全文获取类型
收费全文 | 1119篇 |
免费 | 57篇 |
国内免费 | 1篇 |
专业分类
化学 | 836篇 |
晶体学 | 15篇 |
力学 | 35篇 |
数学 | 76篇 |
物理学 | 215篇 |
出版年
2023年 | 6篇 |
2022年 | 21篇 |
2021年 | 23篇 |
2020年 | 32篇 |
2019年 | 26篇 |
2018年 | 29篇 |
2017年 | 29篇 |
2016年 | 54篇 |
2015年 | 40篇 |
2014年 | 51篇 |
2013年 | 82篇 |
2012年 | 98篇 |
2011年 | 74篇 |
2010年 | 41篇 |
2009年 | 41篇 |
2008年 | 87篇 |
2007年 | 48篇 |
2006年 | 47篇 |
2005年 | 42篇 |
2004年 | 39篇 |
2003年 | 27篇 |
2002年 | 33篇 |
2001年 | 8篇 |
2000年 | 6篇 |
1998年 | 4篇 |
1997年 | 6篇 |
1996年 | 12篇 |
1995年 | 4篇 |
1994年 | 3篇 |
1991年 | 7篇 |
1990年 | 5篇 |
1986年 | 8篇 |
1985年 | 10篇 |
1984年 | 10篇 |
1983年 | 5篇 |
1982年 | 3篇 |
1981年 | 8篇 |
1980年 | 5篇 |
1979年 | 5篇 |
1978年 | 10篇 |
1977年 | 4篇 |
1969年 | 6篇 |
1968年 | 6篇 |
1964年 | 4篇 |
1963年 | 6篇 |
1962年 | 6篇 |
1961年 | 12篇 |
1958年 | 7篇 |
1957年 | 3篇 |
1955年 | 5篇 |
排序方式: 共有1177条查询结果,搜索用时 796 毫秒
101.
102.
Thiol–Ene “Click” Reaction Triggered by Neutral Ionic Liquid: The “Ambiphilic” Character of [hmim]Br in the Regioselective Nucleophilic Hydrothiolation 下载免费PDF全文
Rajesh Kumar Saima Amit Shard Nitin H. Andhare Richa Dr. Arun K. Sinha 《Angewandte Chemie (International ed. in English)》2015,54(3):828-832
Thiol–ene “click” chemistry has emerged as a powerful strategy to construct carbon–heteroatom (C? S) bonds, which generally results in the formation of two regioisomers. To this end, the neutral ionic liquid [hmim]Br has been explored as a solvent cum catalyst for the synthesis of linear thioethers from activated and inactivated styrene derivatives or secondary benzyl alcohols and thiols without the requirement of using a metal complex, base, or free radical initiator. Furthermore, detailed mechanistic investigations using 1H NMR spectroscopy and quadrupole time‐of‐flight electrospray ionization mass spectrometry (Q‐TOF ESI‐MS) revealed that the “ambiphilic” character of the ionic liquid promotes the nucleophilic addition of thiol to styrene through an anti‐Markovnikov pathway. The catalyst recyclability and the extension of the methodology for thiol–yne click chemistry are additional benefits. A competitive study among thiophenol, styrene, and phenyl acetylene revealed that the rate of reaction is in the order of thiol–yne>thiol–ene>dimerization of thiol in [hmim]Br. 相似文献
103.
A new prenylated biflavonoid, named dulcisbiflavonoid A, together with five biflavonoids were isolated from the leaves of Garcinia dulcis. Their structures were elucidated by analysing their spectroscopic data, especially 1D and 2D NMR. 相似文献
104.
Varish Ahmad Qazi Mohammad Sajid Jamal Arun K. Shukla Javed Alam Ahamad Imran Usama Mohamed Abaza 《Journal of Cluster Science》2017,28(4):1775-1802
The search of eco-friendly technologies for nano-synthesis is significant to expand their applications in human welfare. Nowadays, various inorganic nanoparticles with beneficial features have been synthesized via physical, chemical, and biological means. Significant biological applications of silver nanoparticles include on-infectious microbes, target drug delivery, cancer and vector-borne disease control. Their syntheses have been tested from plant fungi, bacteria, and viruses. The bacterial mediated synthesis of silver, gold, zinc and other metal leads to a milestone in nano-medicines. Thus, in this review, we focus on the contribution of Bacilli in the synthesis of silver nanoparticles, the mechanism of action and their potential application in the welfare of human beings. 相似文献
105.
Sharvari Deshmukh Kalyani Kamde Arun Jana Sanjivani Korde Rajib Bandyopadhyay Ravi Sankar Nabarun Bhattacharyya R.A. Pandey 《Analytica chimica acta》2014
Electronic nose systems when deployed in network mesh can effectively provide a low budget and onsite solution for the industrial obnoxious gaseous measurement. For accurate and identical prediction capability by all the electronic nose systems, a reliable calibration transfer model needs to be implemented in order to overcome the inherent sensor array variability. In this work, robust regression (RR) is used for calibration transfer between two electronic nose systems using a Box–Behnken (BB) design. Out of the two electronic nose systems, one was trained using industrial gas samples by four artificial neural network models, for the measurement of obnoxious odours emitted from pulp and paper industries. The emissions constitute mainly of hydrogen sulphide (H2S), methyl mercaptan (MM), dimethyl sulphide (DMS) and dimethyl disulphide (DMDS) in different proportions. A Box–Behnken design consisting of 27 experiment sets based on synthetic gas combinations of H2S, MM, DMS and DMDS, were conducted for calibration transfer between two identical electronic nose systems. Identical sensors on both the systems were mapped and the prediction models developed using ANN were then transferred to the second system using BB–RR methodology. The results showed successful transmission of prediction models developed for one system to other system, with the mean absolute error between the actual and predicted concentration of analytes in mg L−1 after calibration transfer (on second system) being 0.076, 0.1801, 0.0329, 0.427 for DMS, DMDS, MM, H2S respectively. 相似文献
106.
Neelakandan Vidhya LakshmiYuvaraj Arun Paramasivam T. Perumal 《Tetrahedron letters》2011,52(27):3437-3442
A new approach to synthesize a series of spiro-oxindole derivatives via a multicomponent reaction of isatin, 3-phenyl-5-isoxazolone, and sarcosine or l-proline which play a dual role of base and nucleophile in methanol under reflux condition is reported. Also spiroindan-1,3-diones were synthesized from ninhydrin and 3-phenyl-5-isoxazolone. The methodology affords high yields of products in a short reaction time. 相似文献
107.
Mohammad Akbar Ali Aminul Huq Mirza Ray J. Butcher Arun K. Chowdhury 《Transition Metal Chemistry》2011,36(5):471-479
A new tridentate ONS ligand, H2L, has been synthesized by condensing thenoyltrifluoroacetone(4,4,4-trifluoro-1-(2-thienyl)-2,4butaneanedione) with S-benzyldithiocarbazate
and its structure determined by X-ray diffraction. In the solid state, the Schiff base exists as the ketoamine-thioketo tautomer
but in solution and in the presence of copper(II), it converts to the enol-thiol form and deprotonates to give copper(II)
complexes of formula, [CuL] and [CuLL1] (L = doubly deprotonated form of the ligand; L1 = py, bipy or phen] which have been characterized by magnetic, spectroscopic, and X-ray diffraction studies. An X-ray crystallographic
analysis shows that [CuL(py)] has a square-planar geometry with the ligand coordinated to the copper(II) center via the enolate
oxygen, the azomethinic nitrogen and the thiolate sulfur, the fourth coordination position being occupied by pyridine. The
[CuL(bipy)] complex is five-coordinate with a structure close to square-pyramidal in which the Schiff base acts as a doubly
deprotonated tridentate ONS ligand and bipy is bidentate. 相似文献
108.
Three new bicomponent hydrogels of riboflavin (R) with salicylic acid (S), dihydroxybenzoic acid (B) and acetoguanamine (D) in 1:1 molar ratio have been reported. FTIR and UV-vis spectra suggest formation of H-bonded complexes in 1:1 molar ratio of the components. The network consists of tape, bar and helical tubes for RB11, RS11 and RD11 systems, respectively. Reversible first order phase transition and invariant storage modulus (G') with angular frequency (ω) characterise the systems as forming thermoreversible hydrogels. The RD11 gel has the highest gel melting temperature and highest critical strain compared to other gels. WAXS study indicates different crystal structures for different gels. NMR spectra reveals higher shielding of protons in RD11 gel suggesting better π-stacking compared to RS11 and RB11 gels. RD11 gel shows two-fold enhancement of photoluminescence (PL) intensity with a substantial red shift of emission peak but RB11 and RS11 gels show PL-quenching. The gels exhibit a small decrease in lifetime and the PL property is very much temperature and pH dependent. So the complementary molecules have a pronounced effect on morphology, structure, stability and optical property of riboflavin gels. 相似文献
109.
Bar AK Shanmugaraju S Chi KW Mukherjee PS 《Dalton transactions (Cambridge, England : 2003)》2011,40(10):2257-2267
Design and synthesis of three novel [2 + 2] self-assembled molecular rectangles 1-3via coordination driven self-assembly of predesigned Pd(ii) ligands is reported. 1,8-Diethynylanthracene was assembled with trans-Pd(PEt(3))(2)Cl(2) in the presence of CuCl catalyst to yield a neutral rectangle 1via Pd-C bond formation. Complex 1 represents the first example of a neutral molecular rectangle obtained via C-Pd coordination driven self-assembly. A new Pd(2)(II) organometallic building block with 180° bite-angle 1,4-bis[trans-(ethynyl)Pd(PEt(3))(2)(NO(3))]benzene (M(2)) containing ethynyl functionality was synthesized in reasonable yield by employing Sonagashira coupling reaction. Self-assembly of M(2) with two organic clip-type donors (L(2)-L(3)) afforded [2 + 2] self-assembled molecular rectangles 2 and 3, respectively [L(2) = 1,8-bis(4-pyridylethynyl)anthracene; L(3) = 1,3-bis(3-pyridyl)isophthalamide]. The macrocycles 1-3 were fully characterized by multinuclear NMR and ESI-MS spectroscopic techniques, and in case of 1 the structure was unambiguously determined by single crystal X-ray diffraction analysis. Incorporation of Pd-ethynyl bonds helped to make the assemblies π-electron rich and fluorescent in nature. Complexes 1-2 showed quenching of fluorescence intensity in solution in presence of nitroaromatics, which are the chemical signatures of many commercially available explosives. 相似文献
110.
Metal-ligand complexes of Cu(OTf)(2) with an appropriate bisphosphine ligand have been shown to effectively catalyze the formation of substituted tetrahydropyrans via a sequential olefin migration and Prins-type cyclization. This methodology provides convenient access to a variety of functionalized tetrahydropyrans in excellent diastereoselectivities and good to excellent yields. 相似文献