全文获取类型
收费全文 | 7548篇 |
免费 | 269篇 |
国内免费 | 52篇 |
专业分类
化学 | 5612篇 |
晶体学 | 71篇 |
力学 | 191篇 |
综合类 | 1篇 |
数学 | 941篇 |
物理学 | 1053篇 |
出版年
2023年 | 54篇 |
2022年 | 78篇 |
2021年 | 150篇 |
2020年 | 142篇 |
2019年 | 125篇 |
2018年 | 102篇 |
2017年 | 86篇 |
2016年 | 208篇 |
2015年 | 184篇 |
2014年 | 225篇 |
2013年 | 380篇 |
2012年 | 532篇 |
2011年 | 582篇 |
2010年 | 328篇 |
2009年 | 241篇 |
2008年 | 488篇 |
2007年 | 509篇 |
2006年 | 516篇 |
2005年 | 504篇 |
2004年 | 425篇 |
2003年 | 350篇 |
2002年 | 278篇 |
2001年 | 99篇 |
2000年 | 79篇 |
1999年 | 71篇 |
1998年 | 68篇 |
1997年 | 76篇 |
1996年 | 117篇 |
1995年 | 61篇 |
1994年 | 64篇 |
1993年 | 65篇 |
1992年 | 46篇 |
1991年 | 28篇 |
1990年 | 26篇 |
1989年 | 25篇 |
1988年 | 40篇 |
1987年 | 25篇 |
1986年 | 32篇 |
1985年 | 64篇 |
1984年 | 39篇 |
1983年 | 25篇 |
1982年 | 50篇 |
1981年 | 27篇 |
1980年 | 22篇 |
1979年 | 26篇 |
1978年 | 32篇 |
1977年 | 28篇 |
1976年 | 22篇 |
1975年 | 19篇 |
1974年 | 22篇 |
排序方式: 共有7869条查询结果,搜索用时 0 毫秒
11.
Dave J Adams Eric G Hope Peter J Pogorzelec 《Journal of organometallic chemistry》2004,689(8):1413-1417
The hydroformylation of long chain alkenes under fluorous biphase conditions and in neat perfluorocarbon solvents is reviewed. Special emphasis is placed upon the authors' evaluation of the steric and electronic influence of perfluoroalkylation on catalyst activity, regioselectivity and retention in the fluorocarbon phase. 相似文献
12.
13.
14.
Casey Chun Zhou Eric J. Stoner Kent D. Stewart L. Steven Hollis Edmund D. Matayoshi Gregory M. Brill 《Tetrahedron》2004,60(47):10611-10618
Oritavancin is a semi-synthetic glycopeptide antibiotic which is structurally related to vancomycin. When oritavancin bisphosphate is dried in vacuo with heat, a new compound forms. This new compound is stable only in the solid state and reverts to oritavancin in solution. Highly enriched samples of this compound were obtained by preparative HPLC and the structure of this compound was elucidated by using one and two-dimensional (1H and 13C) NMR spectroscopy in conjunction with computer-assisted molecular modeling. It has been determined that oritavancin adopts a conformation similar to that of vancomycin in solution, while the new compound is the unnatural R-AB-biaryl atropisomer of oritavancin. This is the first observation and isolation of an AB-biaryl atropisomer in an intact member of the vancomycin family of glycopeptide antibiotics. 相似文献
15.
Multiple-zero multiple-pole optical filter transfer functions may be implemented more efficiently in an integrated optics architecture if higher order N × M optical couplers are utilized. For example, a coherent ring resonator made from two 3×3 couplers offers some advantages over the three mirror Fabry-Perot etalon, which is its analog. To this end we develop the formalism for obtaining the transfer functions and scattering matrices of ring resonators made from two N × M couplers. We then present a methodology for analyzing serial and parallel systems of N × M optical coupler ring resonators. 相似文献
16.
Sridevi Kaiti Eric Fossum 《Journal of polymer science. Part A, Polymer chemistry》2006,44(6):2099-2106
A thorough study of the polymerization behavior of 4‐fluoro‐4′‐hydroxytriphenyl‐phosphine oxide, 2 , under nucleophilic aromatic substitution reactions has been carried out. The synthesis of 2 was achieved in excellent yields by the reaction of bis(4‐fluorophenyl)phenylphosphine oxide, 1 , with one equivalent of potassium hydroxide in DMSO/water. The structure and purity of 2 were confirmed via 1H, 13C, and 31P NMR spectroscopy along with elemental analysis. Polymerization reactions of 2 in NMP or DMSO at 180 °C provided the corresponding linear poly(arylene ether phosphine oxide)s, PAEPOs, with number average molecular weights, Mn, ranging from 11,700 to 36,500 Da. All of the polymer samples were completely soluble in chloroform, tetrahydrofuran, DMSO, NMP, and DMAc. The polymerization reactions were accompanied by a competing intramolecular process that resulted in the formation of cyclic oligomeric species that were removed via a final precipitation from methanol. Analysis using 31P NMR spectroscopy and size exclusion chromatography (SEC) confirmed that the majority of the lower molecular weight cyclic species were removed via this process. The polymer samples formed tough films when chloroform solutions were slowly evaporated on a glass slide. The PAEPO samples prepared in this study exhibited excellent thermal stability with Td (5%) values between 503 and 542 in air while the glass transition temperatures ranged from 223 to 237 °C. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2099–2106, 2006 相似文献
17.
18.
19.
Leclerc E Buchmann W Taphanel MH Morizur JP 《Rapid communications in mass spectrometry : RCM》2002,16(7):686-695
Ion/molecule reactions between O=P(OCH(3))(2)(+) phosphonium ions and six aromatic hydrocarbons (benzene, toluene, 1,2,4-trimethylbenzene, naphthalene, acenaphthylene and fluorene) were performed in a quadrupole ion trap mass spectrometer. The O=P(OCH(3))(2)(+) phosphonium ions, formed by electron impact from neutral trimethyl phosphite, were found to react with aromatic hydrocarbons (ArHs) to give (i) an adduct [ArH, O=P(OCH(3))(2)](+) and (ii) for ArHs which have an ionization energy below or equal to 8.14 eV, a radical cation ArH(+ *) by charge transfer reaction. Collision-induced dissociation experiments, which produce fragment ions other than the O=P(OCH(3))(2)(+) ions, indicate that the adduct ions are covalent species. Isotope-labeled ArHs were used to elucidate fragmentation mechanisms. The charge transfer reactions were investigated using density functional theory at the B3LYP/6-311 + G(3df,2p)//B3LYP/6-31G(d,p) level of theory. The potential energy surface obtained from B3LYP/6-31G(d,p) calculations for the reaction between O=P(OCH(3))(2)(+) and benzene is described. 相似文献
20.
O atom transfer from epoxides cis-stilbene oxide and styrene oxide to triphenylphosphine catalyzed by Tp'ReO(3) (Tp' = hydridotris(3,5-dimethylpyrazolyl)borate) is shown to proceed via an unexpectedly complex combination of mechanisms. Reduction of Tp'ReO(3) with PPh(3) in THF is rapid above room temperature to form a highly reactive species suggested to be Tp'ReO(2). Spectroscopic examination and attempts to isolate this by chromatography lead only to Tp'Re(O)(OH)(2) (1); exposure of the crude reduction mixture to ethanol results in formation of Tp'Re(O)(OEt)(OH) (3). Both 1 and 3 are as efficient catalysts for O atom transfer as the unpurified mixture resulting from reaction of PPh(3) with Tp'ReO(3); all three rhenium reactants give the same turnover frequency to within 10% at identical [Re](total) and [epoxide]. The kinetic behavior of the catalytic system (epoxide:Re = 20) is complex; an initial "burst" of alkene production is seen, which quickly tapers off and falls into a pseudo-zero-order reaction. The majority of rhenium is observed to exist as the syn-Tp'Re(O)(diolate) complex, formed by ring expansion of the epoxide. However, cycloreversion of this diolate is incapable of accounting for the observed catalytic turnover frequency. An additional intermediate, a coordinated epoxide, is proposed to form and partition between ring expansion and direct fragmentation to alkene; eventually a steady-state concentration of diolate forms. Competition between direct atom transfer and ring expansion followed by diolate cycloreversion is demonstrated by reaction of 3 with excess cis-stilbene oxide and styrene oxide in the absence of reductant to give a 4:1 mixture of alkene and syn-diolate from cis-stilbene oxide or a 5.5:1 mixture of alkene and syn-diolate from styrene oxide under conditions where diolate cycloreversion is a negligible contributor. 相似文献