全文获取类型
收费全文 | 1541篇 |
免费 | 46篇 |
国内免费 | 3篇 |
专业分类
化学 | 1265篇 |
晶体学 | 15篇 |
力学 | 18篇 |
数学 | 101篇 |
物理学 | 175篇 |
综合类 | 16篇 |
出版年
2023年 | 5篇 |
2021年 | 7篇 |
2020年 | 8篇 |
2019年 | 18篇 |
2018年 | 20篇 |
2017年 | 7篇 |
2016年 | 36篇 |
2015年 | 31篇 |
2014年 | 41篇 |
2013年 | 76篇 |
2012年 | 70篇 |
2011年 | 86篇 |
2010年 | 56篇 |
2009年 | 33篇 |
2008年 | 82篇 |
2007年 | 66篇 |
2006年 | 82篇 |
2005年 | 70篇 |
2004年 | 75篇 |
2003年 | 94篇 |
2002年 | 78篇 |
2001年 | 22篇 |
2000年 | 54篇 |
1999年 | 24篇 |
1998年 | 18篇 |
1997年 | 24篇 |
1996年 | 27篇 |
1995年 | 23篇 |
1994年 | 22篇 |
1993年 | 21篇 |
1992年 | 20篇 |
1991年 | 18篇 |
1990年 | 15篇 |
1989年 | 7篇 |
1988年 | 16篇 |
1987年 | 5篇 |
1986年 | 5篇 |
1985年 | 19篇 |
1984年 | 22篇 |
1983年 | 9篇 |
1982年 | 20篇 |
1981年 | 22篇 |
1980年 | 24篇 |
1979年 | 25篇 |
1978年 | 22篇 |
1977年 | 12篇 |
1976年 | 13篇 |
1974年 | 6篇 |
1973年 | 7篇 |
1968年 | 5篇 |
排序方式: 共有1590条查询结果,搜索用时 15 毫秒
111.
Cao B Wakahara T Tsuchiya T Kondo M Maeda Y Aminur Rahman GM Akasaka T Kobayashi K Nagase S Yamamoto K 《Journal of the American Chemical Society》2004,126(30):9164-9165
A new metallofullerene, La2@C78, has been synthesized by DC arc discharge method, isolated by high-performance liquid chromatography, and characterized by laser desorption time-of-flight mass spectrometry, UV-vis-NIR absorption, differential pulse voltammetry, 13C NMR spectroscopy, and theoretical calculations. The La2@C78/CS2 solution is dark violet and presents several characteristic absorption features at 647, 561, 533, and 386 nm, with an onset around 1000 nm. With respect to empty D3-C78, the capability of La2@C78 as an electron acceptor or donor is stronger. Addition of 1,1,2,2-tetrakis(2,4,6-trimethylphenyl)-1,2-disirane to La2@C78 photochemically, as well as thermally, affords bis- and mono-adducts. Theoretical studies and 13C NMR spectroscopic analysis of La2@C78 indicate that it possesses a D3h-C78 cage (78:5). 相似文献
112.
A simple method for the diastereoselective synthesis of racemic 1,2-diol mediated by low-valence niobium generated in situ is described. A 1,4-dioxane-toluene solvent system was found to be essential to achieve higher selectivities and to prevent other reactions of pinacols, such as deoxygenation and acetal formation. Aromatic aldehydes and ketones were converted to the corresponding pinacols with up to 97 and 85% de, respectively. 相似文献
113.
Harada T Ikeda S Hashimoto F Sakata T Ikeue K Torimoto T Matsumura M 《Langmuir : the ACS journal of surfaces and colloids》2010,26(22):17720-17725
A core-shell composite consisting of a palladium (Pd) nanoparticle and a hollow carbon shell (Pd@hmC) was employed as a catalyst for aerobic oxidation of various alcohols. The core-shell structure was synthesized by consecutive coatings of Pd nanoparticles with siliceous and carbon layers followed by removal of the intermediate siliceous layer. Structural characterizations using TEM and N(2) adsorption-desorption measurements revealed that Pd@hmC thus-obtained was composed of a Pd nanoparticle core of 3-6 nm in diameter and a hollow carbon shell with well-developed mesopore (ca. 2.5 nm in diameter) and micropore (ca. 0.4-0.8 nm in diameter) systems. When compared to some Pd-supported carbons, Pd@hmC showed a high level of catalytic activity for oxidation of benzyl alcohol into benzaldehyde using atmospheric pressure of O(2) as an oxidant. The Pd@hmC composite also exhibited a high level of catalytic activity for aerobic oxidations of other primary benzylic and allylic alcohols into corresponding aldehydes. The presence of a well-developed pore system in the lateral carbon shell enabled efficient diffusion of both substrates and products to reach the central Pd nanoparticles, leading to such high catalytic activities. This core-shell structure also provided high thermal stability of Pd nanoparticles toward coalescence and/or aggregation due to the physical isolation of each Pd nanoparticle from neighboring particles by the carbon shell: this specific property of Pd@hmC resulted in possible regeneration of catalytic activity for these aerobic oxidations by a high-temperature heat treatment of the sample recovered after catalytic reactions. 相似文献
114.
115.
Yutaka Maeda Prof. Akiko Sagara Masahiro Hashimoto Yuya Hirashima Katsuya Sode Tadashi Hasegawa Prof. Makoto Kanda Midori O. Ishitsuka Dr. Takahiro Tsuchiya Dr. Takeshi Akasaka Prof. Toshiya Okazaki Prof. Hiromichi Kataura Prof. Jing Lu Prof. Shigeru Nagase Prof. Seiji Takeuchi 《Chemphyschem》2009,10(6):926-930
Reversible and non‐bonding interaction between SWNTs and ODCB is observed from the analyses of visible near‐infrared absorption data and Raman spectroscopies (see spectra). The solvent effect on SWNTs effectively controls the electronic structure of SWNTs under homogeneous conditions.
116.
On-line sample preconcentration by a dynamic pH junction in conjunction with multiplexed capillary electrophoresis (CE) and UV detection represents a sensitive and high-throughput format for future metabolomic research, such as purine analysis. The optimization of purine focusing can be rapidly assessed by systematically altering the sample matrix properties, such as the buffer co-ion, pH and ionic strength using a 96-capillary array format. This method permits focusing of large sample injection volumes, resulting in over a 50-fold improvement in the concentration sensitivity. The limit of detection (S/N = 3) for purine metabolites was less than 8.0 x 10(-8) M under optimum conditions when using UV absorbance. Dynamic pH junction multiplexed CE demonstrated excellent linearity over a hundred-fold concentration range, as well as low inter-capillary precision in terms of normalized migration times and peak areas. The potential for clinically relevant high-throughput analyses of micromolar amounts of purine metabolites in urine was also demonstrated. 相似文献
117.
118.
119.
The respective structures and stabilities of imidazole-imidazole, benzene-imidazole, and benzene-indole dimers have been investigated using different DFT-D functional, MP2, CCSD(T), and SAPT levels of theory with a medium basis set. Comparative analysis of binding energies and structural parameters of the dimers points to a preference for stacking contact or hydrogen bond in an imidazole-imidazole dimer. In contrast, a T-shaped configuration with H-π interaction is maximally advantageous for benzene-imidazole and benzene-indole dimers. High-level ab initio calculations at the CCSD(T)/CBS and DFT-SAPT levels show that classical hydrogen-bonded tilted imidazole-imidazole dimer is a global minimum structure and that it has high electrostatic energy. However, for benzene-imidazole and benzene-indole dimers, the global minimum (N-H···π) structure has high electrostatic energy as well as dispersion energy. 相似文献
120.
Matsumori N Yamaji N Matsuoka S Oishi T Murata M 《Journal of the American Chemical Society》2002,124(16):4180-4181
Polyenemacrolides such as amphotericin B (AmB) were thought to assemble together and form an ion channel across plasma membranes. Their antimicrobial activity has been accounted for by this assemblage, whose stability and activity are dependent on sterol constituents of lipid bilayer membranes. The structure of this channel-like assemblage formed in biomembranes has been a target of extensive investigations for a long time. For the first step to this goal, we prepared several AmB dimers with various linkers and tested for their channel-forming activity. Among these, AmB dimers that bore an aminoalkyl-dicarboxylate tether covalently linked between amino groups of AmB showed potent hemolytic activity. Furthermore, K+ influx actions monitored by measuring the pH of the liposome lumen by 31P NMR revealed that the dimers formed the molecular assemblage similar to that of AmB in phospholipid membrane. Judging from changes in 31P NMR spectra, the dimers appeared to induce "all-or-none"-type ion flux across the liposome membrane in the presence of ergosterol, which suggested that the ion channel formed by ergosterol/dimer is similar to that of AmB. With these data in hand, we are now trying to elucidate the structure of the ion-channel complex by making the labeled conjugates of AmB for NMR measurements. 相似文献