全文获取类型
收费全文 | 3892篇 |
免费 | 265篇 |
国内免费 | 27篇 |
专业分类
化学 | 2424篇 |
晶体学 | 50篇 |
力学 | 120篇 |
数学 | 480篇 |
物理学 | 702篇 |
无线电 | 408篇 |
出版年
2023年 | 29篇 |
2022年 | 145篇 |
2021年 | 122篇 |
2020年 | 121篇 |
2019年 | 160篇 |
2018年 | 128篇 |
2017年 | 121篇 |
2016年 | 197篇 |
2015年 | 145篇 |
2014年 | 162篇 |
2013年 | 330篇 |
2012年 | 233篇 |
2011年 | 258篇 |
2010年 | 173篇 |
2009年 | 185篇 |
2008年 | 229篇 |
2007年 | 240篇 |
2006年 | 170篇 |
2005年 | 133篇 |
2004年 | 119篇 |
2003年 | 104篇 |
2002年 | 99篇 |
2001年 | 63篇 |
2000年 | 50篇 |
1999年 | 39篇 |
1998年 | 23篇 |
1997年 | 20篇 |
1996年 | 24篇 |
1995年 | 15篇 |
1994年 | 13篇 |
1993年 | 18篇 |
1992年 | 17篇 |
1991年 | 11篇 |
1990年 | 13篇 |
1989年 | 7篇 |
1988年 | 10篇 |
1987年 | 18篇 |
1986年 | 12篇 |
1985年 | 16篇 |
1984年 | 29篇 |
1983年 | 11篇 |
1981年 | 16篇 |
1980年 | 22篇 |
1979年 | 11篇 |
1978年 | 12篇 |
1977年 | 8篇 |
1976年 | 7篇 |
1975年 | 9篇 |
1973年 | 7篇 |
1862年 | 8篇 |
排序方式: 共有4184条查询结果,搜索用时 31 毫秒
81.
N. Sh. Lebedeva R. S. Kumeev G. A. Al’per E. V. Parfenyuk A. S. Vashurin T. V. Tararykina 《Journal of solution chemistry》2007,36(6):793-801
For the first time the interactions between zinc(II)tetra-4-alkoxybenzoyloxiphthalocyanine (Zn(4—O—CO—C6H4—OC11H23)Pc) and 1,4-diazabicyclo[2.2.2]octane (DABCO) in o-xylene and chloroform have been studied by calorimetric titration and NMR and electron absorption spectroscopic methods.
It has been found that in o-xylene at concentrations of Zn(4—O—CO—C6H4—OC11H23)Pc higher than 6×10−4 mol⋅L−1
π–π dimers species are formed (λ
max= 685 nm). Additions of DABCO to the solution up to mole ratio 1 : 8 (Zn(4—O—CO—C6H4—OC11H23)Pc : DABCO) lead to a shift of the aggregation equilibrium towards monomer species due to formation of monoligand axial complexes.
Further increasing the DABCO concentration results in formation of Zn(4—O—CO—C6H4—OC11H23)Pc—DABCO—Zn(4—O—CO—C6H4—OC11H23)Pc sandwich dimers (λ
max= 675 nm). 相似文献
82.
Abdullah A. Al‐Karim Al‐Shara'ey 《中国化学会会志》2004,51(3):547-552
6‐Aryl‐5‐cyano‐4‐pyrimidinone‐2‐thion derivatives 1a‐c reacted with methyl iodide (1:2) to give the corresponding 2‐S,N‐dimethyl pyrimidine‐4‐one derivatives 2a‐c . Compounds 2a‐c were in turn, reacted with hydrazine hydrate to give the sulfur free reaction products 3a‐c . These reaction products were taken as the starting materials for the synthesis of several new heterocyclic derivatives. Reaction of 3a‐c with acetic anhydride and formic acid gave pyrimido triazines 4a‐c and 7a‐c , respectively. Their reactions with active methylene containing reagents gave the corresponding 2‐(1‐pyrazonyl)‐N‐methyl pyrimidine derivatives 9a‐c and 10a‐c , respectively. Their reactions with aromatic aldehydes afforded the corresponding 2‐hydrazono pyrimidine derivatives 11a‐c . The structure of these reactions products were established based on both elemental analysis and spectral data studies. 相似文献
83.
Contreras Ricardo R. Fontal Bernardo Bahsas Alí Suárez Trino Reyes Marisela Bellandi Fernando Nava Flor Cancines Pedro 《Transition Metal Chemistry》2004,29(1):51-55
The synthesis of [benzyl-N,N-alkylbis(2-amino-1-cyclopentencarbodithioate)]MII [alkyl = ethene (L2) and propene, (L3) and M = Cu, Ni and Co] complexes and their characterization (u.v.–vis., FT-IR, 1H-n.m.r., mass spectra and cyclic voltametry) are reported. 相似文献
84.
E. D. Totchasov M. Yu. Nikiforov O. V. Eliseeva G. A. Al’per 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2006,80(10):1676-1679
This work presents the results obtained in measurements of the kinematic viscosity and density of the methanol-n-nonane, ethanol-n-nonane, and ethanol-n-decane systems at various temperatures and low n-alkane concentrations (within the concentration range of miscibility). The dynamic viscosities of these systems at 298.15 K were calculated according to free volume theory. The results substantiated the existence of an anomaly in the behavior of viscosity of the methanol-n-nonane system (positive Δlnη values) and its absence for the ethanol-n-alkane systems. 相似文献
85.
L. García Rodenas S. P. Alí S. J. Liberman 《Journal of Radioanalytical and Nuclear Chemistry》1990,141(2):289-294
The hydrogen isotope radiolytic yields, G(H2), G(HD) and G(D2) were determined in H2O/D2O mixtures under chemical conditions close to a LOCA in a PHWR like Atucha I Nuclear Station, that is 2·10–3 MH3BO3 and p(H+D)=8.5±0.2. The total hydrogen radiolytic yield G(H2+HD+D2) as a function of the deuterium atom fraction goes through a flat maximum at about 0.58. This result in dicates that the 4% flammability limit for hydrogen in the reactor's containment with be reached sooner than what is expected assuming a linear combination of pure H2 and D2 radiolytic yields. Hydrogen radiolytic production in 10–3 M KBr in H2O/D2O mixtures gives the same results as in the boric solutions suggesting a bimolecular B(OH)
4
–
+OH reaction. Identical isotope concentration factors were calculated for both solutions. 相似文献
86.
Mustafa R. Ibrahim Zacharia A. Fataftah Paul von Ragu Schleyer Peter D. Stout 《Journal of computational chemistry》1987,8(8):1131-1138
Sets of hydrogen molecule equivalents have been developed which permit the calculation of hydrogenation of different types of carbon-carbon bonds from ab initio total energies (3-21G and 6-31G* basis sets, and, to a more limited extent, for MP2/6-31G* data) of reactants and products. The calculated enthalpies of hydrogenation are in good agreement with experiment for unstrained molecules, with average errors on the order of 2 kcal/mol. The 6-31G* equivalents allow the enthalpies for strained molecules to be calculated accurately, but the 3-21G equivalents do not. The equivalents for both basis sets have been tested by calculating the enthalpies of hydrogenation of carbon-carbon bonds in nitrogen- and oxygen-containing organic molecules, free radicals, and classical carbocations. The results are in good agreement with experiment in most cases. 相似文献
87.
Arzu
zek idem Albayrak Mustafa Odabaolu Orhan Büyükgüngr 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(3):o177-o180
The title compounds, (E)‐2‐[(2‐bromophenyl)iminomethyl]‐4‐methoxyphenol, C14H12BrNO2, (I), (E)‐2‐[(3‐bromophenyl)iminomethyl]‐4‐methoxyphenol, C14H12BrNO2, (II), and (E)‐2‐[(4‐bromophenyl)iminomethyl]‐4‐methoxyphenol, C14H12BrNO2, (III), adopt the phenol–imine tautomeric form. In all three structures, there are strong intramolecular O—H⋯N hydrogen bonds. Compound (I) has strong intermolecular hydrogen bonds, while compound (III) has weak intermolecular hydrogen bonds. In addition to these intermolecular interactions, C—H⋯π interactions in (I) and (III), and π–π interactions in (I), play roles in the crystal packing. The dihedral angles between the aromatic rings are 15.34 (12), 6.1 (3) and 39.2 (14)° for (I), (II) and (III), respectively. 相似文献
88.
The ion exchange between60Co2+ ions contained in residual radioactive water and zeolites of the NaA, NaX and CaA types was studied. The more advanced retaining of60Co2+ ions occurs for the NaA zeolite with the higher exchange capacity, as compared to NaX. With the CaA zeolite, a very weak ion exchange with60Co2+ ions was observed. 相似文献
89.
A simple solid phase extraction procedure for speciation of selenium(IV) and selenium(VI) in environmental samples has been proposed prior to graphite furnace atomic absorption spectrometry. The method is based on the solid phase extraction of the selenium(IV)-ammonium pyrrolidine dithiocarbamate (APDC) chelate on the Diaion HP-2MG. After reduction of Se(VI) by heating the samples in the microwave oven with 4 mol l−1 HCl, the system was applied to the total selenium. Se(VI) was calculated as the difference between the total selenium content and Se(IV) content. The experimental parameters, pH, amounts of reagents, eluent type and sample volume were optimized. The recoveries of analytes were found greater than 95%. No appreciable matrix effects were observed. The adsorption capacity of sorbent was 5.20 mg g−1 Se (IV). The detection limit of Se (IV) (3sigma, n = 11) is 0.010 μg l−1. The preconcentration factor for the presented system was 100. The proposed method was applied to the speciation of selenium(IV), selenium(VI) and determination of total selenium in natural waters and microwave digested soil, garlic, onion, rice, wheat and hazelnut samples harvested various locations in Turkey with satisfactory results. In order to verify the accuracy of the method, certified reference materials (NIST SRM 2711 Montana Soil, NIST SRM 1568a Rice Flour and NIST SRM 8418 Wheat Gluten) were analyzed and the results obtained were in good agreement with the certified values. The relative errors and relative standard deviations were below 6 and 10%, respectively. 相似文献
90.
Peter Gajdoš Soňa Pavlíková Filip Bureš Alžbeta Krutošíková 《Central European Journal of Chemistry》2005,3(2):311-325
The synthesis and reactions of methyl 2-[3-(trifluoromethyl)phenyl]-4H-furo[3,2-b]pyrrole-5-carboxylate (1a) are described. Upon reaction with methyl iodide, benzyl chloride, or acetic anhydride, this compound gave N-substituted products 1b-d. By hydrolysis of compounds 1a-c, the corresponding acids 2a-c were formed, or by reaction with hydrazine-hydrate, the corresponding carbohydrazides 3a-c were formed. By heating 2-[3-(trifluoromethyl)phenly]-4H-furo[3,2-b]pyrrole-5-carboxylic acid (2a) in acetic anhydride, 4-acetyl-2-[3-(trifluoromethyl)phenyl]furo[3,2-b]pyrrole (4) was formed. By hydrolysis of 4, 2-[3-(trifluoromethyl)phenyl]-4H-furo[3,2-b]pyrrole (5a) was formed, and reactions with methyl iodide or benzyl chloride gave N-substituted products 5b-c. The reaction of 4 with dimethyl butynedioate gave substituted benzo[b]furan 6. Compound 3a reacted with triethyl orthoesters giving 7a-c, which afforded with phosphorus (V) sulphide the corresponding thiones 8a-c. The thiones 8a-c reacted with hydrazine hydrate to form hydrazine derivatives 9a-c. The reaction of triethyl orthoformiate with compounds 9a-c led to furo[2′,3′: 4,5]pyrrolo[1,2-d][1,2,4]triazolo[3,4-f][1,2,4]triazines 10a-c. Hydrazones 11a-c were formed from 3a-c and 5-[3-(trifluoromethyl)phenyl]furan-2-carboxaldehyde. The effect of microwave irradiation on some condensation reactions
was compared with “classical” conditions. The results showed that microwave irradiation shortens the reaction time while affording
comparable yields. 相似文献