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91.
Yasuhiro Inada Yoshihisa Nakayama Shigenobu Funahashi 《Journal of solution chemistry》2004,33(6-7):847-862
The equilibrium constants of the hydrogen-bonding interactions between the tetraaqua-beryllium(II) ion ([Be(H2O)4]2+) and water in the second solvation sphere were determined from the dependence of the 9Be NMR chemical shift (δBe) on the water concentration (C W) in propiononitrile (PN). The 9Be NMR line assigned to [Be(H2O)4]2+ is downfield shifted with the increasing C W, and the change in δBe as a function of C W is explained in terms of a two-step hydrogen-bonding interaction to form [Be(H2O)4](H2O) n 2+ (n = 1, 2). Molecular orbital calculations for [Be(H2O)4](H2O) n 2+ (n = 0?2) revealed that the electron density on the Be(II) ion increases with an increase in n due to an enhanced polarization of the bound water molecules accompanied by the hydrogen bonding in the second solvation sphere. The observed downfield shift of δBe is interpreted as a significant compensation of the diamagnetic upfield shift by the paramagnetic contribution due to the mixing of the vacant s and p orbitals of Be with the σ-type lone-pair orbitals of the coordinating water molecules. 相似文献
92.
Shigenobu Hayashi Kikuko Hayamizu Osamu Yamamoto 《Journal of Physics and Chemistry of Solids》1983,44(6):601-606
The behavior of hydrogen in the hydrides of vanadium metal containing small amounts of nickel was studied by 1H NMR spectroscopy. FT spectra and spin-spin and spin-lattice relaxation times for VH0.77, V0.95Ni0.05H0.73, and V0.90Ni0.10H0.65 were measured at temperatures between 77 and 400 K. On the addition of nickel the number of hydrogen atoms on O22 sites decreases and the superstructure of hydrogen is altered. Different effects of nickel on hydrogen diffusion are observed above and below about 200 K, and, therefore, the mechanism of hydrogen diffusion is assumed to change at this temperature. 相似文献
93.
Makoto Obata Eiko Ohtake Shiho Hirohara Masao Tanihara Shigenobu Yano 《Journal of polymer science. Part A, Polymer chemistry》2012,50(17):3592-3597
In this article, we offer clear evidence for the radical copolymerizability of porphyrin rings in 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO)‐mediated radical copolymerizations with styrene. The radical copolymerizations of styrene with 5,10,15,20‐tetrakis(pentafluorophenyl)porphyrin (H2TFPP) was conducted using 1‐phenyl‐1‐(2,2,6,6‐tetramethyl‐1‐piperidinyloxy)ethane as an initiator. The refractive index (RI) traces for the size‐exclusion chromatography of the resulting copolymers were unimodal with narrow molecular weight distributions. The RI traces shifted toward higher molecular weight regions as the polymerization progressed, and the number‐average molecular weights were close to those calculated on the basis of the feed compositions and monomer conversions. These features were in good agreement with a TEMPO‐mediated mechanism. The traces recorded by the ultraviolet‐visible (UV‐vis) detector (430 nm) were identical to those obtained by the RI detector, indicating a statistical copolymerization of styrene with H2TFPP. This also indicated that H2TFPP acted as a monomer and not as a terminator or a chain‐transfer agent under the conditions used. A benzyl radical addition to H2TFPP was conducted as a model reaction for the copolymerization using tributyltin hydride as a chain‐transfer agent, affording a reduced porphyrin, 2‐benzyl‐5,10,15,20‐tetrakis(pentafluorophenyl)chlorin 1 , via radical addition to the β‐pyrrole position. The UV‐vis spectrum of 1 was fairly similar to that of poly(styrene‐co‐H2TFPP), indicating that H2TFPP polymerized at its β‐pyrrole position in the TEMPO‐mediated radical polymerization. TEMPO‐mediated radical copolymerizations of styrene with several porphyrin derivatives were also demonstrated. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
94.
Dr. Jun Kikuchi Kyohei Takano Dr. Yusuke Ota Dr. Shigenobu Umemiya Prof. Dr. Masahiro Terada 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(49):11124-11128
Despite the significant progress of the enantioselective reaction using chiral catalysts, the enantioselective nucleophilic substitution reaction at the chiral sp3-hybridized carbon atom of a racemic electrophile has not been largely explored. Herein, we report the enantioconvergent propargylic substitution reaction of racemic propargylic alcohols with thiols using chiral bis-phosphoric acid as the chiral Brønsted acid catalyst. The substitution products were formed in high yields with high enantioselectivities in most cases. The cation-stabilizing effect of the sulfur functional group introduced at the alkynyl terminus is the key to achieving the efficient enantioconvergent process, in which chiral information originating from not only the racemic stereogenic center but also the formed contact ion pair is completely eliminated from the present system. 相似文献
95.
Nomoto Akihiro Sakamoto Nozomi Sakai Yuta Fukumoto Keisuke Ogura Shun-Ichiro Shouhei Katao Kakiuchi Kiyomi Kikuchi Jun-ichi Yano Shigenobu Ogawa Akiya 《Research on Chemical Intermediates》2019,45(1):3-12
Research on Chemical Intermediates - Phenylalanine ester-introduced palladium(II) and platinum(II) complexes were synthesized. Taking advantage of the formation of Schiff bases by amino acids as an... 相似文献
96.
Shigenobu Fujimoto Kenji Matsumoto Takayuki Iwata Mitsuru Shindo 《Tetrahedron letters》2017,58(10):973-976
We have developed a heterogeneous catalytic oxidative homocoupling reaction of dimethoxyanilides under an oxygen atmosphere. The resulting homo-dimers are useful for the construction of heterocycles, demonstrating the potential of heterogeneous metal catalysts. 相似文献
97.
Onambele LA Koth D Czaplewska JA Schubert US Görls H Yano S Obata M Gottschaldt M Prokop A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(48):14498-14505
Cisplatin analogue complexes with platinum(II) and palladium(II) starting from 3',5'-diamino-3',5'-dideoxy-thymidines were synthesized, both with the D-erythro- and D-threo configurations. Complexes of the general formula [MCl(2)L] were obtained and characterized. NMR spectroscopic measurements and single crystal X-ray structure analysis showed that the metal centers are coordinated to the ligands by the amino groups in 3'- and 5'-positions and not through the thymine moiety. All ligands and complexes showed no significant in vitro activities except thymiplatin (cis-dichloro(3',5'-diamino-3',5'-dideoxy-D-threo-thymidine)platinum(II)). Detailed in vitro studies on the apoptosis pathway in lymphoma (BJAB), leukemia (NALM-6), and melanoma cells (Mel-HO) as well as on transfected or resistant cell lines were carried out. Thymiplatin significantly induced an apoptotic response, which was found to be associated with the loss of mitochondrial membrane potential and with caspase activation. The activity was shown to be independent of Fas-associated protein with death domain (FADD), but dependent on Bcl-2 expression. As a consequence, for thymiplatin a mitochondrial mode of action could be assigned. Moreover, the compound showed activity in cells resistant to common drugs, such as daunorubicin and vincristin, and showed synergistic effects with doxorubicin, vincristin, cytarabin, and daunorubicin. 相似文献
98.
Dopaldehyd (homoprotocatechu aldehyd; 3,4-dihydroxyphenyl acetaldehyd), in form of its (Z)-enol-(E)-caffeic ester, has been detected for the first time as a natural occurring compound. It is a constitutent of the yellow pigments of the glands on the leaves of Plectranthus caninus ROTH (Labiatae). 相似文献
99.
100.
Thermal reaction of alkynyl propargyl sulfoxides 1 afforded novel highly reactive (α-ketovinyl)thioketenes 3. Trapping experiments using a primary or secondary amine, formation of furanophane 4, through head-to-tail type dimerization, as well as direct observation using 1H NMR elucidated the generation pathway of 3 through sequential [2,3]/[3,3] sigmatropic rearrangement. 相似文献