全文获取类型
收费全文 | 10030篇 |
免费 | 1990篇 |
国内免费 | 1091篇 |
专业分类
化学 | 8051篇 |
晶体学 | 43篇 |
力学 | 868篇 |
综合类 | 49篇 |
数学 | 336篇 |
物理学 | 3764篇 |
出版年
2024年 | 20篇 |
2023年 | 123篇 |
2022年 | 218篇 |
2021年 | 249篇 |
2020年 | 340篇 |
2019年 | 382篇 |
2018年 | 425篇 |
2017年 | 393篇 |
2016年 | 409篇 |
2015年 | 519篇 |
2014年 | 741篇 |
2013年 | 914篇 |
2012年 | 686篇 |
2011年 | 818篇 |
2010年 | 639篇 |
2009年 | 707篇 |
2008年 | 683篇 |
2007年 | 626篇 |
2006年 | 634篇 |
2005年 | 575篇 |
2004年 | 530篇 |
2003年 | 449篇 |
2002年 | 299篇 |
2001年 | 212篇 |
2000年 | 221篇 |
1999年 | 168篇 |
1998年 | 164篇 |
1997年 | 148篇 |
1996年 | 119篇 |
1995年 | 136篇 |
1994年 | 100篇 |
1993年 | 79篇 |
1992年 | 71篇 |
1991年 | 30篇 |
1990年 | 46篇 |
1989年 | 33篇 |
1988年 | 26篇 |
1987年 | 28篇 |
1986年 | 18篇 |
1985年 | 16篇 |
1984年 | 22篇 |
1983年 | 6篇 |
1982年 | 16篇 |
1981年 | 10篇 |
1980年 | 10篇 |
1979年 | 13篇 |
1977年 | 8篇 |
1976年 | 5篇 |
1973年 | 5篇 |
1957年 | 6篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
71.
The use of allyl protecting group mediated intramolecular aglycon delivery (IAD) as a strategy for intramolecular glycosylation has been extended to allow the stereoselective synthesis of α-glucofuranosides and β-rhamnopyranosides, in a totally stereoselective fashion. The efficiency of intramolecular glycosylation is dependent on the protecting group pattern of the glycosyl donor, and on the steric bulk of the glycosyl acceptor. 相似文献
72.
氧鎓盐类化合物因具有较强的亲电性,在有机合成[1]及电照相体系[2]中存在着广泛的应用前景.由于它们还表现出较强的荧光发射能力[3],因而在作为激光工作材料[4,5]方面也受到重视.正因如此,这类化合物的光物理和光谱特性引起了许多化学家的兴趣.氧钠盐化合物溶液的荧 相似文献
73.
Yuhua Zhang 《Tetrahedron letters》2004,45(41):7581-7584
Under microwave conditions, tetrahydrofuran (THF), tetrahydropyran and 1,4-dioxane are added directly onto alkynes and generated various vinyl cycloethers. 相似文献
74.
Summary The complete error potential is used for the study of the correlation of molecules. The correlation can be seen as a relaxation of the electrons and a relaxation of the nuclei. From the Fermi sea, the electronic relaxation gives rise to a partial excitation of each orbital which collectively generates a linear, a surface or a volume pressure; the resulting forces acting on the nuclei are defined in a general theory of the intramolecular forces. H3, H
3
+
, the diatoms and the hydrid of the first nine elements are taken as examples. 相似文献
75.
A. V. Larin D. N. Trubnikov D. P. Vercauteren 《International journal of quantum chemistry》2003,92(1):71-84
Three hydrated aluminosilicate frameworks—LiABW, NaNAT, and BaEDI—are partly optimized with the periodic Hartree–Fock CRYSTAL95 code. In particular, we optimized the positions of the adsorbed water molecules including the positions of the framework cations (ABW, NAT) or part of the framework atomic positions (ABW). This allowed us to compare cation–water clusters in the gas and adsorbed states and discuss the influence of hydrogen bonding to the framework oxygen atoms or to the neighbor water molecules on the atomic properties (quadrupole coupling constant, anisotropy of electric field gradient) of the adsorbed water molecules. The LiBIK structure obtained from X‐ray diffraction is also considered to illustrate the hydrogen bonds occurring between adsorbed water molecules. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2003 相似文献
76.
LaZrO催化剂结构相变对甲烷氧化偶联反应性能的影响 《燃料化学学报》2003,48(8):949-959
采用共沉淀法并通过改变焙烧温度制备了一系列具有不同晶相结构的La2Zr2O7催化剂,在微型固定床反应器上评价其甲烷氧化偶联反应性能,并利用XRD、Raman、CO2-TPD、XPS等表征手段,探究催化剂的物相结构、表面碱性以及表面氧物种的变化规律。结果表明,随着焙烧温度从700℃逐渐升高到1200℃,La2Zr2O7催化剂结晶度不断提高,晶相发生明显变化,从无定形结构逐渐向缺陷萤石结构过渡,最终转变成烧绿石结构。焙烧温度提高促使La2Zr2O7晶相转变过程中,催化剂表面的碱性强度减弱,中等碱性位数量以及具有催化活性的表面氧物种O22-和O2-的相对含量不断减少,致使催化剂的CH4转化率和C2+选择性不断降低。其中,无定形LZO-CP-700催化剂表现出最佳的甲烷氧化偶联反应性能。 相似文献
77.
硼酸酯偶联剂的合成与表征 总被引:11,自引:0,他引:11
通过分子结构设计,合成了一种氮一硼内配位结构的硼酸酯偶联剂,解决了硼酸酯水解稳定性差的问题,同时分子结构中含有氨基、丁氧基等活性基团。用傅立叶变换红外光谱对硼酸酯进行了结构表征,讨论了原料配比、合成工艺等对硼酸酯收率及反应速率的影响,并通过实验确定了最佳配方及工艺。对硼酸酯的物理性能、溶解性、水解稳定性及对硼酸铝晶须的表面处理效果进行了表征。结果表明:合成的硼酸酯偶联剂由于具有氮-硼内配位作用,表现出优良的水解稳定性,并且硼酸酯偶联剂对硼酸铝晶须具有良好的表面改性效果。 相似文献
78.
Frédéric Cadoret 《Tetrahedron letters》2007,48(31):5491-5495
Competition experiments were performed by adding pre-formed solutions of diisopropyloxy(η2-cyclopentene)titanium in diethyl ether to various mixtures of unsaturated compounds at low temperature, establishing the following reactivity scale: aldehyde > nitrile > ketone > terminal alkyne > internal alkyne > terminal alkene > ester, carbonate. 相似文献
79.
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
80.
Cl···O intramolecular contacts are analysed here. Hence the Cambridge Structural Database (CSD) search was performed to find
five-membered Cl–C=C–C=O pseudo-rings closed through Cl···O intramolecular contacts. Such rings were analysed and it was found
that some of Cl···O distances are smaller than the corresponding sum of van der Waals radii. Additionally ab initio MP2/6-311++G(d,p)
calculations and AIM analyses were carried out here on 3-chloropropenal and its fluoro derivatives to deepen the nature of
intramolecular Cl···O interactions, some of findings may indicate that they are attractive and stabilizing ones.
This paper is dedicated to Prof. T. M. Krygowski on the occasion of his 70th birthday 相似文献