全文获取类型
收费全文 | 2627篇 |
免费 | 101篇 |
国内免费 | 6篇 |
专业分类
化学 | 2168篇 |
晶体学 | 16篇 |
力学 | 19篇 |
数学 | 136篇 |
物理学 | 395篇 |
出版年
2023年 | 20篇 |
2022年 | 19篇 |
2021年 | 33篇 |
2020年 | 58篇 |
2019年 | 46篇 |
2018年 | 38篇 |
2017年 | 25篇 |
2016年 | 61篇 |
2015年 | 71篇 |
2014年 | 81篇 |
2013年 | 126篇 |
2012年 | 189篇 |
2011年 | 191篇 |
2010年 | 102篇 |
2009年 | 118篇 |
2008年 | 207篇 |
2007年 | 200篇 |
2006年 | 195篇 |
2005年 | 182篇 |
2004年 | 154篇 |
2003年 | 96篇 |
2002年 | 76篇 |
2001年 | 42篇 |
2000年 | 28篇 |
1999年 | 16篇 |
1998年 | 21篇 |
1997年 | 13篇 |
1996年 | 17篇 |
1995年 | 11篇 |
1994年 | 14篇 |
1993年 | 10篇 |
1992年 | 16篇 |
1991年 | 12篇 |
1990年 | 19篇 |
1989年 | 18篇 |
1988年 | 13篇 |
1987年 | 13篇 |
1985年 | 19篇 |
1984年 | 22篇 |
1983年 | 10篇 |
1982年 | 14篇 |
1981年 | 15篇 |
1980年 | 8篇 |
1979年 | 11篇 |
1978年 | 16篇 |
1977年 | 10篇 |
1976年 | 7篇 |
1975年 | 11篇 |
1974年 | 8篇 |
1973年 | 6篇 |
排序方式: 共有2734条查询结果,搜索用时 0 毫秒
71.
Vibrational Raman spectra of C=C stretching modes of ethylene derivates (cis-C(2)H(2)Cl(2), cis-stilbene, and trans-stilbene) were measured in supercritical fluids along an isotherm as functions of their densities. The substitution effect of the Raman shift is so significant that a difference among three solutes can be 20 times and is observed similarly in dipolar (CHF(3)) and non-dipolar (CO(2)) fluids. In particular, the shifts of trans-stilbene were enormously large among all systems for studies of vibrational spectroscopies of supercritical fluids and were equivalent to those of typical hydrogen-bonded fluids. Such large shifts arising from the significant attractive energy between solute and solvent molecules were attributed to a site-selective solvation around a phenyl group, which was driven by a dispersion force in the absence of steric hindrance. We found that the absence of steric hindrance causes the significant local density augmentation. To the best of our knowledge, Raman experiments and their theoretical analysis are the first ones quantifying how the difference of steric hindrance produces solvation structures in solution as well as supercritical solutions. 相似文献
72.
pi-Allyl-nickel complexes initiated addition polymerisation of 2-phenyl-1-methylenecyclopropane to give a polymer with three-membered rings; the formed polymer showed a high Tg and negligible thermal decomposition up to 300 degrees C. 相似文献
73.
Yoshimasa Fukazawa Satoshi Harada Akira Inai Toshiya Okajima 《Tetrahedron letters》1993,34(52):8493-8496
The title compound (2) has been synthesized, the structure and the physical properties of which are investigated by X-ray, spectroscopic analyses, and MO calculations. There exists charge transfer (CT) interaction between the tropylium ion and the facing phenyl ring. From the pKR+ value of 2, it can be clear that the cation 2 is stabilized by the CT interaction. In spite of the presence of bond weakening σ-π orbital mixing, the cation 2 withstands retro[4+4]type bond cleavage, which is quite interesting when compared to a facile cleavage for the congener with anthracene photodimer type structure. 相似文献
74.
Murahashi S Imada Y Kawakami T Harada K Yonemushi Y Tomita N 《Journal of the American Chemical Society》2002,124(12):2888-2889
A chiral titanium complex, Ti(O-i-Pr)(4)/BINOL/tert-butylcatechol, catalyzes enantioselective addition reaction of ketene silyl acetals to nitrones to give optically active beta-amino acid derivatives which are biologically active compounds and useful synthetic intermediates of natural products and pharmaceuticals such as beta-lactam antibiotics. The combined process of catalytic oxidation of secondary amines and enantioselective carbon-carbon bond formation of nitrones thus obtained with ketene silyl acetals provides a useful two-step method for the synthesis of optically active beta-amino acid derivatives and related nitrogen compounds. 相似文献
75.
76.
Synthesis and characterization of 6-O-acyl-2-O-alpha-D-glucopyranosyl-L-ascorbic acids with a branched-acyl chain 总被引:3,自引:0,他引:3
We previously reported the chemical synthesis of a series of novel monoacylated vitamin C derivatives, 6-O-acyl-2-O-alpha-D-glucopyranosyl-L-ascorbic acids (6-Acyl-AA-2G) possessing a straight-acyl chain of varying length from C(4) to C(18), as effective skin antioxidants. In this paper, we describe branched type of 6-Acyl-AA-2G derivatives (6-bAcyl-AA-2G) synthesized by use of a 2-branched-chain fatty acid anhydride as an acyl donor. The stability of 6-bAcyl-AA-2G in neutral solution was much higher than that of 6-Acyl-AA-2G, while they were susceptible to enzymatic hydrolysis for exerting vitamin C effect. These branched derivatives as well as 6-Acyl-AA-2G increased the radical scavenging activity against 1, 1-diphenyl-2-picrylhydrazyl and the lipophilicity in octanol/water-partitioning systems with increasing length of their acyl group. In addition, the 6-bAcyl-AA-2G derivative with an acyl chain of C(12), 6-bDode-AA-2G had the excellent solubility to various solvents, suggesting easy handling in cosmetic use. These characteristics of 6-bAcyl-AA-2G may be available for skin care application as an effective antioxidant. 相似文献
77.
Abstract In this study, the formation of polyion complex micelles from a pair of poly(L-lysine) homopolymers (P(Lys)) and poly(ethylene glycol)-poly(aspartic acid) block copolymers (PEG-P(Asp)) with varying chain length was demonstrated in aqueous medium. There exists the lower critical chain length in the charged segments of both P(Lys) and PEG-P(Asp) to form stable polyion complex micelles in nanometric scale. The scaled average characteristic line width (ΓTK2) was independent on the detection angles for all combinations, suggesting that the formed polyion complex micelles may have a spherical shape. Furthermore, the transitional diffusion coefficient (DT) had no concentration dependence, indicating the micelle system was free from secondary aggregates (the cluster of micelles). It is of interest that the micellar size was almost constant (ca. 50 nm) regardless of the change in the chain length of the charged segments. Size distribution was extremely narrow, and the values of variance μ2/Γ 2) were always less than 0.1. Laser-Doppler electrophoresis measurements revealed that the polyion complex micelles were electrically neutral, suggesting that the PEG corona surrounding the polyion complex core may contribute to their stable dispersion in an aqueous medium through steric repulsion of the tethered hydrophilic chain, in this case, PEG. This system was considerably stable against the change in ionic strength, and it maintained a constant diameter in the region below 0.4 M NaCl. However, they dissociated under high ionic strength condition as 0.6 M NaCl. The system may have potential utility to include charged peptides and nucleotides in the core, delivering these biologically useful substances into a target site in the body. 相似文献
78.
Synthesis and Magnetic Properties of (Pyrrolidin‐1‐oxyl)–(Nitronyl Nitroxide)/(Iminonitroxide)‐Dyads
Haruki Tsujimoto Shuichi Suzuki Masatoshi Kozaki Daisuke Shiomi Kazunobu Sato Takeji Takui Keiji Okada 《化学:亚洲杂志》2019,14(10):1801-1806
Unlike extensively studied diradicals linked by π‐conjugated systems, only a few studies have investigated weakly coupled diradicals linked by an sp3 carbon atom. Herein, we prepared pyrrolidin‐1‐oxyl–(nitronyl nitroxide)‐dyad 5 and pyrrolidin‐1‐oxyl–iminonitroxide‐dyad 6 . From the observed temperature dependence of the magnetic susceptibility, 5 and 6 were determined to be in singlet ground states with 2Jintra/kB=?35.2 K and ?13.6 K, respectively. From these results and theoretical calculations of related diradicals, the spin‐polarization model counting the small spin density of the sp3 carbon atom could be used as a spin‐prediction model. 相似文献
79.
Yuichiro Nishizawa Shusuke Matsui Kenji Urayama Takuma Kureha Mitsuhiro Shibayama Takayuki Uchihashi Daisuke Suzuki 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(26):8901-8905
Despite the tremendous efforts devoted to the structural analysis of hydrogel microspheres (microgels), many details of their structures remain unclear. Reported in this study is that thermoresponsive poly(N‐isopropyl acrylamide) (pNIPAm)‐based microgels exhibit not only the widely accepted core–shell structures, but also inhomogeneous decanano‐sized non‐thermoresponsive spherical domains within their dense cores, which was revealed by temperature‐controlled high‐speed atomic force microscopy (TC‐HS‐AFM). Based on a series of experiments, it is concluded that the non‐thermoresponsive domains are characteristic for pNIPAm microgels synthesized by precipitation polymerization, and plausible structures for microgels prepared by other polymerization techniques are proposed. 相似文献
80.
Vapor–liquid equilibria and saturated density for carbon dioxide + tetrahydrofuran mixtures at high pressures were measured by the analytical method at the temperatures 298.15 and 313.15 K. The experimental apparatus equipped with three Anton Paar DMA 512S vibrating tube density meters was previously developed for measuring vapor–liquid–liquid equilibrium at high pressures. The equilibrium composition and saturated density of each phase were determined by gas chromatograph and vibrating tube density meters, respectively. The bubble point pressure at the temperature 313.15 K was further measured by the synthetic method. The experimental data were correlated with Soave–Redlich–Kwong (SRK) equation of state and the pseudocubic equation of state. 相似文献