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Tadatomi Nishikubo Atsushi Kameyama Hiroto Kudo Kousuke Tsutsui 《Journal of polymer science. Part A, Polymer chemistry》2002,40(9):1293-1302
New photoreactive calixarene derivatives containing spiro ortho ester groups (calixarenes 3a–3c ) were synthesized by the reaction of 2‐bromomethyl‐1,4,6‐trioxaspiro[4.4]nonane with 2,8,14,20‐tetramethyl‐4,6,10,12,16,18,22,24‐octakis(carboxymethoxy)calix[4]resorcinarene, 5,11,17,23,29,35‐hexamethyl‐37,38,39,40,41,42‐hexakis(carboxymethoxy)calix[6]arene, and 5,11,17,23,29,35,41,47‐octa‐tert‐butyl‐49,50,51,52, 53,54,55,56‐octakis‐(carboxymethoxy)calix[8]arene, which were prepared by the reaction of C‐methylcalix[4]resorcinarene, p‐methylcalix[6]arene, and p‐tert‐butylcalix[8]arene, respectively. The thermal stability of the obtained calixarene derivatives containing spiro ortho ester groups was examined with thermogravimetric analysis, and it was found that these calixarene derivatives had good thermal stability. The photoinitiated cationic polymerization of spiro ortho ester groups in calixarene derivatives 3a–3c was examined with certain photoacid generators in the film state. Interestingly enough, the reaction of calixarene derivatives did not proceed with only photoirradiation; however, the reaction proceeded smoothly when the photoirradiation was followed by heating. Furthermore, calixarene 3a , composed of a C‐methylcalix[4]resorcinarene structure, showed the highest photochemical reactivity in this reaction system. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1293–1302, 2002 相似文献
54.
Mikami K Angelaud R Ding K Ishii A Tanaka A Sawada N Kudo K Senda M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2001,7(3):730-737
Asymmetric catalysts, prepared by chiral ligand exchange or chiral modification, can evolve further into highly activated catalysts through engineering with chiral activators. Two new methodologies for "super high-throughput screening" (SHTS) of chiral ligands and activators have been developed as a combination of HPLC-CD/UV (CD/ UV = circular dichroism/ultraviolet spectroscopy) or -OR/RIU (OR/RIU = optical rotation/refractive index unit) with a combinatorial chemistry (CC) factory. With these techniques, the % ee of the product is determined within minutes without separation of the enantiomeric products by using a nonchiral stationary phase. Therefore, those SHTS techniques combined with our 'asymmetric activation' concept can provide a powerful strategy for finding the best activated chiral catalyst. 相似文献
55.
Conformational structures of solvated cobalt(II) ions in several amides and trimethyl phosphate (TMP) have been studied by the X-ray diffraction method using the isomorphous substitution technique. The amides used are formamide (FA), N-methylformamide (NMF), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), and N,N-dimethylpropioamide (DMPA). From the analysis of radial distribution functions around Co2+, the distances from Co2+ to each atom of coordinated solvent molecules were obtained and the coordination numbers were determined to be six, except for DMPA where four-coordinate species coexist. The Co—O bond distances are 2.09(1)–2.11(1) Å for six-coordinate species but is 1.96(2) Å for the four-coordinate species. In the amide solutions the Co—O—C bond angles are 126(3)° (FA), 123(2)° (NMF), 123(2)° (DMF), 134(3)° (DMA), and 137(4)–138(4)° (DMPA). The Co—O—C—N dihedral angles were also estimated to discuss the conformational distortion on the Co2+-amide interactions. For TMP solutions the Co—O—P angle was determined to be 150(4)°, and the conformational structure on the Co2+–TMP interaction is discussed. 相似文献
56.
Hiroaki Saito Kousuke Inoue Keiji Matsumoto Makoto Tadokoro Yukio Nakamura 《Journal of Cluster Science》1998,9(2):145-164
The oxidative addition reaction of 2,6-bis(bromomethyl)pyridine to Ru3(CO)12 gave scarcely soluble {Ru2Br2(-Q)(CO)4}
n
, 1, [Q=C5H3N-2-C(O)CH2-6-CH2] or a mixture of 1 and the mononuclear complex RuBr(Q)(CO)3, 2, [Q=C5H3N-2-C(O)CH2-6-CH2Br] according to the reactant's mole ratio. Further reactions of 1 with some N- and P-donor ligands (L) afforded readily soluble dinuclear complexes, Ru2(-Br)(-Q)Br(CO)
n
(L)
m
[n=4, m=1, L=PPh3
3a, or py 3b; n=3, m=2, L=PPh3
5a, or PPh2(o-tolyl) 5b]. In this paper, the characterization of these products by the elemental analyses and the spectroscopic methods are described. The X-ray crystal structures of Ru2(-Br) (-Q)Br(CO)4(PPh3)(MeOH), 4, which was obtained by crystallization of 3a from MeOH, and of 5a · (2CHCl
3
) are also described. Each of the metal atoms in 4 has a distorted octahedral coordination, while in 5a · (2CHCl
3
) one metal atom takes a distorted octahedral geometry and the other pseudooctahedral, which is completed by presenting a Ru ··· Br secondary bonding interaction. 相似文献
57.
Inside Cover: Supramolecular Porphyrin‐Based Metal–Organic Frameworks with Fullerenes: Crystal Structures and Preferential Intercalation of C70 (Chem. Asian J. 5/2016)
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Senda S Ohki Y Hirayama T Toda D Chen JL Matsumoto T Kawaguchi H Tatsumi K 《Inorganic chemistry》2006,45(24):9914-9925
A series of [Tm(Me)M(mu-Cl)]2 and Tm(R)MCl (Tm(R) = tris(mercaptoimidazolyl)borate; R = Me, tBu, Ph, 2,6-iPr2C6H3 (Ar); M = Mn, Fe, Co, Ni) complexes have been prepared by treatment of NaTm(Me) or LiTm(R) with an excess amount of metal(II) chlorides, MCl2. Treatment of Tm(R)MCl (R = tBu, Ph, Ar) with NaI led to a halide exchange to afford Tm(R)MI. The molecular structures of [Tm(Me)M(mu-Cl)]2 (M = Mn, Ni), [Tm(Me)Ni(mu-Br)]2, Tm(tBu)MCl (M = Fe, Co), Tm(Ph)MCl (M = Mn, Fe, Co, Ni), Tm(Ar)MCl (M = Mn, Fe, Co, Ni), Tm(Ph)MI (M = Mn, Co), and Tm(Ar)MI (M = Fe, Co, Ni) have been determined by X-ray crystallography. The Tm(R) ligands occupy the tripodal coordination site of the metal ions, giving a square pyramidal or trigonal bipyramidal coordination geometry for Tm(Me)M(mu-Cl)]2 and a tetrahedral geometry for the Tm(R)MCl complexes, where the S-M-S bite angles are larger than the reported N-M-N angles of the corresponding hydrotris(pyrazolyl)borate (Tp(R)) complexes. Treatment of Tm(Ph)2Fe with excess FeCl2 affords Tm(Ph)FeCl, indicating that Tm(R)2M as well as Tm(R)MCl is formed at the initial stage of the reaction between MCl2 and the Tm(R) anion. 相似文献