全文获取类型
收费全文 | 789篇 |
免费 | 29篇 |
国内免费 | 7篇 |
专业分类
化学 | 584篇 |
晶体学 | 6篇 |
力学 | 29篇 |
数学 | 43篇 |
物理学 | 163篇 |
出版年
2023年 | 6篇 |
2022年 | 8篇 |
2021年 | 14篇 |
2020年 | 8篇 |
2019年 | 8篇 |
2018年 | 5篇 |
2016年 | 16篇 |
2015年 | 16篇 |
2014年 | 20篇 |
2013年 | 58篇 |
2012年 | 32篇 |
2011年 | 37篇 |
2010年 | 21篇 |
2009年 | 15篇 |
2008年 | 63篇 |
2007年 | 50篇 |
2006年 | 24篇 |
2005年 | 21篇 |
2004年 | 24篇 |
2003年 | 41篇 |
2002年 | 38篇 |
2001年 | 36篇 |
2000年 | 30篇 |
1999年 | 17篇 |
1998年 | 17篇 |
1997年 | 9篇 |
1996年 | 13篇 |
1995年 | 7篇 |
1994年 | 12篇 |
1993年 | 5篇 |
1992年 | 5篇 |
1991年 | 3篇 |
1990年 | 16篇 |
1989年 | 13篇 |
1988年 | 7篇 |
1987年 | 8篇 |
1986年 | 13篇 |
1985年 | 11篇 |
1984年 | 10篇 |
1983年 | 6篇 |
1982年 | 5篇 |
1980年 | 5篇 |
1977年 | 6篇 |
1976年 | 3篇 |
1975年 | 4篇 |
1974年 | 3篇 |
1967年 | 3篇 |
1932年 | 5篇 |
1898年 | 2篇 |
1886年 | 2篇 |
排序方式: 共有825条查询结果,搜索用时 15 毫秒
1.
Ricaurte Rodríguez Manuel Nogueras Justo Cobo John N. Low Christopher Glidewell 《Acta Crystallographica. Section C, Structural Chemistry》2008,64(7):o376-o378
Molecules of the title compound, C12H13ClN4, are linked by two independent N—H...N hydrogen bonds into a chain of edge‐fused R22(8) rings. The significance of this study lies in its attempt to rationalize the patterns of supramolecular aggregation in the title compound and in a range of analogous 4,6‐disubstituted 2‐aminopyrimidines. 相似文献
2.
Shaw NM Blanis D Bodek A Budd H Coombes R Eno S Fry CA Harada H Ho YH Kim YK Kumita T Mori T Olsen SL Sill A Thorndike EH Ueno K Zheng HW Imlay R Kirk P Lim J McNeil RR Metcalf W Myung SS Cheng CP Gu P Li J Li YK Mao ZP Xu YT Zhu YC Abashian A Gotow K Hu K Low EH Mattson ME Naito F Piilonen L Sterner KL Lusin S Rosenfeld C Wang AT Wilson S Frautschi M Kagan H Kass R Trahern CG Breedon RE Kim GN Ko W Lander RL Maeshima K Malchow RL Smith JR Sparks K Williams MC Abe K Fujii Y Higashi Y Kim SK 《Physical review letters》1989,63(13):1342-1345
3.
Abachi S Baringer P Bylsma BG DeBonte R Koltick D Loeffler FJ Low EH McIlwain RL Miller DH Ng CR Rangan LK Shibata EI Derrick M Gan KK Kooijman P Loos JS Musgrave B Price LE Repond J Sugano K Weiss JM Wood DE Blockus D Brabson B Brom J Jung C Ogren H Rust DR Akerlof C Chapman J Errede D Kesten P Meyer DI Nitz D Seidl AA Thun R Willutzky M Cork B 《Physical review letters》1986,57(16):1990-1993
4.
Rapid high-performance liquid chromatographic (HPLC) procedures have been used to isolate and characterize thymosin beta 4 from different species. Crude extracts termed thymosin fraction 5A were prepared from porcine and ovine thymus glands as well as murine spleen. Each fraction 5A preparation was then fractionated by HPLC on a muBondapak C18 reversed-phase column. Porcine and ovine thymus fraction 5A, and murine spleen 5A, each yields a predominant peak at a retention time similar to that of bovine thymosin beta 4. Amino acid analysis as well as HPLC tryptic peptide mapping of these peaks indicate that they have homologous sequences to bovine thymosin beta 4. Chromatographic analysis of fresh murine thymus and spleen tissues also revealed protein peaks at the position of bovine beta 4, suggesting that thymosin beta 4 is the native protein present in the animal tissues. 相似文献
5.
In this paper, we give a construction of partial difference sets in p
2 x p
2 x ... x p
2using some finite local rings.Dedicated to Hanfried Lenz on the occasion of his 80th birthdayThe work of this paper was done when the authors visited the University of Hong Kong. 相似文献
6.
Wang W Low PJ Carty AJ Sappa E Gervasio G Mealli C Ienco A Perez-Carreño E 《Inorganic chemistry》2000,39(5):998-1005
The compound [Ru3(CO)9[mu-P(NPri2)2]3][Ru6(CO)15(mu 6-C)[mu-P(NPri2)2]] (1), obtained via the addition of PCl(NPri2)2 to K2[Ru4(CO)13], crystallizes in the monoclinic space group P2l/c with a = 15.537(8) A, b = 36.151(16) A, c = 19.407(5) A, beta = 91.14(2) degrees, Z = 4, and R = 0.069 for 8006 observed reflections. The unit cell is unusual in that it contains both a typical octahedral Ru6 cluster anion (1a), featuring an encapsulated carbide, and a symmetrical phosphido bridge, in addition to a 50-electron trinuclear cluster cation [Ru3(CO)9[mu-P(NPri2)2]3]+ (1c). The latter, with approximate D3h symmetry, exhibits long Ru-Ru distances (> or = 3.15 A). Among the family of clusters with M3(mu-PR2)3 cores and different numbers of both electrons (TEC) and terminal ligands (LxLyLz), 1c is unique in that it is a 333 stereotype with 50 valence electrons. MO calculations permit us to predict the existence of redox congeners of 1c clusters and related 48e Re3 clusters. This work also presents a summary of the relationships between the electronic and the geometric structures for all known M3LxLyLz(mu-PR2)3 species. The basic stereochemical features are influenced by the total-electron count and, hence, by the degree of M-M bonding, as well as the remarkable flexibility of the phosphido bridging ligands. The mu-PR2 ligands need not necessarily lie in the M3 plane, and a wide range of M-P-M angles (as small as 72 degrees or as large as 133 degrees) have been observed. 相似文献
7.
Dalton GT Viau L Waterman SM Humphrey MG Bruce MI Low PJ Roberts RL Willis AC Koutsantonis GA Skelton BW White AH 《Inorganic chemistry》2005,44(9):3261-3269
Reaction of [WIr3(mu-CO)3(CO)8(eta-C5Me5)] (1c) with [W(C[triple bond]CPh)(CO)3(eta-C5H5)] afforded the edge-bridged tetrahedral cluster [W2Ir3(mu4-eta2-C2Ph)(mu-CO)(CO)9(eta-C5H5)(eta-C5Me5)] (3) and the edge-bridged trigonal-bipyramidal cluster [W3Ir3(mu4-eta2-C2Ph)(mu-eta2-C=CHPh)(Cl)(CO)8(eta-C5Me5)(eta-C5H5)2] (4) in poor to fair yield. Cluster 3 forms by insertion of [W(C[triple bond]CPh)(CO)3(eta-C5H5)] into Ir-Ir and W-Ir bonds, accompanied by a change in coordination mode from a terminally bonded alkynyl to a mu4-eta2 alkynyl ligand. Cluster 4 contains an alkynyl ligand interacting with two iridium atoms and two tungsten atoms in a mu4-eta2 fashion, as well as a vinylidene ligand bridging a W-W bond. Reaction of [WIr3(CO)11(eta-C5H5)] (1a) or 1c with [(eta-C5H5)(CO)2 Ru(C[triple bond]C)Ru(CO)2(eta-C5H5)] afforded [Ru2WIr3(mu5-eta2-C2)(mu-CO)3(CO)7(eta-C5H5)2(eta-C5R5)] [R = H (5a), Me (5c)] in low yield, a structural study of 5a revealing a WIr3 butterfly core capped and spiked by Ru atoms; the diruthenium ethyndiyl precursor has undergone Ru-C scission, with insertion of the C2 unit into a W-Ir bond of the cluster precursor. Reaction of [W2Ir2(CO)10(eta-C5H5)2] with the diruthenium ethyndiyl reagent gave [RuW2Ir2{mu4-eta2-(C2C[triple bond]C)Ru(CO)2(eta-C5H5)}(mu-CO)2(CO)6(eta-C5H5)3] (6) in low yield, a structural study of 6 revealing a butterfly W2Ir2 unit capped by a Ru(eta-C5H5) group resulting from Ru-C scission; the terminal C2 of a new ruthenium-bound butadiyndiyl ligand has been inserted into the W-Ir bond. Reaction between 1a, [WIr3(CO)11(eta-C5H4Me)] (1b), or 1c and [(eta-C5H5)(CO)3W(C[triple bond]CC[triple bond]C)W(CO)3(eta-C5H5)] afforded [W2Ir3{mu4-eta2-(C2C[triple bond]C)W(CO)3(eta-C5H5)}(mu-CO)2(CO)2(eta-C5H5)(eta-C5R5)] [R = H (7a), Me (7c); R5 = H4Me (7b)] in good yield, a structural study of 7c revealing it to be a metallaethynyl analogue of 3. 相似文献
8.
Vaduganathan Yasodha Subbaiah Govindarajan John N. Low Christopher Glidewell 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(5):m207-m215
The structures of five metal complexes containing the 4‐oxo‐4H‐pyran‐2,6‐dicarboxylate dianion illustrate the remarkable coordinating versatility of this ligand and the great structural diversity of its complexes. In tetraaquaberyllium 4‐oxo‐4H‐pyran‐2,6‐dicarboxylate, [Be(H2O)4](C7H2O6), (I), the ions are linked by eight independent O—H...O hydrogen bonds to form a three‐dimensional hydrogen‐bonded framework structure. Each of the ions in hydrazinium(2+) diaqua(4‐oxo‐4H‐pyran‐2,6‐dicarboxylato)calcate, (N2H6)[Ca(C7H2O6)2(H2O)2], (II), lies on a twofold rotation axis in the space group P2/c; the anions form hydrogen‐bonded sheets which are linked into a three‐dimensional framework by the cations. In bis(μ‐4‐oxo‐4H‐pyran‐2,6‐dicarboxylato)bis[tetraaquamanganese(II)] tetrahydrate, [Mn2(C7H2O6)2(H2O)8]·4H2O, (III), the metal ions and the organic ligands form a cyclic centrosymmetric Mn2(C7H2O6)2 unit, and these units are linked into a complex three‐dimensional framework structure containing 12 independent O—H...O hydrogen bonds. There are two independent CuII ions in tetraaqua(4‐oxo‐4H‐pyran‐2,6‐dicarboxylato)copper(II), [Cu(C7H2O6)(H2O)4], (IV), and both lie on centres of inversion in the space group P; the metal ions and the organic ligands form a one‐dimensional coordination polymer, and the polymer chains are linked into a three‐dimensional framework containing eight independent O—H...O hydrogen bonds. Diaqua(4‐oxo‐4H‐pyran‐2,6‐dicarboxylato)cadmium monohydrate, [Cd(C7H2O6)(H2O)2]·H2O, (V), forms a three‐dimensional coordination polymer in which the organic ligand is coordinated to four different Cd sites, and this polymer is interwoven with a complex three‐dimensional framework built from O—H...O hydrogen bonds. 相似文献
9.
Wilson Cunico Claudia R. B. Gomes Solange M. S. V. Wardell John N. Low Christopher Glidewell 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(7):o411-o414
rac‐2‐Isopropyl‐3‐(2‐nitrobenzyl)‐1,3‐thiadiazolin‐4‐one, C13H16N2O3S, is a rare example of a racemate crystallizing in the space group P212121, with one molecule each of S and R configurations, whose conformations are almost mirror images, within the asymmetric unit. The molecules of S configuration are linked by two C—H...O hydrogen bonds into a three‐dimensional framework, and the molecules of R configuration are linked by two further C—H...O hydrogen bonds into a different type of three‐dimensional framework; the two frameworks are linked by a fifth C—H...O hydrogen bond. 相似文献
10.
Choi S Cooley RB Voutchkova A Leung CH Vastag L Knowles DE 《Journal of the American Chemical Society》2005,127(6):1773-1781
Many transition-metal complexes mediate DNA oxidation in the presence of oxidizing radiation, photosensitizers, or oxidants. The DNA oxidation products depend on the nature of the metal complex and the structure of the DNA. Earlier we reported trans-d,l-1,2-diaminocyclohexanetetrachloroplatinum (trans-Pt(d,l)(1,2-(NH(2))(2)C(6)H(10))Cl(4), [Pt(IV)Cl(4)(dach)]; dach = diaminocyclohexane) oxidizes 2'-deoxyguanosine 5'-monophosphate (5'-dGMP) to 7,8-dihydro-8-oxo-2'-deoxyguanosine 5'-monophosphate (8-oxo-5'-dGMP) stoichiometrically. In this paper we report that [Pt(IV)Cl(4)(dach)] also oxidizes 2'-deoxyguanosine 3'-monophosphate (3'-dGMP) stoichiometrically. The final oxidation product is not 8-oxo-3'-dGMP, but cyclic (5'-O-C8)-3'-dGMP. The reaction was studied by high-performance liquid chromatography, (1)H and (31)P nuclear magnetic resonance, and matrix-assisted laser desorption ionization time-of-flight mass spectrometry. The proposed mechanism involves Pt(IV) binding to N7 of 3'-dGMP followed by nucleophilic attack of a 5'-hydroxyl oxygen to C8 of G and an inner-sphere, 2e(-) transfer to produce cyclic (5'-O-C8)-3'-dGMP and [Pt(II)Cl(2)(dach)]. The same mechanism applies to 5'-d[GTTTT]-3', where the 5'-dG is oxidized to cyclic (5'-O-C8)-dG. The Pt(IV) complex binds to N7 of guanine in cGMP, 9-Mxan, 5'-d[TTGTT]-3', and 5'-d[TTTTG]-3', but no subsequent transfer of electrons occurs in these. The results indicate that a good nucleophilic group at the 5' position is required for the redox reaction between guanosine and the Pt(IV) complex. 相似文献