全文获取类型
收费全文 | 2408篇 |
免费 | 199篇 |
国内免费 | 529篇 |
专业分类
化学 | 2642篇 |
晶体学 | 97篇 |
力学 | 26篇 |
综合类 | 7篇 |
数学 | 2篇 |
物理学 | 362篇 |
出版年
2024年 | 4篇 |
2023年 | 23篇 |
2022年 | 60篇 |
2021年 | 59篇 |
2020年 | 74篇 |
2019年 | 79篇 |
2018年 | 56篇 |
2017年 | 74篇 |
2016年 | 104篇 |
2015年 | 99篇 |
2014年 | 129篇 |
2013年 | 264篇 |
2012年 | 162篇 |
2011年 | 149篇 |
2010年 | 112篇 |
2009年 | 137篇 |
2008年 | 148篇 |
2007年 | 142篇 |
2006年 | 149篇 |
2005年 | 137篇 |
2004年 | 146篇 |
2003年 | 129篇 |
2002年 | 104篇 |
2001年 | 64篇 |
2000年 | 65篇 |
1999年 | 75篇 |
1998年 | 50篇 |
1997年 | 46篇 |
1996年 | 53篇 |
1995年 | 58篇 |
1994年 | 37篇 |
1993年 | 18篇 |
1992年 | 26篇 |
1991年 | 22篇 |
1990年 | 15篇 |
1989年 | 12篇 |
1988年 | 12篇 |
1987年 | 5篇 |
1986年 | 10篇 |
1985年 | 7篇 |
1984年 | 3篇 |
1983年 | 3篇 |
1982年 | 2篇 |
1981年 | 3篇 |
1980年 | 4篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1975年 | 2篇 |
1973年 | 1篇 |
排序方式: 共有3136条查询结果,搜索用时 23 毫秒
101.
Ammonium Chloro(thio)phosphate Betaines, a Class of Coordination-stabilized Chloro(thio)metaphosphates Ammonium chloro(thio)phosphate betaines behave like systems being in equilibrium with tert. amine and monomeric chloro(thio)metaphosphate. In solution at room temperature the amine component can be displaced by stronger donors. Mass spectra reveal the presence of ClPS2 as monomer and dimer, of ClPO2 by fragment ions of the dimer, trimer, and tetramer before reorganization takes place to form PXCl3 and P4X10 (X = O, S). Detection of ClPOS fails owing to fast equilibration into ClPO2 and ClPS2. 相似文献
102.
Thermochemical Properties and Decomposition Kinetics of Ammonium Magnesium Phosphate Monohydrate 总被引:1,自引:0,他引:1
Ammonium magnesium phosphate monohydrate NH4MgPO4·H2O was prepared via solid state reaction at room temperature and characterized by XRD, FT-IR and SEM. Thermochemical study was performed by an isoperibol solution calorimeter, non-isothermal measurement was used in a multivariate non-linear regression analysis to determine the kinetic reaction parameters. The results show that the molar enthalpy of reaction above is (28.795 ± 0.182) kJ/mol (298.15 K), and the standard molar enthalpy of formation of the title complex is (-2185.43 ± 13.80) kJ/mol (298.15 K). Kinetics analysis shows that the second decomposition of NH4MgPO4·H2O acts as a double-step reaction: an nth-order reaction (Fn) with n=4.28, E1=147.35 kJ/mol, A1=3.63×10^13 s^-1 is followed by a second-order reaction (F2) with E2=212.71 kJ/mol, A2= 1.82 × 10^18 s^-1. 相似文献
103.
Zirconium(IV) chloride catalyses the nucleophilic opening of epoxide rings by amines leading to the efficient synthesis of β-amino alcohols. The reaction works well with aromatic and aliphatic amines in short times at room temperature in the absence of solvent. Exclusive trans stereoselectivity is observed for cyclic epoxides. Aromatic amines exhibit excellent regioselectivity for preferential nucleophilic attack at the sterically less hindered position during the reaction with unsymmetrical epoxides. However, in case of styrene oxide, selective formation of the benzylic amine was observed during the reactions with aromatic amines. 相似文献
104.
105.
HU Rong TIAN Jinping & YIN Yingwu . College of Chemistry & Environment Protection Engineering Southwest University for Nationalities Chengdu China . TH-UNIS Insight Co. Ltd. Beijing China . Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology Ministry of Education Department of Chemistry Tsinghua University Beijing China 《中国科学B辑(英文版)》2006,49(4):351-356
The formation of peptides and then protein by small abiological molecules clusters such as amino acid is a key stage in the origin of life[1]. More and more ex- perimental results showed that phosphate plays an important role in the formation of biomolecules in prebiotic chemical evolution. The principal reservoirs of biochemical energy are phosphates (such as ATP). The peculiar role of phosphates in contemporary life might suggest its essential role in prebiotic energy conversion, syntheses … 相似文献
106.
107.
108.
Zirconiumphthalocyanines: Synthesis and Properties of Chloride Ligated Phthalocyanines of Ter- and Quadrivalent Zirconium; Crystal Structure of cis-Di(triphenylphosphine)iminium-tri(chloro)phthalocyaninato(2–)zirconate(IV)-di(dichloromethane) cis-Di(chloro)phthalocyaninato(2–)zirconium(IV) is obtained by the reaction of ZrCl4 with phthalodinitrile in 1-chloronaphthaline at 230°C. It reacts with molten di(triphenylphosphine)iminiumchloride ((PNP)Cl) yielding cis-di(triphenylphosphine)iminium-tri(chloro)phthalocyaninato(2-)zirconate(IV), cis-(PNP)[ZrCl3Pc2?]. This crystallizes with two molecules of dichloromethane in the monoclinic space group P21/n with the lattice constants a = 15.219(4) Å, b = 20.262(10) Å, c = 20.719(4) Å, b? = 93.46(2)°, Z = 4. The seven coordinated Zr atom is situated in a “square base-trigonal cap” polyhedron. The plane of the three chlorine atoms runs parallel to the plane of the four isoindole nitrogen atoms Niso. The Zr–Cl distances range from 2.49 to 2.55 Å, the Zr? Niso distances from 2.26 to 2.29 Å. Due to ion packing effects the Pc2? ligand shows an asymmetrical convex distortion. The PNP cation adopts the bent conformation. The P? N? P angle is 139°, the P? N distance 1.58 Å. As confirmed by the cyclovoltammograms cis-(PNP)[ZrCl3Pc2?] is oxidized (anodically or chemically by Cl2) to yield cis-tri(chloro)phthalocyaninato(1–)zirconium(IV) and reduced (cathodically or chemically by [BH4]?) yielding chlorophthalocyaninato(2–)zirconium(III) and cis-di(triphenylphosphine)iminium-di(chloro)phthalocyaninato(2–)zirconate(III). The optical spectra show the typical π–π*-transitions of the Pc2? resp. Pc? ligand not much affected by the different states of oxidation and coordination of zirconium. The same is true for the vibrational spectra of the Pc2? resp. Pc? ligand. In the f.i.r. spectra between 350 and 150 cm?1 the asym. and sym. Zr? Cl stretching and Cl? Zr? Cl deformation vibration as well as the asym. Zr? N stretching vibration of the [ZrClxN4] skeleton (x = 1–3) is assigned. 相似文献
109.
Yu. G. Yatluk N. A. Zhuravlev O. V. Koryakova L. K. Neudachina Yu. A. Skorik 《Russian Chemical Bulletin》2005,54(8):1836-1841
A series of new hybrid organo-inorganic sorbents with the 3-aminopropionate chelating group was synthesized. The synthesis
includes the copolycondensation (sol—gel method) of tetraethoxysilane, 3-aminopropyltriethoxysilane, and several modifiers
(MeSi(OEt)3, EtSi(OEt)3, Ti(OEt)4, AlONO3, ZrOCl2) followed by carboxyethylation with acrylic acid. The obtained chelating sorbents were characterized by elemental analysis,
FT-IR and 1H NMR spectroscopy, and thermogravimetry. The N-carboxylated sorbents have a higher sorption capacity with respect to metal ions (0.5–0.9 mmol g−1, pH 6.3, NH4OAc, 20 °C) than the starting sorbents with the primary amino group (0.05–0.2 mmol g−1) and manifest high selectivity for copper(II) ion extraction.
__________
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1783–1788, August, 2005. 相似文献
110.
Alexei A. Belik Shinya Uji Eiji Takayama-Muromachi 《Journal of solid state chemistry》2005,178(11):3461-3463
Magnetic properties of quasi-one-dimensional S=1/2 Heisenberg antiferromagnet Sr2Cu(PO4)2 were investigated by temperature and field dependence of AC susceptibility down to 0.03 K. A sharp peak was observed at on the temperature dependence of AC susceptibility indicating long-range magnetic ordering. Taking into account the exchange constant, (Hamiltonian =J∑SiSi+1), the ratio kBTN/J is 0.06%. Sr2Cu(PO4)2 is, therefore, one of the best one-dimensional Heisenberg antiferromagnet known so far. 相似文献