全文获取类型
收费全文 | 2163篇 |
免费 | 59篇 |
国内免费 | 4篇 |
专业分类
化学 | 1654篇 |
晶体学 | 4篇 |
力学 | 18篇 |
数学 | 326篇 |
物理学 | 224篇 |
出版年
2023年 | 29篇 |
2022年 | 19篇 |
2021年 | 23篇 |
2020年 | 61篇 |
2019年 | 50篇 |
2018年 | 27篇 |
2017年 | 17篇 |
2016年 | 40篇 |
2015年 | 28篇 |
2014年 | 39篇 |
2013年 | 66篇 |
2012年 | 68篇 |
2011年 | 95篇 |
2010年 | 38篇 |
2009年 | 44篇 |
2008年 | 69篇 |
2007年 | 62篇 |
2006年 | 71篇 |
2005年 | 68篇 |
2004年 | 55篇 |
2003年 | 43篇 |
2002年 | 38篇 |
2001年 | 17篇 |
2000年 | 21篇 |
1999年 | 15篇 |
1998年 | 18篇 |
1996年 | 14篇 |
1995年 | 20篇 |
1994年 | 20篇 |
1991年 | 21篇 |
1990年 | 15篇 |
1987年 | 15篇 |
1986年 | 17篇 |
1985年 | 27篇 |
1984年 | 29篇 |
1983年 | 25篇 |
1982年 | 38篇 |
1981年 | 22篇 |
1980年 | 24篇 |
1979年 | 42篇 |
1978年 | 25篇 |
1977年 | 34篇 |
1976年 | 27篇 |
1975年 | 24篇 |
1974年 | 19篇 |
1973年 | 15篇 |
1967年 | 19篇 |
1959年 | 14篇 |
1956年 | 20篇 |
1934年 | 23篇 |
排序方式: 共有2226条查询结果,搜索用时 0 毫秒
101.
Berthold Fischer Helmut W. Schmalle Markus R. Baumgartner Max Viscontini 《Helvetica chimica acta》1997,80(1):103-110
The first crystal structure of a molybdenum complex 9 with a hydrogenated pterin and a sulfur ligand contributes to the discussion about the active center of molybdenum and tungsten enzymes containing a molybdopterin cofactor. Complex 9 was synthesized through a redox reaction of [MoVIO2 (LN-S2)] ( 8 ; LN-S2 = pyridine-2, 6-bis(methanethiolato)) with 5, 6, 7, 8-tetrahydropterin ( 7 ). 2 HCl (H4Ptr.2 HCl). The complex crystallizes, with a non-coordinating Cl-atom acting as a counterion, in the monoclinic space group C2/c (No. 15) with cell dimensions a = 22.900(5), b = 10.716(2), c = 17.551(4) Å, β = 120.36(3)°, and Z = 8. We interpret 9 as [MoIVO(LN-S2)(H+-q-H2Ptr)]Cl (q = quinonoid; H2Ptr = dihydropterin), i.e., a MoIV monooxo center coordinated by a pyridine-2, 6-bis(methanethiolato) ligand and a protonated dihydropterin. The spectroscopic properties of this new complex are comparable to those of other crystalline molybdenum complexes of hydrogenated pterins without additional S-coordination. The slightly H2O-soluble complex 9 reacts with the natural enzyme substrate DMSO very slowly, possibly due to the lack of easily dissociable ligands at the metal center. 相似文献
102.
Reactions of Ferrocenol and 1,1′-Ferrocendiol with Cyclotriphosphazenes, P3N3F6 and P3N3Cl6 The hexahalogeno-cyclotriphosphazenes, P3N3X6 (X ? F ( 1 a ), Cl ( 1 b )), react with ferrocenol (FcOH) in a molar ratio 1 : 1 to give the ferrocenoxy derivatives, FcO[P3N3X5] (X ? F ( 3 a ), Cl ( 3 b )); in an analogous manner the tetrameric ring P4N4Cl8 ( 2 b ) is converted to FcO[P4N4Cl7] ( 4 b ). 1 Abkürzungen: Fc = Ferrocenyl, (C5H5)Fe(C5H4?); fc = 1,1′-ferrocendiyl, Fe(C5H4?)2; rc = 1,1′-ruthenocendiyl, Ru(C5H4?)2. Fluorphosphazene werden mit a , Chlorphosphazene mit b gekennzeichnet. With 1,1′-ferrocenediol, (fc(OH) 2 ), the cyclo triphosphazenes react in a molar ratio 1 : 1 to produce fcO 2 [P 3 N 3 X 4 ] (X ? F ( 5 a ), Cl ( 5 b )). According to the x-ray structure analysis, the 1,1′-ferrocenediolato group in 5 a , b is bound to two different phosphorus atoms. On the contrary, the 1,1′-ferrocenedithiolato- and 1,1′-ferrocenediselenolato units in fcS 2 [P 3 N 3 X 5 ] (X ? F ( 6 a ), Cl ( 6 b )) and fcSe 2 [P 3 N 3 X 5 ] (X ? F ( 7 a ), Cl ( 7 b )) are attached to only one phosphorus atom, and spirocyclic 1,3-dichalcogena-2-phospha-[3]ferrocenophanes are formed. All new products have been characterized on the basis of their 1 H, 13 C and 31 P NMR as well as EI mass spectra. The molecular structures of 5 a , b and 6 a have been determined by x-ray structure analyses. 相似文献
103.
Karlheinz Ballschmiter Rainer Bacher Angela Mennel Regina Fischer Ulrich Riehle Max Swerev 《Journal of separation science》1992,15(4):260-270
High resolution gas chromatography, with mass selective detection, has been used for the analysis of PCB on methyl 50 % octyl polysiloxane (SB 50 Octyl), methyl octadecyl polysiloxane, and a smectic polysiloxane (SB Smectic); and for the analysis of polychlorodibenzodioxins and polychlorodibenzofurans with 1 to 8 chlorine substituents on 100 % cyanopropyl siloxane (SP 2331), smectic polysiloxane (SB Smectic), a new polar stationary phase (DB-Dioxin). The analysis has also been performed by column coupling. 相似文献
104.
Andrea Schfer Berthold Fischer Henning Paul Ren Bosshard Manfred Hesse Max Viscontinif 《Helvetica chimica acta》1992,75(6):1955-1964
This paper marks the first reported detection of radical cations by Electrospray-Ionization Mass Spectrometry (ESI-MS). Electron Spin Resonance (ESR) measurements have proven that the detected radical cation existed already in solution and has not been generated by the electrospray ionization technique. However, we observed that the radical cation can be generated by changes in the ionization conditions. A molar mixture of 2-amino-5,6,7,8-tetrahydro-5-methylpterin-4(4H)-one dihydrochloride ( = 5,6,7,8-tetrahydro-N(5)-methylpterin-2 HCl, N(5)-MTHP-2 HCl), and tris(pentane-2,4-dionato)iron(III) in MeCN at pH 2–3 leads to the formation of a [bis(pentane-2,4-dionato)(2-amino-5,6,7,8-tetrahydro-5-methylpteridin-4 (4H)-one)]iron complex ( = [bis(pentane-2,4-dionato) (5,6,7,8-tetrahydro-N(5)-methylpteridin)]iron complex) which can be detected by ESI-MS. The results suggest that this complex might be an FeII radical cation, which could possibly be a suitable model complex for the active center of the phenylalanine hydroxylase. In the same solution, the stable radical cation of N(5)-MTHP is identified by ESI-MS and ESR. 相似文献
105.
Jan-Falk Kannengießer Max Briesenick Dr. Dennis Meier Dr. Volker Huch Dr. Bernd Morgenstern Prof. Dr. Guido Kickelbick 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(66):16461-16476
Organosilanols typically show a high condensation tendency and only exist as stable isolable molecules under very specific steric and electronic conditions at the silicon atom. In the present work, various novel representatives of this class of compounds were synthesized by hydrolysis of alkoxy- or chlorosilanes. Phenyl, 1-naphthyl, and 9-phenanthrenyl substituents at the silicon atom were applied to systematically study the influence of the aromatic substituents on the structure and reactivity of the compounds. Chemical shifts in 29Si NMR spectroscopy in solution, correlated well with the expected electronic situation induced by the substitution pattern on the Si atom. 1H NMR studies allowed the detection of strong intermolecular hydrogen bonds. Single-crystal X-ray structures of the alkoxides and the chlorosilanes are dominated by π-π interactions of the aromatic systems, which are substituted by strong hydrogen bonding interactions representing various structural motifs in the respective silanol structures. 相似文献
106.
The X-ray crystal structure analysis of the antibiotic elaiophylin ( 1 ), monoclinic, a = 9.927, b = 10.105, c = 31.183 Å, β = 93.20°, space group P21, confirms the constitution elucidated by spectroscopic methods and chemical degradation. In the crystal the two chemically equivalent halves of the molecule are related by an approximate twofold rotation axis. 相似文献
107.
Chroma to graphic Separation and Identification of Diastereomeric Carotinoids with Distant Chiral Centers The high-performance liquid chromatographic separation of diastereomeric C40-carotinoids is described possessing chiral centers which are separated by 18 C-atoms (nonaene system). The method is applied to the separation of the two diastereomers of 6,6′-dihydrorhodoxanthin 1a and 1b (ε,ε-carotene-3,3′-dione) and the six diastereomers of tunaxanlhin (ε,ε-carotene-3,3′-diol; 2a–2f ). Conditions for the separation of lutein [(3R, 3′R, 6′R)-β,ε-carotene-3.3′-diol, 3a ], 3′-epi-lutein [(3R,3′S,6′R)-β, ε-carotene-3,3′-diol, 3b ] and its 13′-cis- ( 3c ) and 13-cis-stereo-isomers( 3d ) are also reported. Identification of the different chromatographic fractions was possible by use of authentic synthetic samples or by 1H-NMR. spectroscopy. 相似文献
108.
Roland Prewo Jost H. Bieri Subhendu Narayan Ganguly Max Viscontini 《Helvetica chimica acta》1982,65(3):1094-1099
The Configuration at C(6) of Natural 5,6,7,8-Tetrahydro-L-biopterin and of its Pentaacetate The structure of (6.R)-pentaacetyl-5,6,7,8-tetrahydro-L-biopterin, one of two diastereoisomers obtained by catalytic hydrogenation and subsequent acetylation of L-biopterin, has been determined by X-ray diffraction analysis. The space group is P212121, a=8,053(l), b=14,955(3), c= 21,502 (4) Å. The asymmetric unit contains one molecule of the biopterin derivative and one of ethyl acetate. The R-configuration can be assigned to C(6) by reference to the known configurations of the other asymmetric C-atoms. As hydrolysis of this diastereoisomer yields the natural 5, 6,7,8-tetrahydro-L-biopterin, the latter also possesses the (6 R)-configuration. 相似文献
109.
110.