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21.
A micro-reactor system with continual spectrophotometric detection has been operated in Sequential Injection lab-on-valve (SI-LOV) mode and applied to enzyme kinetics and inhibition studies, using acetylcholinesterase (AChE) and angiotensin-converting enzyme (ACE) as model systems. With the advantages of automation, real-time kinetic measurement, and thorough mixing, the SI-LOV micro-reactor system allows for the monitoring of initial reaction rates and determination of reactant concentrations in the reaction mixture, both of which are essential for the determination of kinetic constants for enzymes and inhibitors. Enzyme, substrate, and inhibitor are precisely metered by the syringe pump and delivered to a stirred micro-reactor, followed by a reference scan that establishes the baseline for the following reaction rate measurement. Michaelis constants (Km) for AChE and ACE were determined to be 0.16 mM and 0.30 mM, respectively, which are consistent with literature values. The type of inhibition (competitive, uncompetitive, or mixed), the dissociation constants for the inhibitors, and the inhibitor dose-response curves were also determined. 相似文献
22.
The self‐complementary tetrameric propargyl triols 8, 14, 18 , and 21 were synthesized to investigate the duplex formation of self‐complementary, ethynylene‐linked UUAA, AAUU, UAUA, and AUAU analogues with integrated bases and backbone (ONIBs). The linear synthesis is based on repetitive Sonogashira couplings and C‐desilylations (34–72% yield), starting from the monomeric propargyl alcohols 9 and 15 and the iodinated nucleosides 3, 7, 11 , and 13 . Strongly persistent intramolecular H‐bonds from the propargylic OH groups to N(3) of the adenosine units prevent the gg‐type orientation of the ethynyl groups at C(5′). As such, an orientation is required for the formation of cyclic duplexes, this H‐bond prevents the formation of duplexes connected by all four base pairs. However, the central units of the UAUA and AAUU analogues 18 and 14 associate in CDCl3/(D6)DMSO 10 : 1 to form a cyclic duplex characterized by reverse Hoogsteen base pairing. The UUAA tetramer 8 forms a cyclic UU homoduplex, while the AUAU tetramer 21 forms only linear associates. Duplex formation of the O‐silylated UUAA and AAUU tetramers is no longer prevented. The self‐complementary UUAA tetramer 22 forms Watson–Crick‐ and Hoogsteen‐type base‐paired cyclic duplexes more readily than the sequence‐isomeric AAUU tetramer 23 , further illustrating the sequence selectivity of duplex formation. 相似文献
23.
For ν≥0 let cνk be the k-th positive zero of the cylinder functionC v(t)=J v(t)cosα-Y v(t)sinα, 0≤α>π whereJ ν(t) andY ν(t) denote the Bessel functions of the first and the second kind, respectively. We prove thatC v,k 1+H(x) is convex as a function of ν, ifc νk≥x>0 and ν≥0, whereH(x) is specified in Theorem 1.1. 相似文献
24.
Blaylock GT Bolton T Brown JS Bunnell KO Burnett TH Cassell RE Coffman D Cook V Coward DH Dorfan DE Dubois GP Eigen G Eisenstein BI Freese T Gladding G Grab C Heusch CA Hitlin DG Izen JM Köpke L Li A Lockman WS Mallik U Matthews CG Mir R Mockett PM Mozley RF Nemati B Odian A Parker J Parrish L Partridge R Pitman D Sadrozinski HF Scarlatella M Schalk TL Schindler RH Seiden A Simopoulos C Stockdale IE Stockhausen W Thaler JJ Toki W Tripsas B Villa F Wasserbaech S Wattenberg A Weinstein AJ 《Physical review letters》1987,58(21):2171-2174
25.
Feichtinger Gustav Hartl Richard F. Kort Peter M. Seidl Andrea Wrzaczek Stefan 《Journal of Optimization Theory and Applications》2022,194(3):878-895
Journal of Optimization Theory and Applications - This paper considers a capital accumulation game where the installation costs of investments are lowered by the firm’s own capital stock... 相似文献
26.
Andrea Posilicano 《Potential Analysis》1996,5(3):241-271
We prove a convergence theorem for sequences of Diffusion Processes corresponding to Dirichlet Forms of the kind
.We obtain convergence in total variation norm of the corresponding probability measures on the path space C(+;d) under hypotheses which, for example, are satisfied in the case of H
loc
1
(
d
)-convergence of the 's, but we can allow more singular situations as regards the approximating sequences. We use then these results to give a criterion of convergence for generalized Schrödinger operators in which the potential function should not necessarily exists as a measurable function. We obtain convergence not only in strong resolvent sense, but we also obtain convergence in the uniform operator topology up to sets of arbitrarily small Lebesgue measure. Applications to the problem of the approximation of ordinary Schrödinger operators by generalized ones corresponding to zero-range interactions are given. 相似文献
27.
We revisit the Landau-Teller heuristic approach to adiabatic invariants and, following Rapp, use it to investigate the energy exchanges between the different degrees of freedom, in simple Hamiltonian systems describing the collision of fast rotating or vibrating molecules with a fixed wall. We critically compare the theoretical results with particularly accurate numerical computations (quite small energy exchanges, namely of one part over 1030, are measured). 相似文献
28.
Given aself similar fractal K ? ? n of Hausdorff dimension α>n?2, andc 1>0, we give an easy and explicit construction, using the self similarity properties ofK, of a sequence of closed sets? h such that for every bounded open setΩ?? n and for everyf ∈ L2(Ω) the solutions to $$\left\{ \begin{gathered} - \Delta u_h = f in \Omega \backslash \varepsilon _h \hfill \\ u_h = 0 on \partial (\Omega \backslash \varepsilon _h ) \hfill \\ \end{gathered} \right.$$ converge to the solution of the relaxed Dirichlet boundary value problem $$\left\{ \begin{gathered} - \Delta u + uc_1 \mathcal{H}_{\left| K \right.}^\alpha = f in \Omega \hfill \\ u = 0 on \partial \Omega \hfill \\ \end{gathered} \right.$$ (H ∣ α denotes the restriction of the α-dimensional Hausdorff measure toK). The condition α>n?2 is strict. 相似文献
29.
The low-temperature NMR spectra of 1,4-bis(mesitoyl)durene, 1, and of 1,4-bis(mesitylethenyl)durene, 2, reveal the presence of syn and anti rotamers at the equilibrium, their relative proportions depending on the dielectric constant of the solvent. In solution the more stable rotamer of 1 is the anti whereas, in the case of 2, the more stable is the syn. Depending on the crystallization solvent employed the more (anti) and the less stable (syn) rotamers were both observed (X-ray diffraction) in the solid state of 1. On the other hand, only the less stable rotamer (anti) was found to be present in the solid state of 2. As shown by MM calculations, the syn-to-anti interconversion occurs via a correlated process (cogwheel pathway) involving the mesityl-C and durene-C bond rotations: the dynamic NMR technique yields an experimental barrier of 8.2 kcal mol(-)(1) for 1 and 13.1 kcal mol(-)(1) for 2. In the case of derivative 2 a second barrier, due to a second type of correlated rotation process (torsion), was also determined (8.6 kcal mol(-)(1)). As a consequence of the restriction of this second torsional motion the anti rotamer of 2 displays two distinguishable NMR spectra at -133 degrees C, corresponding to a pair of conformers with different symmetry (anti C(i)() and anti C(2)). 相似文献
30.
A synthesis of 1,2-cis-configurated, non-isosteric phosphonate analogues of aldose-1-phosphates is described. Treatment of 1-O-acyl-glycoses 1 , 7 , 13 , and 19 with trialkyl phosphite in the presence of trimethylsilyl trifluoromethanesulfonate gave the 1,2-cis-configurated glycosylphosphonates 2 , 4 , 8 , 10 , 14 , 16 , 20 , and 22 as the major anomers and the 1,2-trans-configurated glycosylphosphonates 3 , 5 , 9 , 11 , 15 , 17 , 21 , and 23 as the minor anomers. The 1,2-cis-configurated phosphonates 4 , 10 , 16 , and 22 were deprotected to give the (β-D -glucopyranosyl)phosphonate 6 , the (β-D -mannopyranosyl)phosphonate 12 , the (β-D -ribofuranosyl)phosphonate 18 , and the (β-D -arabinofuranosyl)phosphonate 24 , respectively, in high yields. The preferred formation of 1,2-cis-configurated phosphonates is explained by postulating an equilibrium between the anomeric phosphonium-salt intermediates (such as 25 and 26 ) and a stabilization of the cis-configurated salts through formation of a pentacoordinated species (such as 28 ). 相似文献