全文获取类型
收费全文 | 2728篇 |
免费 | 106篇 |
国内免费 | 17篇 |
专业分类
化学 | 1714篇 |
晶体学 | 10篇 |
力学 | 115篇 |
数学 | 403篇 |
物理学 | 609篇 |
出版年
2023年 | 13篇 |
2022年 | 22篇 |
2021年 | 43篇 |
2020年 | 60篇 |
2019年 | 51篇 |
2018年 | 30篇 |
2017年 | 38篇 |
2016年 | 93篇 |
2015年 | 65篇 |
2014年 | 65篇 |
2013年 | 134篇 |
2012年 | 157篇 |
2011年 | 190篇 |
2010年 | 119篇 |
2009年 | 105篇 |
2008年 | 145篇 |
2007年 | 131篇 |
2006年 | 95篇 |
2005年 | 112篇 |
2004年 | 104篇 |
2003年 | 80篇 |
2002年 | 75篇 |
2001年 | 53篇 |
2000年 | 46篇 |
1999年 | 36篇 |
1998年 | 34篇 |
1997年 | 26篇 |
1996年 | 46篇 |
1995年 | 31篇 |
1994年 | 28篇 |
1993年 | 28篇 |
1992年 | 28篇 |
1991年 | 43篇 |
1990年 | 25篇 |
1989年 | 26篇 |
1988年 | 25篇 |
1987年 | 19篇 |
1986年 | 15篇 |
1985年 | 30篇 |
1984年 | 35篇 |
1983年 | 31篇 |
1982年 | 30篇 |
1981年 | 23篇 |
1980年 | 29篇 |
1978年 | 32篇 |
1977年 | 15篇 |
1976年 | 21篇 |
1975年 | 21篇 |
1973年 | 12篇 |
1972年 | 15篇 |
排序方式: 共有2851条查询结果,搜索用时 203 毫秒
71.
Max Winter Karl H. Schulte-Elte Alain Velluz Josef Limacher Wilhelm Pickenhagen Günther Ohloff 《Helvetica chimica acta》1979,62(1):131-134
Aroma Constituents of the Purple Passion Fruit. Two New Edulan Derivatives The isolation of (2R*, 4S*, 4aS*, 8aS*)-4,4a-epoxy-4,4a-dihydroedulan ( 1 ), and (2R*, 3S*, 8aS*)-3-hydroxyedulan ( 2 ), two new constituents of the purple passion-fruit (Passiflora edulis SIMS ), is reported. Racemic epoxide 1 was synthesized by oxidation of edulan 6 with peracidic acid, and racemate of alcohol 2 was obtained by reduction of ketone 7 , one of the chromic acid oxidation-products of edulan 6 . 相似文献
72.
A set of highly preorganized pyrazolate-bridged dimanganese complexes L(Mn)MnX have been prepared and structurally characterized. They can be described as hybrid organometallic/Werner-type systems that consist of a low-spin CpMn(I)(CO)2 subunit (Mn1) and a proximate tripodal tetradentate {N4} binding pocket accommodating a high-spin Mn(II) ion (Mn2), with Mn...Mn distances of approximately 4.3 A and different coligands bound to Mn2. Density functional theory (DFT) calculations (both the hybrid B3LYP and the pure BP86 functionals and the all-electron basis sets 6-311G and 6-311G*) confirm that the valence alpha and beta Kohn-Sham molecular orbitals (MOs) of these mixed-valent Mn(I)Mn(II) compounds have predominant Mn(3d) character and an almost perfectly localized nature: all five unpaired electrons are essentially localized at the Werner-type Mn2, whereas Mn1 possesses an effective closed-shell structure with the MOs of highest energy centered there. One-electron oxidation occurs in a clean process at approximately E(1/2) = -0.6 V (versus ferrocene/ferrocinium), giving the low-spin/high-spin Mn(II)Mn(II) species. UV/vis and IR spectroelectrochemistry as well as a detailed theoretical analysis reveal that the redox process takes place with strict site control at the organometallic subunit, while it does not significantly influence the spin and charge distribution on the Werner-type site. Positions and shifts of the nu(C[triple bond]O) absorptions are largely reproduced by the DFT calculations. These systems thus represent an exceptional example of the effect the unsymmetry of a dinucleating ligand scaffold has on the spin and charge distribution in homobimetallic complexes and might offer interesting prospects for the study of the cooperative effects of bimetallic arrays. 相似文献
73.
74.
Synthesis of 2′-Deoxy-5-(isothiazol-5-yl)uridine and Its Interaction with the HSV-1 Thymidine Kinase
Ingrid Luyten Hans De Winter Roger Busson Theo Lescrinier Isabelle Creuven Franlois Durant Jan Balzarini Erik De Clercq Piet Herdewijn 《Helvetica chimica acta》1996,79(5):1462-1474
2′-Deoxy-5-(isothiazol-5-yl)uridine ( 12 ) was synthesized starting from 2′-deoxy-5-iodouridine using a Pd-catalysed cross-coupling reaction with propiolaldehyde diethyl acetal followed by deprotection and ring closure using thiosulfate. 2′-Deoxyuridine 12 has a particular place among the 5-heteroaryl-substituted 2′-deoxyuridines in that it has a high affinity for herpes simplex virus type 1 (HSV-1)-encoded thymidine kinase (TK) without antiviral activity. Biochemical studies revealed that 12 is a substrate for viral TK. We further investigated the interaction of 12 with the HSV-1 thymidine kinase. The conformation of 12 in solution was established by NMR spectroscopy. The most stable conformer 12A has the S-atom of the isothiazole ring placed in the neighbourhood of the C(4)?O group of the pyrimidine moiety. The compound was docked in its most stable conformation in the active site of HSV-1 TK and subjected to energy minimization. This demonstrated that the isothiazole moiety binds in a cavity lined by the side chains of Tyr-132, Arg-163, Ala-167, and Ala-168 and that the C(3) atom of the isothiazole moiety is located in close proximity of the phenolic O-atom of Tyr-132 and the aliphatic part of the Arg-163 side chain. 相似文献
75.
76.
The thermodynamics and dynamics of a model S(N)1 reaction: t-BuCl --> t-Bu+ + Cl- is studied at the water liquid/vapor interface using molecular-dynamics computer simulations. The empirical valence bond approach is used to couple two diabatic states, covalent and ionic, in the electronically adiabatic limit. Umbrella sampling calculations are used to calculate the potential of mean force along the reaction coordinate (defined as the t-Bu to Cl distance) in bulk water and in several locations at the interface. We find a significant increase of the dissociation barrier height and of the reaction free energy at the interface relative to the bulk. This is shown to be due to the reduced polarity of the interface. Reactive flux correlation function calculations show significant deviation of the rate constant from the transition-state theory: The transmission coefficients range from 0.49 in the bulk to 0.05 above the Gibbs surface. The low transmission coefficient at the interface despite the lower friction is shown to be due to slow vibrational relaxation. 相似文献
77.
Acrylamide complexes of metal nitrates: [M(O‐OC(NH2)CHCH2)n(H2O)m][NO3]2 (M = Co( 1 ), Ni( 2 ) (n = 6 and m = 0) and Zn( 3 ) (n = 4 and m = 2)) have been determined by using single crystal X‐ray diffraction analysis. All complexes crystallize in the triclinic space group . The structures of 1 and 2 represent octahedral species [M(AAm)6]2+ (AAm = O‐OC(NH2)CHCH2 and M = Co or Ni) and uncoordinated nitrate ions. The structure of 3 involves the octahedral cation [Zn(AAm)4(H2O)2]2+ in which the Zn2+ environment includes oxygen atoms of four acrylamide and two water molecules that are stabilized using ionic nitrate ions. The observations of the solid‐state IR spectroscopic vibrational frequencies of these acrylamide complexes are in agreement with the crystal structures. 相似文献
78.
U. Buck J. Kesper Ch. Lauenstein M. Tolle M. Winter 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1989,12(1-4):293-295
(CO2) n , (NO) n and (NH3) n clusters are generated in a supersonic molecular beam and size selected by scattering from an He beam. By measurements of angular dependent mass spectra, TOF distributions and the angular dependence of the scattered signal quantitative information on the fragmentation probability by electron impact is derived. The van der Waals systems (CO2) n and (NO) n appear only at masses which are simply multiples of the monomer mass. The preferred cluster ion is the monomer ion for all investigated cluster sizes withn=2 to 4. The fragment pattern for the quasi-hydrogen bonded (NH3) n -cluster shows, beside a large number of fragment masses, a preference for protonated ions. The results are explained in terms of simple models based on the structural change from the neutral to the ionized configuration and the fragmentation pattern of the monomer followed by ionmolecule reactions. 相似文献
79.
Sarmiento M Mooney P Bishop JM Biswas N Cason NM Dauwe L Godfrey J Kenney VP Pemper R Rojek E Ruchti RC Shephard WD Edelstein RM Forsyth CP Gamarnik K Ginther G Kreymer AE Lipton R McQuade JM Potter DM Russ JS Spiegel L Johnson DE Buchholz D Cremaldi L Delchamps SW Mao HS Rosen JL Sakumoto W Schluter RA Sontz SB Winter C 《Physical review D: Particles and fields》1992,45(7):2244-2248
80.