全文获取类型
收费全文 | 3612篇 |
免费 | 183篇 |
国内免费 | 145篇 |
专业分类
化学 | 1409篇 |
晶体学 | 5篇 |
力学 | 110篇 |
综合类 | 15篇 |
数学 | 546篇 |
物理学 | 937篇 |
无线电 | 918篇 |
出版年
2024年 | 10篇 |
2023年 | 163篇 |
2022年 | 50篇 |
2021年 | 54篇 |
2020年 | 65篇 |
2019年 | 55篇 |
2018年 | 65篇 |
2017年 | 65篇 |
2016年 | 77篇 |
2015年 | 72篇 |
2014年 | 153篇 |
2013年 | 325篇 |
2012年 | 292篇 |
2011年 | 191篇 |
2010年 | 145篇 |
2009年 | 209篇 |
2008年 | 152篇 |
2007年 | 193篇 |
2006年 | 175篇 |
2005年 | 198篇 |
2004年 | 171篇 |
2003年 | 121篇 |
2002年 | 96篇 |
2001年 | 68篇 |
2000年 | 83篇 |
1999年 | 71篇 |
1998年 | 88篇 |
1997年 | 74篇 |
1996年 | 69篇 |
1995年 | 69篇 |
1994年 | 45篇 |
1993年 | 49篇 |
1992年 | 30篇 |
1991年 | 36篇 |
1990年 | 20篇 |
1989年 | 21篇 |
1988年 | 22篇 |
1987年 | 22篇 |
1986年 | 8篇 |
1985年 | 10篇 |
1984年 | 6篇 |
1983年 | 6篇 |
1982年 | 13篇 |
1981年 | 8篇 |
1980年 | 10篇 |
1979年 | 5篇 |
1978年 | 4篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1973年 | 1篇 |
排序方式: 共有3940条查询结果,搜索用时 9 毫秒
51.
神经网络法用于多元混酸同时测定 总被引:1,自引:0,他引:1
利用多层神经网络误差反向传播算法处理酸碱电位滴定数据,求得出多元混合酸各组分的浓度,优化了神经网络的结构和参数,测定了三组分有机酸混合样品,结果良好,平均相对偏差RSD≤4%。 相似文献
52.
提出了控制电位电解和恒电流电解两类电解沉积的压电频移分析法测定的理论公式,用实验结果验证了它的正确性. 相似文献
53.
Preparation, Crystal Structure and Normal Coordinate Analysis of Linkage Isomeric Pentachlororhodanoosmates(IV) By treatment of [OsCl5I]2? with (SCN)2 in dichloromethane the linkage isomers [OsCl5(NCS)]2? and [OsCl5(SCN)]2? are formed which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. The X-ray structure determination on single crystals of (Ph4As)2[OsCl5(NCS)] (monoclinic, space group P21/a, a = 18.872(2), b = 11.6024(2), c = 22.786(1), β = 109.057(1)°, Z = 4) and (Ph4As)2[OsCl5(SCN)] (monoclinic, space group P21/a, a = 19.057(2), b = 11.306(2), c = 22.612(1), β = 106.64(2)°, Z = 4) reveals the complete ordering of the complex anions. The thiocyanate group is located above one of the Cl ligands of the equatorial plane with the Os? N? C angle of 166.1° for N bonding and the Os? S? C angle of 109.9° for S bonding. The IR and Raman spectra of both linkage isomers known from literature are assigned by normal coordinate analysis based on the general valence force field using the molecular parameters of the X-ray determination. The valence force constants are fd(OsN) = 1,81 and fd(OsS) = 1,32 mdyn/Å. Taking into account increments of the trans influence a good adjustment between observed and calculated frequencies is achieved. 相似文献
54.
María Fernanda Martínez-Esperón 《Tetrahedron》2006,62(16):3843-3855
N,N′-aryl- and N,N′-alkyl-buta-1,3-diyne-1,4-ditosylamides have been synthesized for the first time, in good to excellent yields, by copper-catalyzed dimerization of the corresponding N-aryl or N-alkyl tosylynamides. Negishi coupling of N-ethynylzinc tosylamides derivatives with (hetero)aryl iodides in the presence of Pd2dba3 and triphenylphosphine affords N-aryl and N-alkyl arylynamides in yields of up to 90%. Intramolecular [4+2] cycloaddition reactions of N-ethynylphenyl ynamides and arylynamides allow the synthesis of carbazoles and benzannulated and heteroannulated carbazoles in moderate-to-good yields. 相似文献
55.
Mecheril V. Nandakumar 《Tetrahedron》2005,61(41):9775-9782
A Pd2dba3/P(i-BuNCH2CH2)3N catalyzed one-pot synthesis of unsymmetrically substituted trans-4-N,N-diarylaminostilbenes and both symmetrically and unsymmetrically substituted N,N-diarylaminostyrene derivatives is reported. The procedure involves two or more palladium catalyzed sequential coupling reactions (an amination and an inter-molecular Heck reaction) in one-pot using the same catalyst system with two different aryl halides, including aryl chlorides and hetero aryl halides as the coupling partners. 相似文献
56.
Alessandro Ferrali 《Tetrahedron letters》2004,45(27):5271-5274
A δ-valerolactam-derived vinyl triflate has been converted into the corresponding vinyl boronate by Pd-catalyzed coupling with bis(pinacolato)diboron, which results in an umpolung. This boronate efficiently couples under Pd catalysis with aryl and heteroaryl bromides to give the corresponding 2-substituted piperidines in excellent yields. 相似文献
57.
Rongbin Qi Yujun Wang Jiding Li Changwei Zhao Shenlin Zhu 《Journal of membrane science》2006,280(1-2):545-552
Worldwide concerns over environment have stimulated increasing interest both in academic and industry for deep desulfurization of gasoline. Polydimethylsiloxane (PDMS) composite membrane was used to separate the binary and multicomponent alkane/thiophene mixtures by pervaporation. Effect of carbon number and concentration of alkane, and of feed temperature, on the separation efficiency of alkane/thiophene mixtures was investigated experimentally. Experimental results of binary mixtures indicated that the total fluxes for different alkane/thiophene mixtures decrease with increase of carbon number in the alkanes. Corresponding activation energies of permeation for alkanes in PDMS membrane increase with increase of carbon number in the alkanes. Differences of molecular size and structure of the alkanes lead to various selectivities thereof within PDMS membrane. In addition, the permeability and activation energy of thiophene in various systems differ from each other due to coupling effect which should be taken into consideration when dealing with multicomponent systems. Pervaporation results of ternary systems indicated that, the increase of content of lighter alkane in feed would result in a larger total flux, but a smaller selectivity to thiophene simultaneously. A quaternary system, the mixture of n-heptane, n-octane, n-nonane and thiophene, was employed to simulate the desulfurization process of gasoline. With the membrane having a PDMS layer of 11 μm, the total flux was measured to be about 1.65 kg/m2 h, with the corresponding enrichment factor of thiophene 3.9 at 30 °C. 相似文献
58.
Herein, we discuss the analyses and quantification of the different components in porphyrin mixtures, prepared from p-anisaldehyde, p-tolualdehyde, and 5-(4-bromophenyl)-dipyrromethane with acid catalysis, using NMR and HPLC. The advantages and disadvantages of these analytical methods are emphasized. Due to the similar size of a bromine atom and a methyl group it was possible to grow crystals suitable for X-ray crystallographic studies from a mixture of porphyrins, where the 4-position of the meso-phenyl rings was either substituted with methyl groups or bromine atoms. We also show that X-ray studies are inferior to NMR analysis for determining the components in a porphyrin mixture. 相似文献
59.
Grigorii G. Sivets Elena N. Kalinichenko Igor A. Mikhailopulo 《Helvetica chimica acta》2007,90(9):1818-1836
Convergent syntheses of the 9‐(3‐X‐2,3‐dideoxy‐2‐fluoro‐β‐D ‐ribofuranosyl)adenines 5 (X=N3) and 7 (X=NH2), as well as of their respective α‐anomers 6 and 8 , are described, using methyl 2‐azido‐5‐O‐benzoyl‐2,3‐dideoxy‐2‐fluoro‐β‐D ‐ribofuranoside ( 4 ) as glycosylating agent. Methyl 5‐O‐benzoyl‐2,3‐dideoxy‐2,3‐difluoro‐β‐D ‐ribofuranoside ( 12 ) was prepared starting from two precursors, and coupled with silylated N6‐benzoyladenine to afford, after deprotection, 2′,3′‐dideoxy‐2′,3′‐difluoroadenosine ( 13 ). Condensation of 1‐O‐acetyl‐3,5‐di‐O‐benzoyl‐2‐deoxy‐2‐fluoro‐β‐D ‐ribofuranose ( 14 ) with silylated N2‐palmitoylguanine gave, after chromatographic separation and deacylation, the N7‐β‐anomer 17 as the main product, along with 2′‐deoxy‐2′‐fluoroguanosine ( 15 ) and its N9‐α‐anomer 16 in a ratio of ca. 42 : 24 : 10. An in‐depth conformational analysis of a number of 2,3‐dideoxy‐2‐fluoro‐3‐X‐D ‐ribofuranosides (X=F, N3, NH2, H) as well as of purine and pyrimidine 2‐deoxy‐2‐fluoro‐D ‐ribofuranosyl nucleosides was performed using the PSEUROT (version 6.3) software in combination with NMR studies. 相似文献
60.
The intramolecular dynamic behavior of the tetrahedrane-type cluster [Fe2(CO)6(μ-SNH)] 1 was studied by 13C NMR spectroscopy. The 57Fe chemical shift of 1 and the coupling constants 1
J(57Fe,13C) were measured. These NMR parameters, and also 1
J(57Fe,15N), were found to be in good agreement with data calculated by using density functional theory (DFT) methods (B3LYP), based on the geometry calculated at the 6-311+G(d,p) level of theory. The isolobal replacement of the Fe(CO)3 with BH fragments leads to the tetrahedranes [Fe(CO)3(BH)(μ-SNH)] 2 and [(HB)2(μ-SNH)] 3. Both were identified by calculations as minima on the respective potential energy surface (PES). However, the tetrahedrane-type structure of 3 is much higher in energy when compared with the planar cyclic isomers 3a and 3b. 相似文献