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101.
Transesterification of a phosphodiester bond of RNA models has been studied in various buffer solutions, under neutral and slightly alkaline conditions in H2O and D2O. The results show that imidazole is the only buffer system where a clear buffer catalysis on the cleavage of a phosphodiester bond is observed. The rate enhancement in sulphonic acid buffers is smaller, and a sulphonate base, particularly, is inactive as a catalyst. The rate‐enhancing effect of imidazole is, however, catalytic, and the catalytic inactivity of sulphonate buffers can be attributed to their structure and/or charge. The catalysis by imidazole is a complex system which, in addition to first‐order reactions, involves a process that shows a second‐order dependence in imidazole concentration. The latter reaction becomes significant in acidic imidazole buffers (pH < pKa), as the buffer concentration increases. The kinetic solvent deuterium isotope effect kH/kD, referring to first‐order catalysis by imidazole base, is 2.3 ± 0.3. That referring to second‐order catalysis is most probably much larger, but an accurate value could not be obtained. Copyright © 2007 John Wiley & Sons, Ltd.  相似文献   
102.
A scheme of magnetic calorimeter for registration of rare events characterized by small energy release (cosmic rays, WIMPs, solitary X-ray quanta) is proposed. The calorimeter is brought to operation by adiabatic demagnetization, and its magnetic response is measured by a quantum interferometer (SQUID, A. Barone and G. Paterno, Physics and applications of Josephson Effect). Special consideration is given to the specific features of calorimeter operation in the ferromagnetic transition region. The trigger registration of ultrasmall energy release by a ferromagnetic system in the metastable state is described.  相似文献   
103.
In this paper we apply linear control theory to study the effect of various inventory policies on order and inventory variability, which are key drivers of supply chain performance. In particular, we study a two-echelon supply chain with a stationary demand pattern under the influence of three inventory policies: an inventory-on-hand policy that bases orders on the visible inventory at an installation, an installation-stock policy that bases orders on the inventory position (on-hand plus on-order inventory) at an installation, and an echelon-stock policy that bases orders on the inventory position at that installation and all downstream installations. We prove analytically that the inventory-on-hand policy is unstable in practical settings, confirming analytically what has been observed in experimental settings and in practice. We also prove that the installation-stock and echelon-stock policies are stable and analyze their effect on order and inventory fluctuation. Specifically, we show the general superiority of the echelon-stock in our setting and demonstrate analytically the effect of forecasting parameters on order and inventory fluctuations, confirming the results in other research.  相似文献   
104.
Regioselectivity of the Tsuji-Trost reaction on allyl acetates and carbonates substituted with silyl groups at the olefinic moiety has been analyzed. Silicon atom in the central carbon atom increases the stability of the intermediate π-allylpalladium cation with respect to the isomeric π-allylpalladium cation featuring the silicon in a terminal carbon atom.  相似文献   
105.
氯代5-氟脲嘧啶卟啉的红外光谱特性的研究   总被引:6,自引:0,他引:6  
本文对新合成的对位及间位两类氯代苯基 5 氟脲嘧啶卟啉的红外光谱吸收峰进行了归属和总结 ,讨论了其红外吸收频率随取代基位置变化的规律。指出了苯环上的取代基为电负性强的基团时 ,由于场效应的存在 ,使被测化合物的羰基伸缩振动吸收峰的相对强度发生改变。同时 ,表明了嘧啶环上N原子发生了取代 ,形成单、双取代 5 氟脲嘧啶卟啉化合物的红外光谱特性。  相似文献   
106.
High linear alkenes (1-octene and 1-decene) have been hydroformylated using water-soluble rhodium complexes associated with sulfonated diphosphines in the presence of ionic surfactants or methanol. In all cases, the hydroformylation activities were higher than in experiments without additives. The selectivity in aldehydes was higher when we used cetyltrimethylammonium hydrogensulfate (CTAHSO4) as the surfactant or methanol as the co-solvent.  相似文献   
107.
格子Boltzmann数值模拟方法是研究复杂的多孔介质结构特别是Klinkenberg效应的有效方法之一,对处理复杂边值问题尤其有效,用格子Boltzmann方法研究了气流穿越多孔介质问题,并将数值计算结果与实验结果进行了比较,结果表明格子Boltzmann方法是数值模拟气流穿越多孔介质问题的有效方法之一。  相似文献   
108.
By means of improved ligand-field theory, the "pure electronic" pressure-induced shifts (PS's) and the PS's due to electron-phonon interaction (EPI) of R1 line and R2 line of YAG:Cr3 have been calculated, respectively.The calculated results are in very good agreement with the experimental data. It is demonstrated that the admixture of |t22(3T1)e4T2> and |t322E> bases in the wavefunction of R1 level of YAG:Cr3 and its change with pressure play a key role for the PS of R1 line. The behaviors of the "pure electronic" PS of R1 line and the PS of R1 line due to EPI are different. It is the combined effect of them that gives rise to the total PS of R1 line, which has satisfactorily explained the experimental results. The systematic analyses and comparisons between the feature of R1-line PS of YAG:Cr3 and the ones of three laser crystals (GSGG:Cr3 , GGG:Cr3 and ruby) have been made, and the origin of the difference between them has been revealed.  相似文献   
109.
针对激光介质的内热源,以多次吸收作用为基础提出了适用于侧面双向泵浦板状激光介质的不均匀内热源模型,即多次吸收不均匀内热源模型,并与均匀内热源和一次吸收内热源模型进行了对比分析。研究表明,介质厚度及光吸收系数组成的无量纲参数不同时,三种内热源模型得到的内热源分布也有所不同。最后给出了内热源不均匀度及多次吸收模型与一次吸收模型之间的差异在不同目标值下的内热源模型适用准则。  相似文献   
110.
给出了为RHIC-STAR飞行时间探测器设计的多气隙电阻板室(MRPC)的辐照实验结果. 实验采用100mCi60Co γ源, 采用不同的剂量率对MRPC进行辐照. 一个室在大剂量率2.87×10-2Gy/h下辐照了24h后, 其性能如噪声计数率, 暗电流等均大大退化. 另一个室在相对低剂量率5.31×10-4Gy/h下辐照了530h, 其性能没有见到任何变坏. 实验的目的是为了了解这种探测器在几年的运行中经过大剂量的辐照后的性能变化情况.  相似文献   
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