首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   9194篇
  免费   1413篇
  国内免费   1134篇
化学   6628篇
晶体学   88篇
力学   422篇
综合类   103篇
数学   1062篇
物理学   3438篇
  2024年   16篇
  2023年   195篇
  2022年   273篇
  2021年   314篇
  2020年   389篇
  2019年   385篇
  2018年   309篇
  2017年   306篇
  2016年   432篇
  2015年   426篇
  2014年   524篇
  2013年   630篇
  2012年   827篇
  2011年   814篇
  2010年   539篇
  2009年   492篇
  2008年   616篇
  2007年   593篇
  2006年   489篇
  2005年   438篇
  2004年   303篇
  2003年   247篇
  2002年   238篇
  2001年   212篇
  2000年   229篇
  1999年   193篇
  1998年   179篇
  1997年   149篇
  1996年   165篇
  1995年   148篇
  1994年   111篇
  1993年   100篇
  1992年   81篇
  1991年   61篇
  1990年   66篇
  1989年   40篇
  1988年   37篇
  1987年   32篇
  1986年   28篇
  1985年   35篇
  1984年   15篇
  1983年   14篇
  1982年   15篇
  1981年   6篇
  1980年   7篇
  1979年   6篇
  1978年   2篇
  1977年   4篇
  1976年   6篇
  1962年   1篇
排序方式: 共有10000条查询结果,搜索用时 640 毫秒
151.
Cu(I)/Diamine-catalyzed Aryl-alkyne Coupling Reactions   总被引:1,自引:0,他引:1  
Arylalkynes are important building blocks for the synthesis of natural products,pharmaceuticals,and artificial molecular devices1.They are often synthesized via the Pd-catalyzed Sonogashira coupling reactions between aryl halides and terminal alkynes2,3.Unfortunately,it remains difficult to apply the Sonogashira reaction to industrial scale and/or pharmaceutical synthesis,due to the high cost of Pd and the difficulty in removing the toxic Pd residues from the reaction products.Thus it is wor…  相似文献   
152.
A combination of a DNA ligase and a restriction endonuclease provides a DNA polymerase activity, which might suggest a novel strategy for polymer synthesis.  相似文献   
153.
Using the mixture of cetyltrimethylammonium bromide (CTAB) and p‐Octyl polyethylene glycol phenyl ether (OP‐10) as templates, siliceous MCM‐48 materials can be synthesized with low molar ratio of CTAB to silica (0.139:1) and low concentration of mixed surfactants (ca.5%) and within a wide range of OP‐10/CTAB ratio (0.08?0.25). The materials were characterized by X‐ray powder diffraction, N2 adsorption/desorption isotherm, TEM, TG‐DSC and 29Si MAS NMR. Measurements indicated that the use of mixed surfactants allowed better condensation and higher ordering of the cubic mesostructure; at the same time, some properties of these materials were sensitive to the OP‐10/CTAB ratio. It was also found that the reduced pH of the gel which had been crystallized for a certain time gave a highly reproducible synthesis with a high silica yield (about 95%). Furthermore, the reaction mechanism of the synthesis is discussed in detail.  相似文献   
154.
岩,心是油气储层的基本单元,其内部结构和渗流性质反映了油藏的基本特征.岩。心的精细描述是油藏描述、储层动态监测及设计强化采油方案的重要基础.本文利用核磁共振(NMR)自旋密度做成像,快速无损地观测到两类基本储油岩石——砂岩和灰岩的内部结构,提供了岩石渗透性、孔隙性及灰岩沉积环境等重要信息.1实验方法以自旋回波单片NMR成像脉冲序列为基础,设。P平面内样品的目施密度为P(。,v).演化期t。,在。方向梯度场G。作用下,各处横向磁化矢量获得的相移为式中,7为共振核(在成像中一般为质子)的旋磁比,g为坐标位置·…  相似文献   
155.
磷酸铝类分子筛是近年来继Y型和ZSM七分子筛之后的第三代合成分子筛材料,其骨架由A10。和P0。四面体均匀交替地组成问.由于带负电行的A10。和带正电荷的PO。四面体数目相等,整个骨架呈电中性,所以这类分子筛本身无离子交换能力和催化活性.当用硅或某些金属离子(如Mg、Fe、Co、Zn等)对磷酸铝分子筛进行同晶取代,就会在骨架上造成电行不平衡,从而使这类分子筛具有一定的离子交换能力和酸性【习.因而对硅或金属离子在磷酸错类分子筛中取代机理的研究一直是人们感兴趣的问题问.Vpl-5是最近才合成出来的具有18圆环一维孔结构的…  相似文献   
156.
Five new nonalkaloid constituents, a neolignan, japonin A ( 1 ), a macrocyclic lactone, japonin B ( 2 ), a (phenylethyl)benzoquinone, japonin C ( 3 ), a phenanthraquinone, japonin D ( 4 ), as well as a dihydrostilbene, stilbostemin M ( 5 ), were isolated from the roots of Stemona japonica, together with eight known compounds. Their structures were established by spectroscopic analyses.  相似文献   
157.
将一种新型的CuMn催化剂用于由合成气合成甲酸甲酯和甲醇,该催化剂表现出良好的反应活性和甲酸甲酯选择性。考察了反应温度、合成气压力及催化剂制备方法等对合成甲酸甲酯和甲醇的反应活性及选择性的影响。在反应条件下,产物收率最高达60.10g/(L·h),产物甲酸甲酯的选择性很高。用BET、XRD及XPSAuger等测试方法对催化剂的比表面、晶相组成以及铜、锰在催化剂中的价态进行了表征,并探讨了催化剂失活的原因。  相似文献   
158.
Complexes and reactions of 2-methylbutene-2 with hydrohalogen (HCl, HBr) have been studied in solid phase at 80–150 K. It has been found that 2-methylbutene-2 forms with HX complexes of 1:1 and 1:2 composition. Hydrohalogenation proceeds via the rearrangement of complex 2HX·C5H10 into complex of the addition product with HX. Kinetic equation depends on the reagents ratio. In excess of HX (1< HX:C5H10< 10) reaction can be described by the first order kinetic equation. If the ratio HX:C5H10 is more than 10, reaction is described by polychronous kinetic law. The effective activation energy of solid phase hydrohalogenation does not exceed 20 kJ/mole. The molecular mechanism of hydrohalogenation in solid phase has been proposed.  相似文献   
159.
本文用 GPC方法测定了聚 N-乙烯咔唑中残留单体含量,测定精确度约为±2%,聚合物中单体的最小检知量为0.03%。并且讨论了凝胶的孔径、溶剂纯度及不同检测器对结果的影响。  相似文献   
160.
Hemocompatibility is an essential aspect of blood contacting polymers. Knowledge of the relationship between polymer structure and hemocompatibility is important in designing such polymers. In this work, the effect of swelling behavior and states of water on the hemocompatibility of poly(acrylonitrile-co-N-vinyl-2-pyrrolidone) (PANCNVP) films was studied. Platelet adhesion and plasma recalcification time tests were used to evaluate the hemocompatibility of the films. Considering the importance of surface properties on the hemocompatibility of polymers, static water contact angles were measured by both sessile drop and captive bubble methods. It was found that, on the film surface of PANCNVP with a higher NVP content, adhered platelets were remarkably suppressed and the recalcification time was longer. The total water content adsorbed on the PANCNVP film was determined through swelling experiments performed at temperatures of interest. Differential scanning calorimetry and thermogravimetric analysis were used to probe the states of water in the films. Based on the results from these experiments, it was hypothesized that the better hemocompatibility of PANCNVP films with higher NVP contents was due to their higher free water content, because water molecule exchange at the polymer/liquid interface, facilitated by a high free water content, is unfavorable for the formation of surface bound water, which causes poor hemocompatibility. [diagram in text].  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号