全文获取类型
收费全文 | 38822篇 |
免费 | 2924篇 |
国内免费 | 2960篇 |
专业分类
化学 | 26377篇 |
晶体学 | 158篇 |
力学 | 457篇 |
综合类 | 639篇 |
数学 | 6734篇 |
物理学 | 10341篇 |
出版年
2023年 | 404篇 |
2022年 | 488篇 |
2021年 | 1371篇 |
2020年 | 964篇 |
2019年 | 1045篇 |
2018年 | 739篇 |
2017年 | 794篇 |
2016年 | 1118篇 |
2015年 | 1166篇 |
2014年 | 1374篇 |
2013年 | 2744篇 |
2012年 | 1838篇 |
2011年 | 1966篇 |
2010年 | 1892篇 |
2009年 | 2368篇 |
2008年 | 2542篇 |
2007年 | 2677篇 |
2006年 | 2146篇 |
2005年 | 1503篇 |
2004年 | 1433篇 |
2003年 | 1434篇 |
2002年 | 1288篇 |
2001年 | 1128篇 |
2000年 | 794篇 |
1999年 | 658篇 |
1998年 | 625篇 |
1997年 | 451篇 |
1996年 | 516篇 |
1995年 | 471篇 |
1994年 | 492篇 |
1993年 | 535篇 |
1992年 | 511篇 |
1991年 | 342篇 |
1990年 | 287篇 |
1989年 | 218篇 |
1988年 | 249篇 |
1987年 | 200篇 |
1986年 | 217篇 |
1985年 | 321篇 |
1984年 | 240篇 |
1983年 | 146篇 |
1982年 | 299篇 |
1981年 | 477篇 |
1980年 | 431篇 |
1979年 | 466篇 |
1978年 | 379篇 |
1977年 | 282篇 |
1976年 | 248篇 |
1974年 | 77篇 |
1973年 | 151篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
41.
Zhigang Xue Zhen Wang Dan He Xingping Zhou Xiaolin Xie 《Journal of polymer science. Part A, Polymer chemistry》2016,54(5):611-620
Cationic emulsions of triblock copolymer particles comprising a poly(n‐butyl acrylate) (PnBA) central block and polystyrene (PS) outer blocks were synthesized by activator generated by electron transfer (AGET) atom transfer radical polymerization (ATRP). Difunctional ATRP initiator, ethylene bis(2‐bromoisobutyrate) (EBBiB), was used as initiator to synthesize the ABA type poly(styrene‐b‐n‐butyl acrylate‐b‐styrene) (PS‐PnBA‐PS) triblock copolymer. The effects of ligand and cationic surfactant on polymerizations were also discussed. Gel permeation chromatography (GPC) was used to characterize the molecular weight (Mn) and molecular weight distribution (MWD) of the resultant triblock copolymers. Particle size and particle size distribution of resulted latexes were characterized by dynamic light scattering (DLS). The resultant latexes showed good colloidal stability with average particle size around 100–300 nm in diameter. Glass transition temperature (Tg) of copolymers was studied by differential scanning calorimetry (DSC). © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 611–620 相似文献
42.
Domino Radical Addition/Oxidation Sequence with Photocatalysis: One‐Pot Synthesis of Polysubstituted Furans from α‐Chloro‐Alkyl Ketones and Styrenes 下载免费PDF全文
Shuang Wang Wen‐Liang Jia Lin Wang Prof. Dr. Qiang Liu Prof. Dr. Li‐Zhu Wu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(39):13794-13798
A new domino reaction has been developed that allows the combination of styrenes and α‐alkyl ketone radicals to afford a wide array of polysubstituted furans in good to excellent yields under mild and simple reaction conditions. The key to success of this novel protocol is the use of photocatalyst fac‐Ir(ppy)3 and oxidant K2S2O8. Mechanistic studies by a radical scavenger and photoluminescence quenching suggest that a radical addition/oxidation pathway is operable. 相似文献
43.
In this study lanthanum trilactate was prepared by neutralization reaction of lactic acid and lanthanum oxide, purified and identified by X-ray powder diffraction. Infrared spectra (Mid-IR region 4000–650 cm−1) and Raman spectra (Stokes region 4000–100 cm−1) of the high quality crystalline samples have been recorded and presented for the first time. For comparison DFT calculations were performed using Gaussian 09 D.01 and agreement between predicted and measured spectral data has been achieved. Acquired information can be utilized for substance identification for example in various industrial applications or in biological systems. 相似文献
44.
Romain Bénéteau Anne Boussonnière Jean‐Christophe Rouaud Prof. Dr. Jacques Lebreton Dr. Jérôme Graton Prof. Dr. Denis Jacquemin Dr. Muriel Sebban Prof. Dr. Hassan Oulyadi Ghanem Hamdoun Dr. Amber N. Hancock Prof. Dr. Carl H. Schiesser Dr. Fabrice Dénès 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(14):4809-4824
α‐Bromo aluminium acetals are suitable substrates for Ueno–Stork‐like radical cyclisations affording γ‐lactols and acid‐sensitive methylene‐γ‐lactols in high yields. The mechanistic study herein sets the scope and limitation of this reaction. The influence of the halide (or chalcogenide) atom X (X=Cl, Br, I, SPh, SePh) in the precursors α‐haloesters, as well as influence of the solvent and temperature was studied. The structure of the aluminium acetal intermediates resulting from the reduction of the corresponding α‐haloesters has been investigated by low‐temperature 13C‐INEPT diffusion‐ordered NMR spectroscopy (DOSY) experiments and quantum calculations, providing new insights into the structures of these thermally labile intermediates. Oxygen‐bridged dimeric structures with a planar Al2O2 ring are proposed for the least hindered aluminium acetals, while monomeric structures seem to prevail for the most hindered species. A comparison against the radical cyclisation of aluminium acetals derived from allyl and propargyl alcohols with the parent Ueno–Stork has been made at the BHandHLYP/6‐311++G(d,p) level of theory, highlighting mechanistic similarities and differences. 相似文献
45.
价廉易得的L-亮氨酸先以苄基同时保护氨基及羧基得(S)-2-(二苄胺基)-4-甲基戊酸苄酯,进而在碱性条件下与乙腈发生亲核取代反应得(S)-4-(二苄胺基)-6-甲基-3-氧代庚腈,再经硼氢化钠选择性还原羰基得(3S,4S)-4-(二苄胺基)-3-羟基-6-甲基庚腈,用双氧水氧化得(3S,4S)-4-(二苄胺基)-3-羟基-6-甲基庚酸,最后在Pd(OH)2/C-H2作用下脱掉苄基得到(3S,4S)-4-氨基-3-羟基-6-甲基庚酸,即(3S,4S)-statine。整个合成路线总产率为33.6%。 相似文献
46.
Novel self activated green phosphors; K2ZnV2O7 (KZV) and K2MgV2O7 (KMV) have been prepared and characterized in details. Both KZV and KMV were prepared by solid state reaction and systematically characterized by a number of techniques like X-ray diffraction (XRD), Fourier transformed Infrared (FTIR), Raman spectroscopy, Scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), diffuse reflectance spectroscopy (DRS) and time resolved photoluminescence spectroscopy (TRPLS). XRD studies confirm tetragonal melilite type layered phase for both of them. The presence of pyrovanadate group in both is supported by FTIR and Raman spectroscopic investigations. Raman bands of KMV are blue shifted w.r.t to KZV which may be due to shorter bond lengths of MgO compared to ZnO and lower atomic weight of magnesium compared to zinc. DRS measurements indicated the optical band gap of KMV and KZV are 3.14 and 3.12 eV, respectively. Optical measurements on these samples show the emission of green color on ultra violet light irradiation. The origin of such emission is attributed to electronic transition (charge transfer) from filled 2p orbital of oxygen ion (O2−) to vacant 3d orbital of vanadium ion (V5+). In KZV there are dual emission band (PL1 and PL2) which are respectively attributed to 3T2 → 1A1 and 3T1 → 1A1transition, and the emission zone varies slightly compared to KMV. KZV emits bluish green (cool green) where KMV emits in yellowish green (warm green) region. This is indeed an important step towards realization of cost effective rare earth free luminescence material. It is also oberved that PL intensity of KZV is very high compared to KMV which is supported by the lifetime measurements. 相似文献
47.
Intermolecular Stetter reaction of aromatic aldehydes with (E)-(2-nitrovinyl)cyclohexane catalyzed by thiazolium A has been developed. The reaction rate and efficiency are profoundly impacted by the presence of thiourea B. The reaction affords moderate to good yields of the Stetter product. Some factors influencing yield were discussed. 相似文献
48.
Naphthalic anhydride derivatives: Structural effects on their initiating abilities in radical and/or cationic photopolymerizations under visible light 下载免费PDF全文
Pu Xiao Frédéric Dumur Jing Zhang Bernadette Graff Fabrice Morlet‐Savary Jean Pierre Fouassier Didier Gigmes Jacques Lalevée 《Journal of polymer science. Part A, Polymer chemistry》2015,53(24):2860-2866
Only one naphthalic anhydride derivative has been reported as light sensitive photoinitiator, this prompted us to further explore the possibility to prepare a new family of photoinitiators based on this scaffold. Therefore, eight naphthalic Naphthalic anhydride derivatives (ANH1‐ANH8) have been prepared and combined with an iodonium salt (and optionally N‐vinylcarbazole) or an amine (and optionally 2,4,6‐tris(trichloromethyl)‐1,3,5‐triazine) to initiate the cationic polymerization of epoxides and the free radical polymerization of acrylates under different irradiation sources, that is, very soft halogen lamp (~ 12 mW cm?2), laser diode at 405 nm (~1.5 mW cm?2) or blue LED centered at 455 nm (80 mW cm?2). The ANH6 based photoinitiating systems are particularly efficient for the cationic and the radical photopolymerizations, and even better than that of the well‐known camphorquinone based systems. The photochemical mechanisms associated with the chemical structure/photopolymerization efficiency relationships are studied by steady state photolysis, fluorescence, cyclic voltammetry, laser flash photolysis, and electron spin resonance spin‐trapping techniques. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2860–2866 相似文献
49.
Novel hyperbranched polymers synthesized via A3 + B(B′) approach by radical addition‐coupling polymerization 下载免费PDF全文
In this study, a novel application of radical addition‐coupling polymerization (RACP) for synthesis of hyperbranched polymers is reported. By Cu/PMDETA‐mediated RACP of 2‐methyl‐2‐nitrosopropane with trimethylolpropane tris(2‐bromopropionate) or a bromo‐ended 3‐arm PS macromonomer, two types of hyperbranched polymers with high degree of polymerization are synthesized under mild conditions, respectively. The chemical structures of the hyperbranched polymers are carefully characterized. By selective degradations of the ester groups and weak bonds of NO? C in the polymers, high degree of alternative connection of the two monomers in the synthesized polymers have been identified. Based on the experimental results, mechanism of formation of the hyperbranched polymer is proposed, which includes formation of carbon radicals from the tribromo monomer through single electron transfer, its capture by 2‐methyl‐2‐nitrosopropane that results in nitroxide radical, and cross‐coupling reaction of the nitroxide radical with other carbon radicals. Hyperbranched polymer can be formed in a step‐growth mode after multiple steps of such reactions. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 904–913 相似文献
50.
《Comptes Rendus Chimie》2015,18(6):619-625
A new terdentate acyclic pincer ligand, 2,6-bis(tert-butylthiomethyl)pyridine (tbtmp), was synthesized and reacted with several complexes of iron, zinc, nickel, cobalt, and copper. The ligand and its coordination compounds were characterized using elemental analysis, infrared, 1H- and 13C-NMR-spectroscopy, thermal analyses, plus—for the Zn complex—single-crystal X-ray diffractometry. The structure of [Zn(L)Br2] was solved in the tetragonal crystal system, chiral space groups P41212 and P43212 (No. 92 and No. 96, a = 947.2(1) pm, c = 2265.2(5) pm), revealing five-fold coordination of the metal atoms. According to spectroscopy, all complexes share the same coordination environment around the metal atoms, consisting of two halide anions and a sulfur-methylene-pyridine-methylene-sulfur entity; tbtmp acts as a tridentate ligand with the pyridine N atom and both tert-butylthio S atoms coordinating to the metal ions (NS2). The analysis results indicate that the metal ions are coordinated as distorted pseudo-bipyramids, LMX2, with the chelate ligand meridionally arranged. One of the complexes contains ethanol as an additional ligand, resulting in a pseudo-octahedral coordination sphere [Ni(L)Cl2EtOH]. The latter was obtained in the form of green crystals, which turn into a red powder with loss of the ethanol molecule. Fe (III), Co(II), Ni(II) and Cu(II) metal complexes [M(L)Cl2] were screened for their antibacterial activity against B. subtilis G(+) and Escherichia coli G(−) bacteria, and fungus (Candida albicans and Aspergillus flavus). 相似文献