全文获取类型
收费全文 | 2234篇 |
免费 | 90篇 |
国内免费 | 11篇 |
专业分类
化学 | 1605篇 |
晶体学 | 20篇 |
力学 | 51篇 |
综合类 | 1篇 |
数学 | 303篇 |
物理学 | 355篇 |
出版年
2022年 | 12篇 |
2021年 | 27篇 |
2020年 | 36篇 |
2019年 | 27篇 |
2018年 | 28篇 |
2017年 | 15篇 |
2016年 | 38篇 |
2015年 | 28篇 |
2014年 | 29篇 |
2013年 | 119篇 |
2012年 | 96篇 |
2011年 | 124篇 |
2010年 | 82篇 |
2009年 | 53篇 |
2008年 | 104篇 |
2007年 | 121篇 |
2006年 | 131篇 |
2005年 | 99篇 |
2004年 | 101篇 |
2003年 | 65篇 |
2002年 | 84篇 |
2001年 | 45篇 |
2000年 | 56篇 |
1999年 | 37篇 |
1998年 | 34篇 |
1997年 | 33篇 |
1996年 | 31篇 |
1995年 | 40篇 |
1994年 | 30篇 |
1993年 | 30篇 |
1992年 | 17篇 |
1991年 | 33篇 |
1990年 | 18篇 |
1989年 | 19篇 |
1988年 | 21篇 |
1987年 | 19篇 |
1986年 | 22篇 |
1985年 | 35篇 |
1984年 | 32篇 |
1983年 | 22篇 |
1982年 | 31篇 |
1981年 | 20篇 |
1980年 | 32篇 |
1979年 | 31篇 |
1978年 | 24篇 |
1977年 | 30篇 |
1976年 | 14篇 |
1975年 | 22篇 |
1974年 | 22篇 |
1973年 | 17篇 |
排序方式: 共有2335条查询结果,搜索用时 35 毫秒
121.
Daniele Giallombardo Adam C. Nevin William Lewis Christopher C. Nawrat Russell R.A. Kitson Christopher J. Moody 《Tetrahedron》2014
A synthesis of the naturally occurring xanthone toxyloxanthone B is described, in which the key step is the regioselective addition of a methyl salicylate to a substituted benzyne, followed by cyclization of the intermediate aryl anion to form the xanthone, the regiochemistry of the aryne addition being confirmed by X-ray crystallography. Subsequent introduction of the pyran ring by [3,3]-rearrangement and deprotection completed the synthesis. 相似文献
122.
Russell G. Baughman Gabriel B. Hall 《Acta Crystallographica. Section C, Structural Chemistry》2014,70(10):975-977
Structural studies performed in this laboratory of organophosphorus pesticides continue with these related compounds. The –NO2 groups of methyl parathion (systematic name: dimethyl 4‐nitrophenyl phosphorothioate, C8H10NO5PS) and dicapthon (systematic name: 2‐chloro‐4‐nitrophenyl dimethyl phosphorothioate, C8H9ClNO5PS) make dihedral angles of 10.67 (8) and 5.8 (1)°, respectively, with the planes of their attached rings, which accompanies angular distortion at the ring C atoms to which the –NO2 groups are attached. Similar distortions are observed at the C atom to which the thiophosphate groups are attached. Significant differences in distances and angles around the phenolic O, versus the –OMe groups, explain why it is the site of hydrolysis for these compounds. A comparison of a torsion angle involving the thiophosphate group and phenolic O atom with similar pesticide structures is given and indicates steric influences on that angle. 相似文献
123.
Natalia G. Petrochko R. Gregory Peters Russell G. Baughman 《Acta Crystallographica. Section C, Structural Chemistry》2014,70(5):508-511
The crystal structures of the title compounds, [Mo{(C4H8NO)2P(C2F5)}(CO)5], (1a), and [Mo{(C5H10N)2P(C2F5)}(CO)5], (2a), were determined as part of a larger project that focuses on the synthesis and coordination chemistry of phosphane ligands possessing moderate (electroneutral, i.e. neither electron‐rich nor electron‐deficient) electronic characteristics. Both complexes feature a slightly distorted octahedral geometry at the metal center, due to the electronic and steric repulsions between two of the four equatorial CO groups and the pentafluoroethyl group attached to the phosphane ligand. Bond length and angle data for (1a) and (2a) support the conclusion that the free phosphane ligands are electroneutral. For complex (1a), the Mo—P, Mo—Cax and Mo—Ceq(ave) bond lengths are 2.5063 (5), 2.018 (2) and 2.048 (2) Å, respectively, and for complex (2a) these values are 2.5274 (5), 2.009 (3) and 2.050 (3) Å, respectively. Geometric data for (1a) and (2a) are compared with similar data reported for analogous Mo(CO)5 complexes. 相似文献
124.
Ryan M. Tipker Jake A. Muldoon Daniel H. Pham Balazs R. Varga Russell P. Hughes David S. Glueck Gary J. Balaich Arnold L. Rheingold 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2022,134(1):e202110753
Tetrahedral main-group compounds are normally configurationally stable, but P-epimerization of the chiral phosphiranium cations syn- or anti-[Mes*P(Me)CH2CHPh][OTf] (Mes*=2,4,6-(t-Bu)3C6H2) occurred under mild conditions at 60 °C in CD2Cl2, resulting in isomerization to give a syn-enriched equilibrium mixture. Ion exchange with excess [NBu4][Δ-TRISPHAT] (Δ-TRISPHAT=Δ-P(o-C6Cl4O2)3) followed by chromatography on silica removed [NBu4][OTf] and gave mixtures of syn- and anti-[Mes*P(Me)CH2CHPh][Δ-TRISPHAT]?x[NBu4][Δ-TRISPHAT]. NMR spectroscopy showed that isomerization proceeded with epimerization at P and retention at C. DFT calculations are consistent with a mechanism involving P-C cleavage to yield a hyperconjugation-stabilized carbocation, pyramidal inversion promoted by σ-interaction of the P lone pair with the neighboring β-carbocation, and ring closure with inversion of configuration at P. 相似文献
125.
In situ and operando techniques providing information regarding adsorbate bonding and atomic arrangements on the electrode surface along with pure electrochemical measurements are needed to more fully understand the detailed mechanism of electrocatalytic reactions on high surface areas/nanoparticle electrocatalysts. X-ray adsorption spectroscopy (XAS) is a powerful tool to interrogate the electronic structure and local coordination environment of such electrocatalysts under working conditions, but it should be acknowledged that standard XAS methods are not intrinsically surface sensitive. This review will present recent in situ XAS studies on single-atom, metal, and metal oxide electrocatalysts, highlighting the approaches taken to achieve surface sensitivity by careful designing of the sample under investigation. 相似文献
126.
127.
Effect of forewing and hindwing interactions on aerodynamic forces and power in hovering dragonfly flight 总被引:1,自引:0,他引:1
Dragonflies are four-winged insects that have the ability to control aerodynamic performance by modulating the phase lag (phi) between forewings and hindwings. We film the wing motion of a tethered dragonfly and compute the aerodynamic force and power as a function of the phase. We find that the out-of-phase motion as seen in steady hovering uses nearly minimal power to generate the required force to balance the weight, and the in-phase motion seen in takeoffs provides an additional force to accelerate. We explain the main hydrodynamic interaction that causes this phase dependence. 相似文献
128.
Comparative Studies of Thermally Induced Homolytic CarbonCarbon Bond Cleavage Reactions of Strained Dicarba[2]ferrocenophanes and Their Ring‐Opened Oligomers and Polymers 下载免费PDF全文
Andrew D. Russell Prof. Joe B. Gilroy Prof. Ian Manners 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(14):4077-4085
Reactivity studies of dicarba[2]ferrocenophanes and also their corresponding ring‐opened oligomers and polymers have been conducted in order to provide mechanistic insight into the processes that occur under the conditions of their thermal ring‐opening polymerisation (ROP) (300 °C). Thermolysis of dicarba[2]ferrocenophane rac‐[Fe(η5‐C5H4)2(CHPh)2] (rac‐ 14 ; 300 °C, 1 h) does not lead to thermal ROP. To investigate this system further, rac‐ 14 was heated in the presence of an excess of cyclopentadienyl anion, to mimic the postulated propagating sites for thermally polymerisable analogues. This afforded acyclic [(η5‐C5H5)Fe(η5‐C5H4)‐CH2Ph] ( 17 ) through cleavage of both a Fe?Cp bond and also the C?C bond derived from the dicarba bridge. Evidence supporting a potential homolytic C?C bond cleavage pathway that occurs in the absence of ring‐strain was provided through thermolysis of an acyclic analogue of rac‐ 14 , namely [(η5‐C5H5)Fe(η5‐C5H4)(CHPh)2‐C5H5] ( 15 ; 300 °C, 1 h), which also afforded ferrocene derivative 17 . This reactivity pathway appears general for post‐ROP species bearing phenyl substituents on adjacent carbons, and consequently was also observed during the thermolysis of linear polyferrocenylethylene [Fe(η5‐C5H4)2(CHPh)2]n ( 16 ; 300 °C, 1 h), which was prepared by photocontrolled ROP of rac‐ 14 at 5 °C. This afforded ferrocene derivative [Fe(η5‐C5H4CH2Ph)2] ( 23 ) through selective cleavage of the ?H(Ph)C?C(Ph)H? bonds in the dicarba linkers. These processes appear to be facilitated by the presence of bulky, radical‐stabilising phenyl substituents on each carbon of the linker, as demonstrated through the contrasting thermal properties of unsubstituted linear trimer [(η5‐C5H5)Fe(η5‐C5H4)(CH2)2(η5‐C5H4)Fe(η5‐C5H4)(CH2)2(η5‐C5H4)Fe(η5‐C5H5)] ( 29 ) with a ?H2C?CH2? spacer, which proved significantly more stable under analogous conditions. Evidence for the radical intermediates formed through C?C bond cleavage was detected through high‐resolution mass spectrometric analysis of co‐thermolysis reactions involving rac‐ 14 and 15 (300 °C, 1 h), which indicated the presence of higher molecular weight species, postulated to be formed through cross‐coupling of these intermediates. 相似文献
129.
The Assembly‐Disassembly‐Organization‐Reassembly Mechanism for 3D‐2D‐3D Transformation of Germanosilicate IWW Zeolite 下载免费PDF全文
Pavla Chlubná‐Eliášová Yuyang Tian Dr. Ana B. Pinar Dr. Martin Kubů Prof. Jiří Čejka Prof. Russell E. Morris 《Angewandte Chemie (International ed. in English)》2014,53(27):7048-7052
Hydrolysis of germanosilicate zeolites with the IWW structure shows two different outcomes depending on the composition of the starting materials. Ge‐rich IWW (Si/Ge=3.1) is disassembled into a layered material (IPC‐5P), which can be reassembled into an almost pure silica IWW on treatment with diethoxydimethylsilane. Ge‐poor IWW (Si/Ge=6.4) is not completely disassembled on hydrolysis, but retains some 3D connectivity. This structure can be reassembled into IWW by incorporation of Al to fill the defects left when the Ge is removed. 相似文献
130.
Dr. Paul S. Wheatley Dr. Pavla Chlubná‐Eliášová Dr. Heather Greer Prof. Wuzong Zhou Dr. Valerie R. Seymour Dr. Daniel M. Dawson Prof. Sharon E. Ashbrook Dr. Ana B. Pinar Dr. Lynne B. McCusker Dr. Maksym Opanasenko Prof. Jiří Čejka Prof. Russell E. Morris 《Angewandte Chemie (International ed. in English)》2014,53(48):13210-13214
Zeolites are important materials whose utility in industry depends on the nature of their porous structure. Control over microporosity is therefore a vitally important target. Unfortunately, traditional methods for controlling porosity, in particular the use of organic structure‐directing agents, are relatively coarse and provide almost no opportunity to tune the porosity as required. Here we show how zeolites with a continuously tuneable surface area and micropore volume over a wide range can be prepared. This means that a particular surface area or micropore volume can be precisely tuned. The range of porosity we can target covers the whole range of useful zeolite porosity: from small pores consisting of 8‐rings all the way to extra‐large pores consisting of 14‐rings. 相似文献