全文获取类型
收费全文 | 1013篇 |
免费 | 34篇 |
国内免费 | 3篇 |
专业分类
化学 | 775篇 |
晶体学 | 37篇 |
力学 | 24篇 |
数学 | 59篇 |
物理学 | 155篇 |
出版年
2022年 | 15篇 |
2021年 | 19篇 |
2020年 | 9篇 |
2019年 | 17篇 |
2018年 | 30篇 |
2017年 | 14篇 |
2016年 | 17篇 |
2015年 | 29篇 |
2014年 | 21篇 |
2013年 | 72篇 |
2012年 | 55篇 |
2011年 | 64篇 |
2010年 | 34篇 |
2009年 | 33篇 |
2008年 | 47篇 |
2007年 | 68篇 |
2006年 | 49篇 |
2005年 | 44篇 |
2004年 | 32篇 |
2003年 | 25篇 |
2002年 | 43篇 |
2001年 | 24篇 |
2000年 | 18篇 |
1999年 | 10篇 |
1998年 | 12篇 |
1997年 | 14篇 |
1996年 | 12篇 |
1995年 | 8篇 |
1994年 | 12篇 |
1993年 | 9篇 |
1992年 | 20篇 |
1991年 | 13篇 |
1990年 | 12篇 |
1989年 | 14篇 |
1988年 | 4篇 |
1987年 | 8篇 |
1986年 | 10篇 |
1985年 | 6篇 |
1984年 | 18篇 |
1983年 | 15篇 |
1982年 | 7篇 |
1980年 | 6篇 |
1979年 | 3篇 |
1978年 | 6篇 |
1977年 | 8篇 |
1976年 | 7篇 |
1975年 | 9篇 |
1974年 | 6篇 |
1973年 | 4篇 |
1972年 | 4篇 |
排序方式: 共有1050条查询结果,搜索用时 15 毫秒
161.
162.
163.
A new method to synthesize 1,4-naphthoquinone and 9,10-anthraquinone from naphthalene and anthracene functionalized with either –CHO or –COOH groups, using N-bromosuccinimide (NBS) in aqueous N,N-dimethylformamide at 75–80 °C, has been developed. Further, –CN and –CONH2 functionalized naphthalenes and anthracenes can also be transformed into respective para-quinones in a one pot reaction, after successive acid hydrolysis and subsequent reaction with NBS. We believe that the present finding may serve as a valuable alternative to the classical approaches for the synthesis of polycyclic quinones from polyaromatic carbaldehydes through Dakin oxidation followed by further oxidation of the resulting hydroquinone by heavy metal oxides. 相似文献
164.
Natarajan Arumugam Abdulrahman I. Almansour Raju Suresh Kumar Vaiyapuri Subbarayan Periasamy Jegan Athinarayanan Ali A. Alshatwi Periyasami Govindasami Mohammad Altaf J. Carlos Menéndez 《Tetrahedron》2018,74(38):5358-5366
A small library of novel hybrid spiroheterocycles containing spirooxindole, pyrrolidine and indole/imidazole moieties were synthesized with complete regio- and diastereoselectively in good to excellent yields from a three-component process starting from a series of variously substituted (E)-(2-nitrovinyl)benzenes, indoline-2,3-dione derivatives and l-tryptophan or l-histidine in an ionic liquid. The key step of this transformation is a 1,3-dipolar cycloaddition reaction involving a rare class of in situ-generated azomethine ylides derived from aromatic amino acids. The compounds thus synthesized were evaluated for their anticancer activity and were shown to inhibit the proliferation of FaDu cells, a human epithelial cell line isolated from a squamous cell carcinoma of the hypopharynx, via apoptotic cell death. 相似文献
165.
Resendiz MJ Natarajan A Garcia-Garibay MA 《Chemical communications (Cambridge, England)》2008,(2):193-195
A diastereoselective procedure to obtain N-para-methoxybenzyl bis-alpha,alpha'-3-(3-phenyl-2-pyrrolidinone)yl substituted ketones with non-adjacent quaternary stereocenters, DL-2 and meso-3 was followed by a photoinduced, spin-dependent, and diastereoselective decarbonylation to give compounds DL-4 and meso-5, with adjacent all-carbon quaternary stereogenic centers. 相似文献
166.
The cubic transition metal phosphonates [(t)BuPO3M(2-apy)]4 (M= Zn (1), Co (2)), whose core resembles the D4R SBU of zeolites, have been synthesized from a reaction between the corresponding metal acetate, tert-butylphosphonic acid and 2-aminopyridine (2-apy) at room temperature. X-Ray structure determination reveals that the molecules of 1 and 2, which crystallize in the tetragonal I4(1)/a space group with crystallographically imposed 4 symmetry, form a 3-D supramolecular assembly aided by N-H...O hydrogen bonding. When the same reaction was carried out by using a bridging bidentate Lewis base such as 4,4'-bipyridine, insoluble precipitate is obtained for both zinc and cobalt. In the case of other metal salts such as copper, manganese and nickel, however, one-dimensional polymeric compounds such as [M((t)BuPO3H)2(4,4'-bipy)(H2O)2]n (M= Cu (3), Mn (4)), [(Ni(4,4'-bipy)(H2O)4)((t)BuPO3H)2(H2O)]n (5) have been isolated. The solid-state structures of 3-5 have been determined by single crystal X-ray diffraction studies. Compounds 3 and 4 are isostructural and crystallize in the triclinic P1 space group with two phosphonate ligands coordinated to the metal centers in a [1.100] fashion, whereas in the case of compound 5, the polymeric backbone is formed by Ni-4,4'-bipy units and the phosphonate anions show no bonding interaction to the metal. The 1-D polymeric chains of 3-5 organize in the solid-state as 3-D supramolecular assemblies with the aid of extensive hydrogen bonding interaction between coordinated water molecules and P-OH or P=O groups of the phosphonate ligands. 相似文献
167.
A series of Ru(II) and Ru(III) complexes of the types [RuX(CO)(EPh3)2L] (X = H, E = P; X = Cl, E = P or As) and [RuX2(EPh3)2L] (X = Cl, E = P or As; X = Br, E = As, L = monoanion of dehydroacetic acid) have been synthesized in order to explore their biological activities, such as DNA-binding and antibacterial activity. The complexes were characterized by analytical and spectroscopic techniques. The crystal and molecular structure of [RuCl2(AsPh3)2(L)] has been determined by single crystal XRD. The cyclic voltammograms of the complexes in acetonitrile displayed either quasi-reversible or irreversible redox couples based on the metal centre. The ligand, dehydroacetic acid (DHA) and its metal complexes were tested against five pathogenic bacteria. Absorption titration and cyclic voltammetric studies revealed that the complexes interact with Herring Sperm ds DNA through different binding modes to different extents. 相似文献
168.
Quencher-free molecular beacons: a new strategy in fluorescence based nucleic acid analysis 总被引:1,自引:0,他引:1
Molecular beacons (MBs) have been used as viable fluorescent probes in nucleic acid analysis. Many researchers around the world continue to modify the MBs to suit their needs. As a result, a number of nucleic acid probing systems with close resemblance to the MBs are being reported from time to time. Quencher-free molecular beacons (QF-MBs) are a significant modification of the conventional MB; in QF-MBs the quencher part has been eliminated. Despite the absence of the quencher, the QF-MBs can identify specific target DNA. They can also be used in SNP typing and in real-time PCR analysis for quantification of DNAs. The design, factors behind functioning and applications of different types of QF-MBs and closely related quencher-free nucleic acid probing systems (QF-NAPs) have been described in this tutorial review. 相似文献
169.
A crystalline triply bridged molecular gyroscope has been prepared and analyzed by single-crystal X-ray diffraction. A convergent synthetic strategy was developed to control the direction of the three bridges, from the preferred two zonal and one meridional arrangement of a one-step cylclization process to the directed three meridional bridges achieved by a north-south desymmetrization. 相似文献
170.
Thomas M. Cooper Lalgudi V. Natarajan Cory G. Miller 《Photochemistry and photobiology》1999,69(2):173-176
Abstract— In order to develop new systems that couple photochromism with molecular conformation change, a series of spiropyrans having different ring substituents were attached to poly(L-glutamic acid). The polypeptides were dissolved in hexafluoroisopropanol and dark adapted so that the dye was in the merocyanine form. Following adaptation by white light and dye photoconversion from the merocyanine to spiropyran forms, polypeptide dark-adaptation kinetics were monitored by circular dichroism (CD) and dye dark adaptation was monitored by UV/ visible. Light adaptation caused a light-induced coil-to-helix transition, with dark adaptation resulting in relaxation back to the coil. The dark-adaptation rate constant measured by UV/visible was equal to that measured by CD, demonstrating close coupling between dye state and polypeptide conformation. By varying the substituents on the spiropyran ring, dark-adaptation half lives were varied from less than a minute to 2 h, representing nearly three orders of magnitude. 相似文献