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131.
Toshimasa Katagiri Yasuyuki Fujiwara Satoshi Takahashi Kenji Uneyama 《Journal of fluorine chemistry》2005,126(8):1134-1139
A structural feature of hydrogen bonding chains found in the crystals of trifluoromethylated amino alcohols is reported. Hydrogen bondings of 3-(N,N-dialkylamino)-1,1,1-trifluoro-2-propanols construct chiral spiral hydrogen bonding chains. Lone pairs on the nitrogen atoms of the amino alcohols participate in two hydrogen bondings. Detailed structural analysis of the hydrogen bonds of the 3-(N,N-dimethylamino)-1,1,1-trifluoro-2-propanol suggested that the chain built up with alternating intermolecular-medium and intramolecular-weak hydrogen bonds. The medium intermolecular hydrogen bond, which transfers a proton from the hydroxy group to the amino nitrogen, would make a tentative zwitterionic form of the molecule. Then, electrostatic attraction between the charges in the zwitterion centers induced a weak intramolecular hydrogen bond. 相似文献
132.
Kobayashi K Ishii K Sakamoto S Shirasaka T Yamaguchi K 《Journal of the American Chemical Society》2003,125(35):10615-10624
The guest- or solvent-induced assembly of a tetracarboxyl-cavitand 1 and a tetra(3-pyridyl)-cavitand 2 into a heterodimeric capsule 1.2 in a rim-to-rim fashion via four intermolecular CO(2)H.N hydrogen bonds has been investigated both in solution and in the solid state. In the (1)H NMR study, a 1:1 mixture of1a and 2a (R = (CH(2))(6)CH(3)) in CDCl(3) gave a mixture of various complicated aggregates, whereas this mixture in CDCl(2)CDCl(2) or p-xylene-d(10) exclusively produced the heterodimeric capsule 1a.2a. It was found that an appropriate 1,4-disubstituted-benzene is a suitable guest for inducing the exclusive formation of 1a.2a in CDCl(3). The ability of a guest to induce the formation of guest-encapsulating heterodimeric capsule, guest@(1a.2a), increased in the order p-ethyltoluene < 1-ethyl-4-methoxybenzene < or = 1-ethyl-4-iodobenzene < or = 1,4-dibromobenzene < 1-iodo-4-methoxybenzene < or= 1,4-dimethoxybenzene < or = 1,4-diiodobenzene. The (1)H NMR study revealed that a CH-halogen interaction between the inner protons of the methylene-bridge rims (-O-H(out)CH(in)-O-) of the 1a and 2a units and the halogen atoms of 1,4-dihalobenzenes and a CH-pi interaction between the methoxy protons of 1,4-dimethoxybenzene and the aromatic cavities of the 1a and 2a units play important roles in the formation of 1,4-dihalobenzene@(1a.2a) and 1,4-dimethoxybenzene@(1a.2a), respectively. A preliminary single-crystal X-ray diffraction analysis of guest@(1b.2b) (R = (CH(2))(2)Ph; guest = 1-iodo-4-methoxybenzene or p-xylene) confirmed that the guest encapsulated in 1b.2b is oriented with the long axis of the guest along the long axis of 1b.2b and that the iodo and the methoxy groups of the encapsulated 1-iodo-4-methoxybenzene are specifically oriented with respect to the cavities of the 2b and 1b units, respectively. 相似文献
133.
Kondo M Irie Y Shimizu Y Miyazawa M Kawaguchi H Nakamura A Naito T Maeda K Uchida F 《Inorganic chemistry》2004,43(20):6139-6141
Reversible construction of a nanoporous framework from a nonporous framework has been found in the zinc(II) coordination polymer with 4,4'-oxybis(benzoate) (oba). [Zn(2)(oba)(2)(dmf)(2)].2DMF (1), which has 1 nm scale channels, transforms to the nonporous coordination polymer [Zn(oba)(H(2)O)] (2) with the loss of the open framework. Compound 2 on treatment with DMF reversibly yields nanoporous compound 1. 相似文献
134.
Chromatographic separation of styrene-methyl methacrylate (MMA) copolymers depending on the chemical composition was studied using liquefied carbon dioxide as an adsorption promoting solvent, and tetrahydrofuran, chloroform containing ethanol as a desorption promoting solvent in the mobile phase and the column packed non-bonded silica gel by a solvent gradient method. With the increase of MMA content, the elution was retarded indicating that the typical normal-phase type of adsorption occurred. The effects of type of desorption solvents, molecular mass of sample, and column temperature on the elution were investigated. 相似文献
135.
Ando M Takizawa M Suwabe S Yamato S Shimada K 《European journal of mass spectrometry (Chichester, England)》2003,9(6):619-622
Analysis of selenium in biological samples is very important and numerous analytical methods for the element have been developed. One of the most convenient and widely used methods for routine determination of serum selenium is a fluorometric method using 2,3-diaminonaphthalene (DAN); however, this method lacks specificity. We observed that 4,5-benzopiazselenol (BPS), a selenium derivative of DAN, is ionized with electron capture in an atmospheric pressure chemical ionization (APCI) interface, and subsequently established a method for determining total human serum selenium by means of liquid chromatography/atmospheric pressure chemical ionization mass spectrometry. All pretreatment procedures were carried out in a single test tube to minimize selenium loss. The recovery of organic or inorganic selenium spiked to human serum was 97-103%.The detection limit of BPS was equivalent to 0.2 ng of selenium and the lower quantitative limit of serum selenium was 10 ng mL(-1). The coefficient of variation of standard concentrations in control serum samples was 4.5%. The purity of the observed peak obtained from serum samples was confirmed using the ion cluster technique. 相似文献
136.
Kenji Yamamoto Toshinobu Higashimura 《Journal of polymer science. Part A, Polymer chemistry》1974,12(3):613-626
Ring-substituted phenyl propenyl ethers were found to form homopolymers without any rearrangement by metal halides. Phenyl propenyl ethers were less reactive than the corresponding phenyl vinyl ethers in cationic polymerization. In order to study the electronic effect of a substituent on the reactivity, cis-p-Cl,p-CH3, and p-CH3O-phenyl propenyl ethers were copolymerized with phenyl propenyl ether in methylene chloride at ?78°C with stannic chloride–trichloroacetic acid, and their 1H- and 13C-NMR spectra were measured. The reaction constant ρ against Hammett σp was ?2.1. The cis-phenyl propenyl ethers were slightly more reactive than the corresponding trans isomers. On the other hand, an o-methyl group decreased the reactivity of phenyl propenyl ether. The low reactivity of o-methyl phenyl propenyl ether was attributed to the steric hindrance between the propagating carbocation and the monomer. 相似文献
137.
138.
Pentacyanoferrate-bound poly(1-vinylimidazole) (PVI[Fe(CN)5]) was selected as a mediator for amperometric creatinine determination based on the reductive H2O2 detection. Creatinine amidohydrolase (CNH), creatine amidohydrolase (CRH), sarcosine oxidase (SOD), peroxidase (POD), and PVI[Fe(CN)5] were crosslinked with poly(ethylene glycol) diglycidyl ether (PEGDGE) on a glassy carbon (GC) electrode for a creatinine biosensor fabrication. Reduction current was monitored at −0.1 V in the presence of creatinine and O2. It is revealed that PVI[Fe(CN)5] is suitable as a mediator for a bioelectrocatalytic reaction of POD, since PVI[Fe(CN)5] neither reacts with reactants nor works as an electron acceptor of SOD. The amounts of PVI[Fe(CN)5], PEGDGE, and enzymes were optimized toward creatinine detection. Nafion as a protecting film successfully prevented the enzyme layer from interferences. The detection limit and linear range in creatinine determination were 12 μM and 12–500 μM (R2 = 0.993), respectively, and the sensitivity was 11 mA cm−2 M−1, which is applicable for urine creatinine tests. The results of the creatinine determination for four urine samples measured with this proposed method were compared with Jaffe method, and a good correlation was obtained between the results. 相似文献
139.
Kenji TAKAHASHI 《Proceedings of the Japan Academy. Series B, Physical and biological sciences》2013,89(6):201-225
A group of enzymes, mostly hydrolases or certain transferases, utilize one or a few side-chain carboxyl groups of Asp and/or Glu as part of the catalytic machinery at their active sites. This review follows mainly the trail of studies performed by the author and his colleagues on the structure and function of such enzymes, starting from ribonuclease T1, then extending to three major types of carboxyl peptidases including aspartic peptidases, glutamic peptidases and serine-carboxyl peptidases. 相似文献
140.