全文获取类型
收费全文 | 6817篇 |
免费 | 1291篇 |
国内免费 | 2032篇 |
专业分类
化学 | 5122篇 |
晶体学 | 215篇 |
力学 | 412篇 |
综合类 | 150篇 |
数学 | 1064篇 |
物理学 | 3177篇 |
出版年
2024年 | 24篇 |
2023年 | 108篇 |
2022年 | 255篇 |
2021年 | 264篇 |
2020年 | 294篇 |
2019年 | 300篇 |
2018年 | 282篇 |
2017年 | 321篇 |
2016年 | 297篇 |
2015年 | 378篇 |
2014年 | 405篇 |
2013年 | 516篇 |
2012年 | 572篇 |
2011年 | 632篇 |
2010年 | 562篇 |
2009年 | 630篇 |
2008年 | 639篇 |
2007年 | 524篇 |
2006年 | 493篇 |
2005年 | 418篇 |
2004年 | 312篇 |
2003年 | 203篇 |
2002年 | 253篇 |
2001年 | 221篇 |
2000年 | 247篇 |
1999年 | 171篇 |
1998年 | 100篇 |
1997年 | 96篇 |
1996年 | 105篇 |
1995年 | 103篇 |
1994年 | 85篇 |
1993年 | 61篇 |
1992年 | 49篇 |
1991年 | 45篇 |
1990年 | 34篇 |
1989年 | 31篇 |
1988年 | 24篇 |
1987年 | 13篇 |
1986年 | 20篇 |
1985年 | 11篇 |
1984年 | 6篇 |
1983年 | 7篇 |
1982年 | 5篇 |
1981年 | 4篇 |
1980年 | 4篇 |
1979年 | 6篇 |
1974年 | 2篇 |
1965年 | 3篇 |
1964年 | 1篇 |
1936年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 46 毫秒
121.
Bao J Baker RK Doss GA Kayser F Kotliar A Miao S Parsons WH Rupprecht KM 《Organic letters》2002,4(11):1871-1873
[reaction: see text] Pentacyclic triterpenoid natural product correolide (1) was converted to ketone 2 via ozonolysis. An unusual fragmentation reaction of ketone 2 with LiCl was discovered. This reaction is general among several similar substrates examined and appears to be specific for the correolide-type E-ring structure (ketone). A mechanism involving a retroaldol reaction, a nucleophilic opening of the epoxide, and a subsequent acetoxy elimination reaction was proposed. 相似文献
122.
123.
Tao Miao 《Tetrahedron letters》2007,48(1):95-99
The immobilization of copper in organic-inorganic hybrid materials catalyzing the Ullmann reaction has been described. Phenols reacted with aryl iodides, aryl bromides and aryl chlorides smoothly in the presence of a 3-(2-aminoethylamino)propyl functionalized silica gel immobilized copper catalyst. The protocol involved the use of DMSO as the solvent, and potassium fluoride as the base. The reactions generated the corresponding cross-coupling products in good to excellent yields. Furthermore, the silica-supported copper could be recovered and recycled by a simple filtration of the reaction solution and used for 10 consecutive trials without loss of its reactivity. 相似文献
124.
铝酸钠和含硅铝酸钠溶液结构和性质的研究 总被引:1,自引:0,他引:1
本文通过对铝酸钠和硅铝酸钠溶液的红外光谱、拉曼光谱、粘度、表面张力、丁达尔现象和聚沉等光谱和物理化学性质的研究测定,分析了硅在铝酸钠溶液中的行为.认为硅主要是取代Al-O-Al结构中的Al,形成Al-O-Si结构和Al-O-Si-O-Al-O结构等多种形式硅氧铝键以及由氢键相连的大分子结构.这种结构直接影响其物理化学性质,表现为随硅含量增加表面张力增加,粘度上升,具有丁达尔现象等.说明含硅铝酸钠溶液中存在大分子的胶性基团,属于无机高分子溶液,这种网络状"大分子"结构是硅铝酸钠溶液稳定的原因. 相似文献
125.
The reaction of Mn(2)(CO)(7)(mu-S2) (1) with [CpMo(CO)(3)](2) (Cp = C(5)H(5)) and [Cp*Mo(CO)(3)](2) (Cp* = C(5)(CH(3))(5)) yielded the new mixed-metal disulfide complexes CpMoMn(CO)(5)(mu-S2) (2) and Cp*MoMn(CO)(5)(mu-S2) (3) by a metal-metal exchange reaction. Compounds 2 and 3 both contain a bridging disulfido ligand lying perpendicular to the Mo-Mn bond. The bond distances are Mo-Mn = 2.8421(10) and 2.8914(5) A and S-S = 2.042(2) and 1.9973(10) A for 2 and 3, respectively. A tetranuclear metal side product CpMoMn(3)(CO)(13)(mu3-S)(mu4-S) (4) was also isolated from the reaction of 1 with [CpMo(CO)(3)](2). Compounds 2 and 3 react with CO to yield the dithiocarbonato complexes CpMoMn(CO)(5)[mu-SC(=O)S] (5) and Cp*MoMn(CO)(5)[mu-SC(=O)S] (6) by insertion of CO into the S-S bond. Similarly, tert-butylisocyanide was inserted into the S-S bond of 2 and 3 to yield the complexes CpMoMn(CO)(5)[mu-S(C=NBu(t))S] (7) and Cp*MoMn(CO)(5)[mu-S(C=NBu(t))S] (8), respectively. Ethylene and dimethylacetylene dicarboxylate also inserted into the S-S bond of 2 and 3 at room temperature to yield the ethanedithiolato ligand bridged complexes CpMoMn(CO)(5)(mu-SCH(2)CH(2)S) (9), Cp*MoMn(CO)(5)(mu-SCH(2)CH(2)S) (10), CpMoMn(CO)(5)[mu-SC(CO(2)Me)=C(CO(2)Me)S] (11), and Cp*MoMn(CO)(5)[mu-SC(CO(2)Me)=C(CO(2)Me)S] (12). Allene was found to insert into the S-S bond of 2 by using one of its two double bonds to yield the complex CpMoMn(CO)(5)[mu-SCH(2)C(=CH(2))S] (13). The molecular structures of the new complexes 2-7 and 9-13 were established by single-crystal X-ray diffraction analyses. 相似文献
126.
On the Criteria of Instability for Electrochemical Systems 总被引:7,自引:0,他引:7
Both cyclic-voltammetry-based and impedance-based experimental criteria that have been developed recently for the oscillatory electrochemical systems are critically appraised with two typical categories of oscillators.Consistent conclusions can be drawn by the two criteria for the category of oscillators that involve the coupling of charge transfer mainly with surface steps(e.g.ad-and desorption)such as in the electrooxidation of C1 organic molecules.Whereas,impedance-based criterion is not applicable to the category of oscillators that involve the coupling of charge transfer mainly with mass transfer(e.g.diffusion and convection) such as in the Fe(CN)6^3- reduction accompanying periodic hydrogen evolution.The reason is that the negative impedance cannot include the feedback information of convection mass transfer induced by the hydrogen evolution.However,both positive and negative nonlinear feedbacks,i.e., the diffusion-limited depletion and convection-enhanced replenishment of the Fe(CN)6^3- surface concentration,that coexist between the bistability,i.e.,Fe(CN)6^3- reduction with and without hydrogen evolution at lower and higher potential sides respectively,are all reflected in the crossed cyclic voltammogram(CCV).It can be concluded that the voltammetry-based criterion(in time domain)is more intuitive,less time-consuming and has a wider range of applications than the impedancebased one (in frequency domain). 相似文献
127.
本文借助李对称分析研究了一类自伴随的Lubrication方程,此类方程可用来描述液体薄膜动力学行为.基于非奇异的局域守恒律乘子和李对称方法,我们系统地推导出了此类方程的局域守恒律,非局域相关系统,李对称和一些有趣的精确解.此模型的非局域相关系统在本文中被首次研究,可用于寻找原方程更丰富的解空间.此外,基于局域守恒律和变分原则,我们推导出原方程的四类拉格朗日函数. 相似文献
128.
以一个损失厌恶销售商与一个损失中性供应商组成的两级供应链为背景,利用期望损失厌恶理论对销售商在期权契约下的最优采购策略进行了研究,并证明了期望损失厌恶理论能有效克服传统基于前景理论的研究中因参考点外生且固定假设带来的弊端。在此基础上,进一步给出了供销双方在期权契约下实现协调共赢的条件,分析了销售商损失厌恶程度,期权契约价格等参数对供应链协调共赢机制的影响。结果显示:销售商的损失厌恶偏好并不会改变权利金分配整体供应链利润的作用,但会增强销售商分享收益的能力,改变供销双方利润或效用水平对权利金,产品销售价格和生产成本的敏感程度,且较高的损失厌恶偏好还会阻碍供销双方协调共赢目标的达成。 相似文献
129.
130.