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Kenji Hara Keiji Iwahashi Satoru Takakusagi Kohei Uosaki Masaya Sawamura 《Surface science》2007,601(22):5127-5132
Functionalization of self-assembled monolayer (SAM) of alkanethiolate with metal containing unit is one of the versatile methods to obtain functional surfaces such as heterogeneous catalysts. However, organic molecules that strongly bind to transition metals at SAM terminal are limited. Recently N-heterocyclic carbenes (NHCs) such as cyclic diaminocarbenes have emerged as strongly σ-donating ligands forming a robust bond with broad spectrum of transition metals. In the present study, for the purpose of establishment of a new robust basement for heterogeneous metal catalysts, a SAM of the alkanethiolate terminated with NHC-rhodium(I) complex moiety was prepared by utilizing a newly designed disulfide molecule bearing NHC-metal complex terminals. X-ray photoelectron spectroscopy (XPS) analysis and angle resolved XPS measurement revealed successful formation of the Rh-complex-terminated SAM on a gold substrate. Infrared reflection absorption spectroscopy (IRRAS) analysis suggested that the linker methylene chains connecting the rhodium complex moiety and the gold surface are in a loosely packed structure. This unique chemical species, NHC, would be a promising candidate as a basement for the construction of functional surface. 相似文献
3.
Yoshitomo Ono Naoyuki Kawashima Hiroto Kudo Tadatomi Nishikubo Takabumi Nagai 《Journal of polymer science. Part A, Polymer chemistry》2007,45(14):2978-2988
The ring‐opening copolymerization of a glycidyl ester derivative having a benzophenone group and the donor–acceptor norbornadiene (D‐A NBD) dicarboxylic acid, 5‐(4‐methoxyphenyl)‐1,4,6,7,7‐pentamethyl‐2,5‐norbornadiene‐2,3‐dicarboxylic acid, monoglycidyl ester derivatives with D‐A NBD dicarboxylic anhydride using tetraphenylphosphonium bromide as a catalyst proceeded smoothly to give novel self‐photosensitizing NBD polymers in good yields. The molecular weight of these polyesters was about 4,000, and lower than that of analogous NBD polymers having no benzophenone group. All the synthesized NBD polymers isomerized smoothly to the corresponding quadricyclane (QC) polymers upon UV irradiation in tetrahydrofuran (THF) solution and in the film state. The rate of the photoisomerization of the D‐A NBD moieties in these polymers was higher than that of the D‐A NBD moieties in the polymer having no photosensitizing group. Furthermore, the rate of the photoisomerization of the D‐A NBD moieties in these polymers was also higher than that of the NBD polymer with low molecular weight photosensitizer in dilute solution. The photo‐irradiated polymers having QC moieties released thermal energies of 146–180 J/g. The D‐A NBD moieties contained in these NBD polymers possessed fair to good fatigue resistance. The degradation of the NBD moieties in these polymers was 15–30% after 50 repeated cycles of interconversion. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2978–2988, 2007 相似文献
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Ono K Yoshida A Saito N Fujishima T Honzawa S Suhara Y Kishimoto S Sugiura T Waku K Takayama H Kittaka A 《The Journal of organic chemistry》2003,68(19):7407-7415
Six novel 2-substituted analogues of 1alpha,25-dihydroxy-19-norvitamin D(3), 6a,b-8a,b, were efficiently synthesized utilizing (-)-quinic acid as the A-ring precursor. The C2-modified A-rings were prepared as 4-alkylated (3R,5R)-3,5-dihydroxycyclohexanones 12-15 from (-)-quinic acid based on radical allylation at the C4 position of methyl (-)-quinicate. The new type of the CD-ring coupling partner 23 was synthesized from 25-hydroxy Grundmann's ketone 19 to apply to the modified Julia olefination to construct a diene unit between the A-ring and the CD-ring. The coupling yields, including a deprotection step, were 47-62%. After the separation of the diastereomers based on C2 stereochemistry, the structure (2alpha or 2beta) was determined by (1)H NMR experiments and compared to DeLuca's 2-methyl- and 2-ethyl-1alpha,25-dihydroxy-19-norvitamin D(3). Thus, the synthesized 2alpha-(3-hydroxypropyl)-1alpha,25-dihydroxy-19-norvitamin D(3) (8a) showed almost the same potency in binding to the bovine thymus vitamin D receptor (VDR) as the natural hormone 1, while its beta-isomer 8b had only a 3% affinity. Both 2alpha-allyl- and 2alpha-propyl-1alpha,25-dihydroxy-19-norvitamin D(3) (6a and 7a) and their 2beta-analogues (6b and 7b) possessed a weak affinity for the VDR. The strong VDR ligand 8a was ca. 36-fold more potent in induction of HL-60 cell differentiation than 1, and interestingly, even the weaker ligand 8b showed a 6.7-fold higher potency in the cell differentiation activity than that of 1. 相似文献
7.
In the reaction of soybean lipoxygenase (EC 1.13.11.12) with polyunsaturated fatty acids such as linoleic, linolenic and arachidonic acids, some radical species were detected using the electron spin resonance (ESR) spin-trapping technique. The radical species derived from the three polyunsaturated fatty acids were not distinguishable because the ESR spectra of the spin adducts of nitrosobenzene with their three radical species showed no difference in their hyperfine splittings. To overcome this defect of the spin-trapping technique, these spin-adducts were separated by employing high-performance liquid chromatography (HPLC) combined with ESR spectroscopy. The spin adducts were eluted from a C18 reversed-phase column in the order linolenic acid, linoleic acid and arachidonic acid. The half-lives of the spin adducts separated by HPLC-ESR were determined as linoleic acid 600 min, linolenic acid 360 min and arachidonic acid 160 min. The use of an ultraviolet detector together with the HPLC-ESR technique resulted in a 500-fold increase in sensitivity in the detection of the radical species. 相似文献
8.
Ken-ichi Sato Shoji Akai Akira Yoshitomo Yoshimitsu Takai 《Tetrahedron letters》2004,45(44):8199-8201
The merits of an indirect protecting method for hydroxyl groups using allyl groups via allyloxycarbonyl groups in the synthesis of antennary β-d-mannopyranosyl disaccharides from β-d-galactopyranosyl disaccharides were studied. Regioselective allyloxycarbonylation and conversion reactions involving simultaneous double SN2 nucleophilic substitution at C-2′ and C-4′ of benzyl O-[β-d-galactopyranosyl]-(1-4)-3,6-di-O-benzyl-2-deoxy-2-N-phthalimido-β-d-glucopyranoside were examined for comparison with the direct allylation method. The required β-d-mannopyranosyl disaccharide having proper protecting groups was obtained using this indirect method in 52% yield. In contrast, the reported direct allylation method using methyl O-(β-d-galactopyranosyl) disaccharide gave the corresponding β-d-mannopyranosyl disaccharide in only 7.5% yield. 相似文献
9.
Kittaka A Kurihara M Peleg S Suhara Y Takayama H 《Chemical & pharmaceutical bulletin》2003,51(3):357-358
Hereditary vitamin D-resistant rickets (HVDRR) is a genetic disorder caused by mutations in the vitamin D receptor, which lead to resistance to 1alpha,25-dihydroxyvitamin D(3) [1alpha,25(OH)(2)D(3)]. We found that the A ring-modified analogues, 2alpha-(3-hydroxypropyl)- and 2alpha-(3-hydroxypropoxy)-1alpha,25(OH)(2)D(3), (O1C3 and O2C3) can bind better than the natural hormone to the mutant VDR (R274A), which similar to the HVDRR mutant, R274L, had lost the hydrogen bond to the 1alpha-hydroxyl group of 1alpha,25(OH)(2)D(3). 相似文献
10.
Sun Z Zheng X Hoshi T Kashiwagi Y Anzai J Li G 《Analytical and bioanalytical chemistry》2004,380(3):545-550
Ligustrazine is one of the active ingredients contained in Ligusticum chuanxiong Hort. (Umbelliferae), which is widely used in traditional Chinese medicine for the treatment of cardiovascular problems. In this work, the electrochemistry of Ligustrazine hydrochloride (LZC) and its determination are investigated. The detection limit is estimated to be 8.0×10–8 M, with three linear ranges from 1.0×10–6 to 1.0×10–4 M, 1.0×10–4 to 5.0×10–4 M, and 6.5×10–4 to 1.6×10–3 M. The method has been proved to be highly sensitive, selective, and stable, and has been successfully applied to determining LZC in LZC injections. 相似文献