with 2 equivalents of the other reagents (formaldehyde and a >P(O)H species, such as dialkyl phosphites, diphenylphosphine oxide, as well as the related dioxaphosphorine and oxaphosphorine derivatives) carried out under microwave conditions afforded the title products in 79–94% yields. The bis(phosphinoxidomethyl)amines were converted, after double deoxygenation, to the corresponding ring platinum complexes.
994.
Ákos Szabó András Wacha Ralf Thomann Györgyi Szarka Attila Bóta 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(4):252-259
Novel, unique amphiphilic pentablock terpolymers consisting of the highly hydrophobic polyisobutylene (PIB) mid-segment attached to the hydrophilic combshaped poly(poly(ethylene glycol) methacrylate) (PPEGMA) polymacromonomer chains, which are coupled to poly(methyl methacrylate) (PMMA) outer segments were synthesized by the combination of quasiliving carbocationic polymerization and atom transfer radical polymerization (ATRP). First, a bifunctional PIB macroinitiator was prepared by quasiliving carbocationic polymerization and subsequent quantitative chain end derivatizations. Quasiliving ATRP of PEGMAs with different molecular weights (Mn = 188, 300 and 475 g/mol) led to triblock copolymers which were further reacted with MMA under ATRP conditions to obtain PMMA-PPEGMA-PIB-PPEGMA-PMMA ABCBA-type pentablock copolymers. It was found that slow initiation takes place between the PIB macroinitiator and PEGMA macromonomers with higher molecular weights via ATRP. ATRP of MMA with the resulting block copolymers composed of PIB and PPEGMA chain segments led to the desired block copolymers with high initiating efficiency. Investigations of the resulting pentablock copolymers by DSC, SAXS and phase mode AFM revealed that nanophase separation occurs in these new macromolecular structures with average domain distances of 11-14 nm, and local lamellar self-assembly takes place in the pentablocks with PPEGMA polymacromonomer segments of PEGMAs with Mn of 118 g/mol and 300 g/mol, while disordered nanophases are observed in the block copolymer with PEGMA having molecular weight of 475 g/mol. These new amphiphilic block copolymers composed of biocompatible chain segments can find applications in a variety of advanced fields. 相似文献
995.
József Kökösi Istvan Hermecz György Szász Zoltán Mészáros 《Tetrahedron letters》1981,22(48):4861-4862
Rutecarpine has been synthetised from hydrazone , in high yield by Fischer indole synthesis, Hydrazone has been prepared from with benzenediazonium chloride or with phenylhydrazine. Shows a solvent dependent E-Z isomerism. 相似文献
996.
Attila Bóta Krisztina László Lajos György Nagy Günter Subklew Heide Schlimper Milan J. Schwuger 《Adsorption》1997,3(1):81-91
The possibility of using pyrolyzed wastes produced in already working incineration plants, as adsorbents for waste water treatment,
was studied. Showing very poor adsorption properties, they were improved by steam activation technique used in the conventional
activated carbon manufacturing. It is concluded that various organic waste materials can be converted to carbonaceous final
products with a character similar to activated carbon. Their adsorption properties and pore size distribution are determined
by the structure of the starting material. Although most of these samples have a low specific surface area, their pore volume
is not negligible in the meso-and micropore range. Adsorption tests with model waste waters confirmed that adsorption properties
are strongly influenced by the character of the suface. The adsorption capacity of these samples can be utilized for the treatment
of strongly polluted industrial waste waters. Considering that the raw material ‘needed’ to manufacture these adsorbent is
produced permanently and the adsorbents do not have to be regenerated, it might be worthwhile using these kinds of adsorbents
in the primary treatment of industrial waste waters. 相似文献
997.
Zsolt Rapi Péter Bakó György Keglevich Péter Baranyai Miklós Kubinyi Olívia Varga 《Journal of inclusion phenomena and macrocyclic chemistry》2014,80(3-4):253-261
Two new chiral glucopyranoside-based crown ethers incorporating acridine fluorescent signalling units, 15-membered ligand 1 and 21-membered ligand 2 were synthesized. Their complexation properties toward alkali and alkali earth metal ions, and their enantioselectivity towards chiral ammonium salts were studied by absorption and fluorescence spectroscopic experiments. Macrocycle 1 formed 1:1 complexes with all the metal ions selected and the stability constants were low (lg K < 2.3). The cavity-size of 2 allowed only the complexaton of organic ammonium ions. Crown 2 showed chiral discrimination in case of all the four ammonium salts used as model guest compounds; the highest enantioselectivity (K(R)/K(S) ~3) was observed for the enantiomers of phenylethyl ammonium perchlorate. Ligand 2 forms much more stable complexes with metal ions; the highest stability constant was obtained for the Ca2+ complex (lg K = 6.15). The coordination of metal ions by ligand 2 was accompanied by marked fluorescence enhancement, whereas the binding of ammonium ions by the same species resulted in significant fluorescence quenching. 相似文献
998.
Gergely A Szász G Szentesi A Gyimesi-Forrás K Kökösi J Szegvári D Veress G 《Analytical and bioanalytical chemistry》2006,384(7-8):1506-1510
The biological importance of dehydroepiandrosterone (DHEA) is reflected by the fact that DHEA is a crucial precursor of the biosynthesis of the steroidal sex hormones. Simultaneous separation of DHEA, dehydroepiandrosterone sulfate (DHEA-S), pregnenolone, androstenedione and testosterone has been accomplished by reversed-phase ion-pair high-performance liquid chromatography (RP-IP-HPLC) based on isocratic elution applying circular dichroism (CD) detection at 295 nm. Addition of tetrabutylammonium hydrogensulfate to the mobile phase increases the retention of DHEA-S on the C8-silica column by an apparent ion-pairing mechanism without affecting the retention of the other (non-ionic) steroids. CD spectroscopy provides highly selective detection of compounds possessing optically active absorption bands and the separation is even more selective in the higher wavelength range applied. The linearity of the steroid concentration (c, mg mL−1) versus peak area was tested in the concentration range of 0.5–2 mg mL−1 (injected quantities were 10–40 μg). The relative standard deviation (RSD) values for DHEA and DHEA-S indicated a good intra-assay and inter-assay precision of the method.
相似文献
999.
In the main result of this paper, some sharp conditions are obtained for global attractivity in a scalar perturbed linear delay differential equation. The proof of the main theorem is based on a new estimate for the infinite integral of the absolute value of the fundamental solution of a linear delay differential equation. We also derive sufficient conditions for asymptotic stability of a system of linear delay differential equations. 相似文献
1000.
A graph G is called \(C_4\)-free if it does not contain the cycle \(C_4\) as an induced subgraph. Hubenko, Solymosi and the first author proved (answering a question of Erd?s) a peculiar property of \(C_4\)-free graphs: \(C_4\)-free graphs with n vertices and average degree at least cn contain a complete subgraph (clique) of size at least \(c'n\) (with \(c'= 0.1c^2\)). We prove here better bounds \(\big ({c^2n\over 2+c}\) in general and \((c-1/3)n\) when \( c \le 0.733\big )\) from the stronger assumption that the \(C_4\)-free graphs have minimum degree at least cn. Our main result is a theorem for regular graphs, conjectured in the paper mentioned above: 2k-regular \(C_4\)-free graphs on \(4k+1\) vertices contain a clique of size \(k+1\). This is the best possible as shown by the kth power of the cycle \(C_{4k+1}\). 相似文献