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21.
P. G. J. van Dongen 《Journal of statistical physics》1989,54(1-2):221-271
A general method is used for describing reaction-diffusion systems, namely van Kampen's method of compounding moments, to study the spatial fluctuations in reaction-limited aggregation processes. The general formalism used here and in subsequent publications is developed. Then a particular model is considered that is of special interest, since it describes the occurrence of a phase transition (gelation). The corresponding rate constants for the reaction between two clusters of sizei and sizej areK
ij=ij (i, j=1, 2,). For thediffusion constants D
j of clusters of sizej the following class of models is considered:D
j=D if 1Js andD
j=0 ifj>s. The casess= ands< are studied separately. For the models= the equal-time and the two-time correlation functions are calculated; this modelbreaks down at the gel point. The breakdown is characterized by a divergence of the density fluctuations, and is caused by the large mobility of large clusters. For all models withs< the density fluctuations remain finite att
c, and the equal-time correlation functions in the pre- and in the post-gel stage are calculated. Many explicit and asymptotic results are given. From the exact solution the upper critical dimension in this gelling model isd
c=2. 相似文献
22.
几种改进的CoMFA方法比较研究血小板活化因子拮抗剂 总被引:6,自引:1,他引:6
由于传统的比较分子场分析(CoMFA)方法本身存在一些缺陷,使得分子的叠合 规则以及叠合分子的空间取向和空间位置等因素对q~2的影响很大,因此相继提出 了几种改进的CoMFA方法。为了优化CoMFA结果,应用传统的CoMFA方法和交叉验证 的R~2引导的区域选择法(q~2-GRS)、全取向搜索法(AOS)、全空间搜索法(APS) 以及比较分子相似性指数(CoMSIA)等四种改进的CoMFA方法,对18个pinusolide类 衍生物这类新发现的血小板活化因子(PAF)拮抗剂进行了比较研究。结果表明四 种改进的CoMFA方法得到的q~2值均比传统CoMFA的高。q~2-GRS方法得到的q~2值有 所提高,但综合结果并不理想,AOS与APS得到的q~2较为理想,而在CoMSIA中, q~2几乎不受空间取向或空间位置的影响。同时我们引人基于样本的偏最小二乘法 (SAMPLS)取代原AOS/APS程序中的传统PLS进行统计分析,明显提高了其运行速 度。最后,根据q~2最高的CoMFA模型和CoMSIA模型设计了几个预测活性更高的 pinusolide类似物。 相似文献
23.
本文通过异氰酸酰化反应合成了含有脲基的苯乙炔新型配体及以它作为辅助配体的4′-(对甲基苯基)-6-苯基-2,2′-二联吡啶铂(II)络合物,初步研究了铂(II)络合物的光物理性质,发现由于脲基的存在,当浓度大于3.32×10-5mol/L时铂(II)络合物能够发生分子间簇集. 相似文献
24.
In this study, we report the design and synthesis of a series of new simplified fumitremorgin C analogues. The preliminary biological study indicated some of these simplified fumitremorgin C might be developed into breast cancer resistance inhibitors. 相似文献
25.
26.
The ethanol effect on the Trichoderma reesei cellulases was studied to quantify and clarify this inhibition type. To determine inhibition parameters of crude cellulase
and purified exoglucanase Cel7A, integrated Michaelis-Menten equations were used assuming the presence of two inhibitors:
cellobiose as the reaction product and ethanol as a possible bioproduct of cellulose fermentation.
It was found that hydrolysis of cellulose by crude enzyme follows a model that considers noncompetitive inhibition by ethanol,
whereas Cel7A is very slightly competitively inhibited. Crude cellulase is much more inhibited (K
iul=K
icl=151.9 mM) than exoglucanase Cel7A (K
icl=1.6 × 1015 mM). Also, calculated inhibition constants showed that cellobiose inhibition is more potent than ethanol inhibition both for
the crude enzyme as well as exoglucanase Cel7A. 相似文献
27.
The discovery of selective cyclooxygenase-2 (COX-2) inhibitors represents a major achievement of the efforts over the past few decades to develop therapeutic treatments for inflammation. To gain insights into designing new COX-2-selective inhibitors, we address the energetic and structural basis for the selective inhibition of COX isozymes by means of a combined computational protocol involving docking experiment, force field design for the heme prothetic group, and free energy perturbation (FEP) simulation. We consider both COX-2- and COX-1-selective inhibitors taking the V523I mutant of COX-2 to be a relevant structural model for COX-1 as confirmed by a variety of experimental and theoretical evidences. For all COX-2-selective inhibitors under consideration, we find that free energies of binding become less favorable as the receptor changes from COX-2 to COX-1, due to the weakening and/or loss of hydrogen bond and hydrophobic interactions that stabilize the inhibitors in the COX-2 active site. On the other hand, COX-1-selective oxicam inhibitors gain extra stabilization energy with the change of residue 523 from valine to isoleucine because of the formations of new hydrogen bonds in the enzyme-inhibitor complexes. The utility of the combined computational approach, as a valuable tool for in silico screening of COX-2-selective inhibitors, is further exemplified by identifying the physicochemical origins of the enantiospecific selective inhibition of COX-2 by -substituted indomethacin ethanolamide inhibitors. 相似文献
28.
In this paper,p-tricyanovinyl-N,N-dialkylanilines were synthesized as model compounds and through their spectroscopic behavior,the photo-induced electron transfer,charge separation were discussed and the aggregation in DMSO-H_2O system was investigated. 相似文献
29.
We developed a new method to measure the average aggregation number of large rod-like micelles using static fluorescence self-quenching of a solubilized fluorophore. The method is based on the increase of self-quenching of micelle-solubilized pyrene through excimer formation. We consider the effect of random distribution of pyrene in micelles and the micellar size distribution. The measured average aggregation <n> M is based on a new M-weighted raging similar to our exponential-weighted averaging in the transient decay method. We apply this method to study the effect of a large concentration of salt on the average aggregation behavior of sodium dodecyl sulfate (SDS) and cetyle tetraammonium bromide (CTAB). The sizes increase with increasing ionic concentrations. For SDS, we used the thermodynamic model developed by Missel et al. to calculate < n > M which we compare with experimental results. 相似文献
30.
The incorporation of explicit ions to mimic the effect of ionic strength or to neutralize the overall charge on a system in free energy calculations using molecular dynamics simulations is investigated. The difference in the free energy of hydration between two triosephosphate isomerase inhibitors calculated at five different ion concentrations is used as an example. We show that the free energy difference can be highly sensitive to the presence of explicit ions even in cases where the mutation itself does not involve a change in the overall charge. The effect is most significant if the molecule carries a net charge close to the site mutated. Furthermore, it is shown that the introduction of a small number of ions can lead to very severe sampling problems suggesting that in practical calculations convergence can best be achieved by incorporating either no counterions or by simulating at high ionic strength to ensure sufficient sampling of the ion distribution. 相似文献