全文获取类型
收费全文 | 1292篇 |
免费 | 54篇 |
国内免费 | 142篇 |
专业分类
化学 | 389篇 |
晶体学 | 8篇 |
力学 | 20篇 |
综合类 | 12篇 |
数学 | 897篇 |
物理学 | 162篇 |
出版年
2024年 | 3篇 |
2023年 | 11篇 |
2022年 | 23篇 |
2021年 | 29篇 |
2020年 | 43篇 |
2019年 | 57篇 |
2018年 | 42篇 |
2017年 | 54篇 |
2016年 | 33篇 |
2015年 | 26篇 |
2014年 | 36篇 |
2013年 | 318篇 |
2012年 | 31篇 |
2011年 | 43篇 |
2010年 | 28篇 |
2009年 | 53篇 |
2008年 | 48篇 |
2007年 | 70篇 |
2006年 | 62篇 |
2005年 | 46篇 |
2004年 | 42篇 |
2003年 | 46篇 |
2002年 | 89篇 |
2001年 | 40篇 |
2000年 | 32篇 |
1999年 | 36篇 |
1998年 | 30篇 |
1997年 | 21篇 |
1996年 | 28篇 |
1995年 | 20篇 |
1994年 | 12篇 |
1993年 | 9篇 |
1992年 | 3篇 |
1991年 | 2篇 |
1990年 | 2篇 |
1989年 | 2篇 |
1988年 | 1篇 |
1987年 | 4篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1983年 | 1篇 |
1982年 | 3篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1978年 | 2篇 |
1973年 | 1篇 |
1970年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有1488条查询结果,搜索用时 15 毫秒
101.
Theab initio SCF method is used for computing the main electronic properties of the ribose unit of the nucleic acids. The present study is devoted to the ribose in the C3-endo,gg conformation. The properties investigated include the distribution of the electronic charges, the electrostatic molecular potential around the four oxygens of the unit, the hydration and the Na+ binding schemes studied in the supermolecule approximation. The possibilities of through-water binding of the cation to the sugar are also explored. The predictions of the computation in particular with regard to cation binding to the ribose ring are correlated with recent experimental results. 相似文献
102.
103.
104.
近年来,伽罗瓦环上的序列理论成为人们研究的热点问题.有限域上的No序列是一类伪随机序列,它在序列密码中占具十分重要的角色.本文利用伽罗瓦环上的置换,构造了伽罗瓦环Z_(p~e)上的一类新的No序列,并且研究了其线性复杂度.研究的结果表明此类No序列具有相当大的线性复杂度. 相似文献
105.
The methods for the synthesis of oxazolo[3,2-a]pyridinium and oxazolo[3,2-a]pyrimidinium salts and their reactivities are reviewed. Both systems exhibit ambident properties in reactions with nucleophiles;
depending on the substituents and the reagents, both the oxazole and azine rings can undergo opening and transformations.
A number of new methodologies involving oxazolopyridinium and oxazolopyrimidinium salts for the design of functionalized oxazoles,
imidazoles, fused pyrroles, and other heterocyclic systems are generalized.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 831–848, April, 2008. 相似文献
106.
Hong‐Jian Wang Paul v. R. Schleyer Judy I. Wu Yan Wang Hai‐Jun Wang 《International journal of quantum chemistry》2011,111(5):1031-1038
The resonance energies (REs) of neutral three membered ring analogs of the cyclopropenyl cation, computed using block localized wave function (BLW) methods, reveal considerable variations. The RE's of cyclopropenes substituted with exocyclic double bonded groups C?X, (X = O, NH, CH2, S, PH, SiH2) increase with the electronegativity of X in the same row (SiH2 < PH < S and CH2 < NH < O). The extra cyclic resonance energies (ECREs) (an energetic measure of aromaticity based on comparisons with the RE's of acyclic models) of these derivatives range from +10.5 kcal/mol for cyclopropenone (X = O) (somewhat aromatic; the benzene ECRE is 29.3 kcal/mol) to ?2.4 kcal/mol (slightly antiaromatic) for X = SiH2. Additional disubstitution of the C?C double bond by X′ groups (X′ = CH3, NH2, OH, SiH3, PH2, SH) increases the REs considerably, but has only small effects on the ECREs. Even the ECRE of deltic acid (X = O, X′ = OH) is only increased to +13.3 kcal/mol. The conclusion based on ECRE's, that all 12 of the three membered rings are only marginally aromatic/antiaromatic, is supported by the satisfactorily plot (R2 = 0.92) of ECRE against values of NICS(0)πzz (a superior nucleus chemical independent shift magnetic index of aromaticity), which range only from ?6.1 ppm (diatropic) for deltic acid (cf., ?35.5 ppm for benzene and ?14.2 ppm for the parent cyclopropenium ion) to +8.9 ppm (paratropic) for the silicon derivative, X = SiH2, X′ = SiH3. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011 相似文献
107.
Dr. Ryu Yamasaki Dr. Masato Ohashi Kyotaro Maeda Takuya Kitamura Minami Nakagawa Korehito Kato Tetsushi Fujita Ryohei Kamura Kazuto Kinoshita Dr. Hyuma Masu Prof. Dr. Isao Azumaya Prof. Dr. Sensuke Ogoshi Prof. Dr. Shinichi Saito 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(10):3415-3425
A detailed study of the Ni‐catalyzed [4+3+2] cycloaddition reaction between ethyl cyclopropylideneacetate and dienynes has been conducted, resulting in the development of a new method for the synthesis of compounds containing nine‐membered rings. We studied the reactivity of various dienynes, together with their substituent and conformational effects. The mechanism of the reaction was probed by examining the stoichiometric reactions of the Ni complexes and dienynes. 相似文献
108.
Angelika B. Boeer David Collison Prof. Christopher A. Muryn Dr. Grigore A. Timco Dr. Floriana Tuna Dr. Richard E. P. Winpenny Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(47):13150-13160
The synthesis and structural characterization of three heterometallic rings templated about imidazolium cations is reported. The compounds are [2,4‐DiMe‐ImidH][Cr7NiIIF8(O2CtBu)16] 1 (2,4‐DiMe‐ImidH=the cation of 2,4‐dimethylimidazole), [ImidH]2[Cr6NiII2F8(O2CCtBu)16] 2 (ImidH=the cation of imidazole), and [1‐Bz‐ImidH]2 [Cr7NiII2F9(O2CtBu)18] 3 (1‐Bz‐ImidH=the cation of 1‐benzylimidazole). The structures show the formation of octagonal arrays of metals for 1 and 2 and a nonagon of metal centers for 3 . In all cases the edges of the polygon are bridged by a single fluoride and two pivalate ligands, and the position of the divalent metal centers cannot be distinguished by X‐ray diffraction. Magnetic studies combined with EPR spectroscopy allow the characterization of the magnetic states of the compounds. In each case the exchange is antiferromagnetic with a magnetic exchange parameter J≈?5.8 cm?1, and it is not possible to differentiate the exchange between two CrIII centers (JCrCr) from the exchange between a CrIII and a NiII center (JCrNi). For 2 there is evidence for the presence of at least two, possibly four, linkage isomers of the heterometallic ring, caused by the presence of two divalent metal centers in the ring. The EPR spectroscopy of 3 suggests an S=1/2 ground state of the ring and that it is likely that only one linkage isomer is present. 相似文献
109.
Noemí Andrade-López Tracy A. Hanna José G. Alvarado-Rodríguez Adriana Luqueño-Reyes Bernat A. Martínez-Ortega Daniel Mendoza-Espinosa 《Polyhedron》2010
Cis-diaquobis{di-(2-pyridyl)-N-ethylimine}nickel(II) chloride (2) was obtained from the reaction of di-(2-pyridyl)-N-ethylimine (1) and [NiCl2dppe] [dppe = cis-1,2-bis(diphenylphosphino)ethylene] in a 2:1 ratio in hot acetonitrile. Cis-dichloro{di-(2-pyridyl)-N-ethylimine}palladium(II) (3) and cis-dichloro{di-(2-pyridyl)-N-ethylimine}platinum(II) (4) complexes were obtained from the reaction of MCl2 (M = Pd, Pt) and (1) in equimolar ratio in hot acetonitrile. Compounds 1–4 were characterized by IR spectroscopy, elemental analysis, and mass spectrometry; the complexes 3 and 4 were characterized in solution by NMR. In addition, solid state structures of compounds 1–4 were determined using single crystal X-ray diffraction analyses. X-ray diffraction data of the complexes 3 and 4 showed a distorted square planar local geometry at palladium and platinum atoms with the chlorine atoms in a cis-coordination; in 2 a local octahedral geometry at nickel atom was observed. Complexes 3 and 4 are arranged as dimers with a M?M distance of 3.4567(4) Å (M = Pd) and 3.4221(4) Å (M = Pt), respectively; 2 consists of units linked by intermolecular hydrogen bonding. 相似文献
110.
Hisatoyo Morinaga Hiroshi Morikawa Atsushi Sudo Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》2010,48(20):4529-4536
A new water‐soluble poly(ethylene imine)‐derivative having imidazolidine moieties was developed. With using branched poly(ethylene imine) (BPEI) as a precursor, it was modified by Michael addition reaction of its primary amino group to an acrylate having poly(ethylene glycol) (PEG) chain. The modified BPEI was reacted with octanal to give the corresponding BPEI derivative having octanal‐derived imidazolidine moieties. The obtained polymer inherited the high hydrophilicity of the attached PEG chains to allow hydrolysis of the imidazolidine moieties under homogeneous conditions in aqueous media, leading to long‐lasting release of octanal. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010 相似文献