全文获取类型
收费全文 | 4854篇 |
免费 | 231篇 |
国内免费 | 31篇 |
专业分类
化学 | 3462篇 |
晶体学 | 55篇 |
力学 | 156篇 |
数学 | 298篇 |
物理学 | 1145篇 |
出版年
2024年 | 6篇 |
2023年 | 40篇 |
2022年 | 105篇 |
2021年 | 105篇 |
2020年 | 89篇 |
2019年 | 115篇 |
2018年 | 85篇 |
2017年 | 76篇 |
2016年 | 173篇 |
2015年 | 179篇 |
2014年 | 200篇 |
2013年 | 319篇 |
2012年 | 386篇 |
2011年 | 431篇 |
2010年 | 260篇 |
2009年 | 232篇 |
2008年 | 357篇 |
2007年 | 309篇 |
2006年 | 293篇 |
2005年 | 275篇 |
2004年 | 204篇 |
2003年 | 180篇 |
2002年 | 187篇 |
2001年 | 85篇 |
2000年 | 89篇 |
1999年 | 45篇 |
1998年 | 39篇 |
1997年 | 27篇 |
1996年 | 39篇 |
1995年 | 41篇 |
1994年 | 21篇 |
1993年 | 21篇 |
1992年 | 13篇 |
1991年 | 18篇 |
1990年 | 20篇 |
1989年 | 8篇 |
1988年 | 6篇 |
1987年 | 5篇 |
1986年 | 3篇 |
1983年 | 3篇 |
1982年 | 2篇 |
1981年 | 3篇 |
1979年 | 3篇 |
1976年 | 3篇 |
1974年 | 4篇 |
1971年 | 1篇 |
1970年 | 1篇 |
1968年 | 3篇 |
1963年 | 1篇 |
1961年 | 1篇 |
排序方式: 共有5116条查询结果,搜索用时 0 毫秒
81.
Takehiko Yamato Fumika Kitajima Jeong Tae Gil 《Journal of inclusion phenomena and macrocyclic chemistry》2005,53(3):257-262
The lower rim functionalized hexahomotrioxacalix[3]arene triamide 4 with cone-conformation was synthesized from triol 1 by a stepwise reaction. The different extractability for alkali metal ions, transition metal ions, and alkyl ammonium ions from water into dichloromethane is discussed. Due to the strong intramolecular hydrogen bonding between the neighboring NH and CO groups in triamide 4, its affinity to metal cations was weakened. Triamide 4 shows a single selectivity to n-BuNH3+. The anion complexation of triamide 4 was also studied by 1H NMR titration experiments. Triamide 4 binds halides through the intermolecular hydrogen bonding among the NH hydrogens of amide in a 1:1 fashion in CDCl3. The association constants calculated from these changes in chemical shifts of the amide protons are Ka = 223 M−1 for Cl− and Ka = 71.7 M−1 for Br−. Triamide 4 shows a preference for Cl− complexation than Br− complexation. 相似文献
82.
Choi YA Lee DJ Lim HK Jeong JH Sonn JK Kang SS Baek SH 《Experimental & molecular medicine》2004,36(3):226-232
IL-1beta is known promote cyclooxygenase-2 (COX- 2) and matrix metalloproteinase-2 (MMP-2) expression. This study focuses on the characterization of the signaling cascade associated with IL-1beta-induced matrix metalloproteinase-2 (MMP-2) regulation in human chondrocytes. The decrease in collagen levels in the conditioned media was prevented by a broad spectrum MMP inhibitor, suggesting that IL-1beta promotes the proteolytic process leading to MMP-2 activation. IL-1beta-related MMP-2 expression was found to be dependent on prostaglandin E2 (PGE2) production. In addition, the induction of COX-2 and MMP-2 was inhibited by the pretreatment of chondrocytes with a SB203580 or Ro 31-8220, indicating the involvement of protein kinase C (PKC) or p38 mitogen-activated protein kinase (MAPK). However, there is no cross-talk between PKC and p38 MAPK in the IL-1beta-induced MMP-2 activation. Taken together, these results demonstrated that IL-1beta induces MMP-2 expression through the PGE2-dependent mechanism in human chondrocytes. 相似文献
83.
Jew SS Jeong BS Lee JH Yoo MS Lee YJ Park BS Kim MG Park HG 《The Journal of organic chemistry》2003,68(11):4514-4516
Systematic investigations to develop an efficient enantioselective synthetic method for alpha-alkyl-alanine by catalytic phase-transfer alkylation were performed. The alkylation of 2-naphthyl aldimine tert-butyl ester, 1E, with RbOH and O(9)-allyl-N-2',3',4'-trifluorobenzylhydrocinchonidinium bromide, 6, at -35 degrees C showed the highest enantioselectivities, up to 96% ee. 相似文献
84.
Chan Sik Cho Na Young Lee Tae‐Jeong Kim Sang Chul Shim 《Journal of heterocyclic chemistry》2004,41(3):423-429
Nitroarenes are reductively cyclized with an array of tetraalkylammonium halides and trialkylarnmonium chlorides in the presence of a catalytic amount of a ruthenium catalyst along with tin(II) chloride dihydrate at 180° to afford the corresponding quinolines in moderate to good yields. The addition of tin(II) chloride dihydrate is necessary for the effective formation of quinolines and toluene is the solvent of choice. A reaction pathway involving initial reduction of nitroarenes to anilines and conversion of alkylammonium halides to alkylamines, alkyl group transfer from alkylamines to anilines to form an imine, dimerization of imine, and heteroannulation is proposed for this catalytic process. 相似文献
85.
Mixing enhancement has drawn great attention from designers of micromixers, since the flow in a microchannel is usually characterized by a low Reynolds number (Re) which makes the mixing quite a difficult task to accomplish. In this paper, a novel integrated efficient micromixer named serpentine laminating micromixer (SLM) has been designed, simulated, fabricated and fully characterized. In the SLM, a high level of efficient mixing can be achieved by combining two general chaotic mixing mechanisms: splitting/recombination and chaotic advection. The splitting and recombination (in other terms, lamination) mechanism is obtained by the successive arrangement of "F"-shape mixing units in two layers. The advection is induced by the overall three-dimensional serpentine path of the microchannel. The SLM was realized by SU-8 photolithography, nickel electroplating, injection molding and thermal bonding. Mixing performance of the SLM was fully characterized numerically and experimentally. The numerical mixing simulations show that the advection acts favorably to realize the ideal vertical lamination of fluid flow. The mixing experiments based on an average mixing color intensity change of phenolphthalein show a high level of mixing performance was obtained with the SLM. Numerical and experimental results confirm that efficient mixing is successfully achieved from the SLM over the wide range of Re. Due to the simple and mass producible geometry of the efficient micromixer, SLM proposed in this study, the SLM can be easily applied to integrated microfluidic systems, such as micro-total-analysis-systems or lab-on-a-chip systems. 相似文献
86.
Five metallocycles 1 a-e have been self-assembled from S-shaped bispyridyl ligands 2 a-e and a palladium complex, [Pd(dppp)(OTf)(2)] (dppp=1,3-bis(diphenylphosphanyl)propane), and have been characterized by elemental analysis and various spectroscopic methods including (1)H NMR spectroscopy and electrospray ionization (ESI) mass spectrometry. These metallocycles all are monocyclic compounds, but can fold to generate two binding domains bearing hydrogen-bonding sites based on pyridine-2,6-dicarboxamide units. The binding properties of the metallocycles with N,N,N',N'-tetramethylterephthalamide (G) have been probed by means of ESI mass spectrometry and (1)H NMR spectroscopy. The results both in the gas phase and in solution are consistent with the fact that the metallocycles accommodate two molecules of the guest G. Thus, the ESI mass spectra clearly show fragments corresponding to the 1:2 complexes in all cases. (1)H NMR studies on 1 a and G support the formation of a 1:2 complex in solution; the titration curves are nicely fitted to a 1:2 binding isotherm, but not to a 1:1 binding isotherm. In addition, a Job plot also suggests a 1:2 binding mode between 1 a and G, showing maximum complexation at approximately 0.33 mol fraction of the metallocycle 1 a in CDCl(3). The binding constants K(1) and K(2) are calculated to be 1600 and 1400 M(-1) (+/-10 %), respectively, at 25 degrees C in CDCl(3), indicative of positively cooperative binding. This positive cooperativity was confirmed by the Hill equation, affording a Hill coefficient of n = 1.6. Owing to insufficient solubility in CDCl(3), for comparison purposes the binding properties of the metallocycles 1 b-e were investigated in a more polar medium, 3 % CD(3)CN/CDCl(3). (1)H NMR titrations revealed that the metallocycles all bind two molecules of the guest G with Hill coefficients ranging from 1.4 to 1.8. This positive cooperativity may be attributed to a structural reorganization of the second binding cavity when the first guest binds to either one of the subcavities present in the metallocycles. 相似文献
87.
Nak Bae Kim Young Suk Kim Joon Kon Kim Keung Shik Park 《Journal of Radioanalytical and Nuclear Chemistry》1988,125(2):403-417
A Peak Identification and Activity Determination (PIAD) computer program has been developed. A new concept of peak significance is introduced and a great change has been made to the currently used associated gamma lines technique in calculating the confidence index; confidence factor is also given to the gamma line of a nuclide that is not seen in the spectrum. The program is written in Fortran IV under the operating system of RSX-11M. 相似文献
88.
Yong-Chul Jeong 《Tetrahedron letters》2004,45(50):9249-9252
Sterically hindered chiral Schiff base ligands 4a-d were prepared from an aldehyde derived from BINOL. The vanadium complexes of the ligands catalyze an efficient, enantioselective H2O2-promoted sulfoxidation of alkyl aryl sulfides, and enantioselectivities as high as 98-99% ee are observed in the sulfoxidation of benzyl aryl sulfides. 相似文献
89.
90.
Jang-Woo Kim Frank S. Davis Liang-Fu Huang Salma M. Abdelaal Subhash P. Upadhyaya Jae Jeong Lee Ludwig Bauer 《Journal of heterocyclic chemistry》1996,33(1):65-74
Aryl 2-[(2-imidazolyl)ethyl or 3-(2-imidazolyl)propyl]ketones were ketalized by glycerol or 3-mercapto-1,2-propanediol in boiling benzene in the presence of 4-toluenesulfonic acid to provide the title compounds. The aryl substituents are 4-chloro-, 4-bromo-, 4-fluoro-, or 2,4-dichlorophenyl. While aryl (2-imidazolyl)methyl ketones condensed with glycerol to form cis- and trans-{2-aryl-2-[(2-imidazolyl)methyl]-4-(hydroxymethyl)}-1,3-dioxolanes, related condensations with 3-mercapto-1,2-propanediol, under similar, or even more stringent reaction conditions, produced no 1,3-oxathiolane analogs, with the starting ketones being recovered. Separation and structure determination of these racemic cis and trans isomeric products are described. The structure of these stereoisomers was established by means of 1H and 13C nmr correlation and nOe experiments. Selective methylation of the N-unsubstituted 2-imidazolyl alcohols with one equivalent sodium hydride and methyl iodide provided the corresponding N-methyl alcohols in excellent yields. With excess benzoyl chloride, N-unsubstituted 2-imidazolyl alcohols were initially converted to O, N-dibenzoates from which the N-benzoyl group was easily cleaved by ammonium hydroxide in ethanol to provide benzoate esters. 相似文献