全文获取类型
收费全文 | 1972篇 |
免费 | 40篇 |
国内免费 | 6篇 |
专业分类
化学 | 1376篇 |
晶体学 | 30篇 |
力学 | 43篇 |
数学 | 335篇 |
物理学 | 234篇 |
出版年
2022年 | 20篇 |
2021年 | 15篇 |
2020年 | 26篇 |
2019年 | 21篇 |
2016年 | 23篇 |
2015年 | 27篇 |
2014年 | 35篇 |
2013年 | 70篇 |
2012年 | 62篇 |
2011年 | 95篇 |
2010年 | 40篇 |
2009年 | 42篇 |
2008年 | 84篇 |
2007年 | 95篇 |
2006年 | 82篇 |
2005年 | 68篇 |
2004年 | 69篇 |
2003年 | 73篇 |
2002年 | 63篇 |
2001年 | 26篇 |
2000年 | 18篇 |
1999年 | 16篇 |
1998年 | 22篇 |
1997年 | 26篇 |
1996年 | 42篇 |
1995年 | 30篇 |
1994年 | 24篇 |
1993年 | 25篇 |
1992年 | 25篇 |
1991年 | 18篇 |
1990年 | 20篇 |
1989年 | 25篇 |
1988年 | 19篇 |
1987年 | 28篇 |
1986年 | 21篇 |
1985年 | 42篇 |
1984年 | 38篇 |
1983年 | 36篇 |
1982年 | 37篇 |
1981年 | 31篇 |
1980年 | 13篇 |
1979年 | 27篇 |
1978年 | 38篇 |
1977年 | 32篇 |
1976年 | 33篇 |
1975年 | 35篇 |
1974年 | 23篇 |
1973年 | 20篇 |
1972年 | 13篇 |
1966年 | 16篇 |
排序方式: 共有2018条查询结果,搜索用时 27 毫秒
331.
Harry W. Gibson Zhenbin Niu Minjae Lee Terry L. Price Daniel V. Schoonover Michael A.G. Berg 《Tetrahedron letters》2018,59(11):1055-1058
Reaction of isoquinoline Reissert compound 1 with NaH and then isopropyl iodide in DMF at 22?°C led to four isolated products. Ketone 3 is the expected product of the well-known rearrangement of the intermediate Reissert anion. Cyano lactam 4 results from SNAr intramolecular displacement of the fluoride ion from the activated aroyl moiety of the anion. Isopropyl lactam 5 is proposed to result from a SET (single electron transfer) process via formation of the radical anion of 4, subsequent loss of the cyanide ion, and coupling of the resultant radical with isopropyl radicals formed via copper used to “stabilize” the alkyl iodide. The expected alkylated product 2 is also formed via a SET process involving electron transfer from the Reissert anion to 4, leading to the Reissert radical. Use of “non-stabilized” bromide or iodide led to 3 and 4, but did not produce 2 or 5. 相似文献
332.
Compound I crystallizes in the space groupP21/c withZ=4,a=5.889(5),b=30.755(10),c=10.815(3) Å,=92.95(6)°. Compound II crystallizes in the space groupP21/n withZ=4,a=10.235(2),b=10.144(1),c=18.346(2) Å,=92.00(1)°. The structures were solved by direct methods and refined by full-matrix least squares, from room-temperature data obtained with an Enraf-Nonius CAD4 diffractometer, to conventionalR factors of 0.041 for I and 0.048 for II.In both isomers the dioxin ring has an approximate envelope conformation with a pseudoequatorial –CC12·CHCl·CH3 group in the 2-position and a pseudoaxial –CCl2·CHCl·CH3 group in the 4-position. The molecular structures of I and II differ in that the group at the 2-position is rotated by about 120° in one isomer relative to its position in the other. Both compounds have packing patterns with a wave motif. In II there are interactions of the –NO2 group with other atoms both between molecules in the same wave and also between molecules in adjacent waves. In I the interactions of the –NO2 group with other atoms are in the same wave only with adjacent waves being packed together by van der Waals forces alone. 相似文献
333.
Crystals of 6-methyl-8-N,N-diacetylamino-2,4-bis(trichloromethyl)-1,3-benzdioxin are triclinic, P¯1,Z=2,a=9.586(3),b=9.914(2),c=12.308(5) Å,=67.19(3),=71.95(3), =74.14(2)°. The structure was solved by direct methods, from data collected at room temperature on an Enraf-Nonius CAD4 difFractometer, and refined by least squares to a finalR value of 0.039 using 3038 reflections. The heterocyclic ring has an envelope conformation. Of thecis-CCl3 groups one CC13 group is pseudoequatorial while the –(CAr·C)CCl3 group is pseudoaxial. (CAr)O-C 1.405(4); (CAr·O)C-O 1.387(4) Å; CAr-C(Cax)-0 112.3(3); C(Cax)-O-C(Ceq) 116.1(2)°; (CAr)O-C-O-C(CAr)58.2(3)°. The configuration of the diacetylamino group (DAA) issyn-anti. The -systems of the DAA and of the aromatic ring are approximately orthogonal, the deviations from orthogonality probably being caused by an intermolecular bifurcated hydrogen bond, each such interaction involving two molecules only, between thesyn O(=C) of the DAA and both hydrogen atoms bonded to the heterocyclic ring in a molecule of the enantiomer. The geometry of the DAA-benzene fragment is compared with those found in the other three published X-ray structures containing this group. 相似文献
334.
6-Nitro-1,3-benzdioxin is orthorhombic,Pbca,a=7.278(4),b=19.292(3),c=10.978(1) Å,Z=8. The structure was solved by direct methods from data collected at room temperature on an Enraf-Nonius CAD4 diffractometer and refined by least squares to a finalR value of 0.041 using 725 reflections. Some parameters associated with the heterocycle are torsion angle (CAr)O-C-O-C(CAr) 69.1(4)°; bond lengths CAr-O 1.362(3), (CAr)O-C 1.434(5), (CAr.O)C-O 1.377(5), O-C(CAr) 1.431(5), C-CAr 1.501(5) Å; bond angles CAr-O-C 113.5(3), O-C-O 111.5(3), C-O-C(CAr) 110.3(3), O-C-CAr 109.9(3)°;HaxHax 2.52(5) Å. 相似文献
335.
The higher-melting (mp 236°C)-isomer of dithioparachloral, i.e.,-2,4,6-tris(trichloromethyl)-1-oxa-3,5-dithian, is orthorhombic,Pnma,a=9.983(2),b=15.318(2),c=10.416(2) Å,V=1592.81 Å3,Z=4. The structure was solved by direct methods, from data collected at room temperature on an Enraf-Nonius CAD4 diffractometer, and refined by least-squares to a finalR value of 0.040 using 1017 reflections. The molecule is in the chair conformation with all threecis-CCl3 groups located pseudoequatorially. Endocyclic parameters are: torsion angles (deg) C-O-C-S 75.1(3), O-C-S-C –63.2(3), C-S-C-S 62.4(3); angles (deg) C-O-C 111.9(2), O-C-S 112.6(3), C-S-C 94.8(2), S-C-S 113.2(1); bond lengths (Å) O-C 1.426(5), C-S 1.824(4), S-C 1.818(3) (quoted in cyclic order). 相似文献
336.
6,8-dinitro-2,4-bis(trichloromethyl)-1,3-benzdioxin is monoclinic,P21/c,Z=4,a=12.348(2),b=11.575(3),c=12.183(4) Å,=107.48(2)°. The structure was solved by direct methods, from data collected at room temperature on an Enraf-Nonius CAD4 diffractometer, and refined by least-squares to a finalR value of 0.032 using 2192 reflections. The heterocyclic ring is an envelope structure, the dihedral angle between the plane of the aromatic ring and that containing five of the atoms of the heterocycle being 4.98(6)°. One -CCl3 group is pseudoequatorial while the (Ar-C)CCl3 group is pseudoaxial. C-Ceq 1.526(3) Å; C-Cax 1.537(3) Å; C-C(Cax)-O 112.4(2)°; C(Cax)-O-C(Ceq) 115.2(2)°. 相似文献
337.
Grabenauer M Bernstein SL Lee JC Wyttenbach T Dupuis NF Gray HB Winkler JR Bowers MT 《The journal of physical chemistry. B》2008,112(35):11147-11154
Aggregation of alpha-synuclein (alpha-syn), a protein implicated in Parkinson's disease (PD), is believed to progress through formation of a partially folded intermediate. Using nanoelectrospray ionization (nano-ESI) mass spectrometry combined with ion mobility measurements we found evidence for a highly compact partially folded family of structures for alpha-syn and its disease-related A53T mutant with net charges of -6, -7, and -8. For the other early onset PD mutant, A30P, this highly compact population was only evident when the protein had a net charge of -6. When bound to spermine near physiologic pH, all three proteins underwent a charge reduction from the favored solution charge state of -10 to a net charge of -6. This charge reduction is accompanied by a dramatic size reduction of about a factor of 2 (cross section of 2600 A2 (-10 charge state) down to 1430 A2 (-6 charge state)). We conclude that spermine increases the aggregation rate of alpha-syn by inducing a collapsed conformation, which then proceeds to form aggregates. 相似文献
338.
The standard oxidation states of central metal atoms in C
4v
nitrido ([M(N)(L)5]
z
) complexes are four units higher than those in corresponding nitrosyls ([M(NO)(L)5]
z
) (L=CN: z = 3−, M = Mn, Tc, Re; z = 2−, M = Fe, Ru, Os; L = NH3: z = 2+, M = Mn, Tc, Re; z = 3+, M = Fe, Ru, Os). Recent work has suggested that [Mn(NO)(CN)5]3− behaves electronically much closer to Mn(V)[b
2(xy)]2, the ground state of [Mn(N)(CN)5]3−, than to Mn(I)[b
2(xy)]2[e(xz,yz)]4. We have employed density functional theory and time-dependent density functional theory to calculate the properties of the
ground states and lowest-lying excitations of [M(N)(L)5]
z
and [M(NO)(L)5]
z
. Our results show that [M(N)(L)5]
z
and [M(NO)(L)5]
z
complexes with the same z value have strikingly similar electronic structures. 相似文献
339.
340.
Money VA Cartmell A Guerreiro CI Ducros VM Fontes CM Gilbert HJ Davies GJ 《Organic & biomolecular chemistry》2008,6(5):851-853
The substrate binding regions of a beta-1,3:1,4 glucanase are revealed through structural analysis with a thio-oligosaccharide and kinetics of enzyme variants. 相似文献