全文获取类型
收费全文 | 3326篇 |
免费 | 291篇 |
国内免费 | 462篇 |
专业分类
化学 | 3833篇 |
晶体学 | 15篇 |
力学 | 7篇 |
综合类 | 18篇 |
数学 | 1篇 |
物理学 | 205篇 |
出版年
2024年 | 7篇 |
2023年 | 31篇 |
2022年 | 108篇 |
2021年 | 101篇 |
2020年 | 166篇 |
2019年 | 136篇 |
2018年 | 107篇 |
2017年 | 132篇 |
2016年 | 140篇 |
2015年 | 141篇 |
2014年 | 145篇 |
2013年 | 320篇 |
2012年 | 201篇 |
2011年 | 170篇 |
2010年 | 147篇 |
2009年 | 164篇 |
2008年 | 177篇 |
2007年 | 164篇 |
2006年 | 161篇 |
2005年 | 152篇 |
2004年 | 161篇 |
2003年 | 148篇 |
2002年 | 98篇 |
2001年 | 74篇 |
2000年 | 70篇 |
1999年 | 75篇 |
1998年 | 78篇 |
1997年 | 51篇 |
1996年 | 70篇 |
1995年 | 53篇 |
1994年 | 57篇 |
1993年 | 58篇 |
1992年 | 52篇 |
1991年 | 28篇 |
1990年 | 20篇 |
1989年 | 15篇 |
1988年 | 13篇 |
1987年 | 9篇 |
1986年 | 15篇 |
1985年 | 10篇 |
1984年 | 15篇 |
1983年 | 7篇 |
1982年 | 10篇 |
1981年 | 6篇 |
1980年 | 6篇 |
1979年 | 5篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1973年 | 2篇 |
1972年 | 1篇 |
排序方式: 共有4079条查询结果,搜索用时 0 毫秒
51.
Reaction of 2,3,7,8,12,13,17,18-octaethylporphyrin with LiR reagents containing functional groups readily yields meso substituted derivatives suitable for further transformations with residues such as -p-C6H5Br, -p-C6H5-CCH, -p-C6H5-NH2 or -(CH2)3-CHCH2. Similar reactions of tetrabenzoporphyrin with alkyllithium reagents afforded the first entry into meso mono- and dialkylsubstituted tetrabenzoporphyrins while reaction of bicyclo[2.2.2]oct-type masked isoindole precursors with LiR followed by in situ retro-Diels-Alder reaction also afforded the 5-phenyl and 5,10-diphenyltetrabenzoporphyrins in high purity. 相似文献
52.
Electrolysis of the system Ti(IV)–NH2OH–C6H6 in an 11 M H2SO4 solution shows that using an organic solvent (acetic acid, acetonitrile) during cathodically initiated amination of aromatic substrates permits the production of aromatic amines with the overall yield by hydroxylamine reaching 91%. Due to a chain mechanism of radical substitution, the benzene amination in electrolytes containing 5 M CH3COOH and 5.5 M CH3CN terminates largely upon consuming 70–75 and 50–55% of the charge required theoretically for a one-electron process. The maximum efficiency of electrochemical amination is observed at low hydroxylamine conversions and the overall current efficiency for mono- and disubstituted products of the benzene amination may exceed in these conditions 750%. 相似文献
53.
本文研究了氢硼酸根(B_(12)H_(12)~(2-)、B_(10)H_(10)~(1-)、B_(11)H_(14)~-)和π-芳烃-π-环戊二烯基铁阳离子的反应,合成了36个氢硼酸π-芳烃-π-环戊二烯基铁化合物。通过元素分析和红外光谱测定确定了化合物的组成。部份化合物还作了~1H NMR鉴定。对化合物的性质,包括它们的热行为,进行了较详细的研究。DTA仪测得的结果表明,(1)当阳离子相同时,化合物的热稳定性的顺序为:[ArFeC_5H_5]_2B_(12)H_(12)>[ArFeC_5H_5]_2B_(10)H_(10)>[ArFeC_5H_5]B_(11)H_(14);(2)当氢硼酸根相同时,其热稳定性受芳环上取代基的影响。 相似文献
54.
In this study, we explore the reactions of coordinated arenes, e.g., hydrogenation, nitration, and bromination, to prepare compounds which are not accessible from conventional organic synthesis. The reaction products formed from reactions with the coordinated and the uncoordinated arenes are compared. The polycyclic aromatic hydrocarbons (PAHs) employed for this study include phenanthrene, methyl- and acetyl-phenanthrene, and benz[a]anthracene (BA), The tricarbonylchromium group demonstrated various characteristics which influence the reactions in this work, such as an electronic effect to deactivate hydrogenation, a steric effect to exhibit, highly positional selective nitration, and a free radical mechanism to direct bromine to attack at the ring coordinated to tricarbonylchromium. 相似文献
55.
Shaul M. Aharoni 《先进技术聚合物》1995,6(6):373-382
The preparation of rigid aromatic, highly branched polyamides is described. Owing to the method of preparation and the chosen ratio of difunctional to trifunctional monomers, these entities are highly porous and not dendrimeric in nature. They better conform with the fractal model and are therefore called fractal polyamides (FPs). The effects of variations in the polymerization procedure, in total monomer concentration, in the ratio of amine to carboxyl groups and in the duration of the polycondensation reaction are investigated. Some characterization was performed and the results are presented and briefly discussed. 相似文献
56.
H. Pongratz K. K. Mayer W. Wiegrebe 《Monatshefte für Chemie / Chemical Monthly》1997,128(6-7):659-673
Summary N-Butoxy- and N-propoxy-imines derived fromo-,m-, andp-substituted benzaldehydes (X = F, Cl, Br, I) decompose upon electron impact to the respective aldoximes by loss of C
n
H2n
and competitivelyvia 1,5-distonic radical cations by loss of CH2O to 1,3-distonic ions which eliminate H and/or a halogen atom in the course of homolytic aromatic substitution, giving rise to cyclic (M-CH2O-H)+ or (M-CH2O-X
)+ ions.Dedicated with warm regards to Prof. Dr.D. Seebach, Zürich, on the occasion of his 60th birthday 相似文献
57.
Shu Jiang ZHANG Yan Feng LI Xiao Long WANG Da Xue YIN Yu SHAO Xin ZHAO 《中国化学快报》2005,16(9):1165-1168
A new aromatic diamine monomer containing pyridine unit, 2,6-bis (4-aminophenoxy- 4'-benzoyl)pyridine(BABP), was synthesized in three steps, starting from 2,6-pyridinedicarboxyl chloride. A series of novel pyridine-containing polyimides were prepared v/a the polycondensation of BABP with various aromatic dianhydrides through poly(amic acid) precursors, and thermal or chemical imidization of the precursors. The polyimides exhibit desirable properties, e.g., good solubility in N-methyl-2-pyrrolidone and m-cresol, excellent thermal stability and film-forming capability, as well as high inherent viscosity, indicating high molecular weight. 相似文献
58.
V. G. Berezkin E. G. Sumina S. N. Shtykov V. Z. Atayan D. A. Zagniboroda G. A. Nekhoroshev 《Chromatographia》2006,64(1-2):105-108
A new variant of thin-layer chromatography (TLC), based on a gradual change of mobile phase acidity during elution, is proposed.
The pH change occurs in the mobile phase moving along the TLC plate as a result of its contact with an acidic or a basic gas
phase that replaces the initial mobile phase vapor in the TLC chamber. The potential of this approach has been demonstrated
by using carbon dioxide and ammonia gases to improve the resolution of benzoic acids and aromatic amines on polyamide TLC
plates. 相似文献
59.
A. Szafranek J. Szafranek 《Journal of inclusion phenomena and macrocyclic chemistry》1993,15(4):351-358
This paper reports TG analyses of inclusion complexes of-cyclodextrin with benzene, acetylsalicylic acid and methyl salicylate. The data were used for calculation of the compositions of the three body complexes and the apparent kinetic parameters of the thermal decompositions. Water exclusion proceeds as a reaction with ordern=1 and an activation energy about 20 kJ/mol. The expulsion of aromatic guest molecules follows ann=1 order process with the activation energy above 155 kJ/mol, except that for the methyl salicylate complex, which was found to be ca. 64 kJ/mol. 相似文献
60.
H. G. Struppe F. Franke J. Hofmann B. Ondruschka 《Journal of chromatography. A》1996,750(1-2):239-244
In contrast to usability of Curie-point pyrolysis at 700°C directly attached to gas chromatography-mass spectrometry (GC-MS) for determination of organic wood preservatives in waste wood samples the investigation method reported here consists of thermal desorption at temperatures about 260°C in connection with GC-MS for peak identification or GC with flame ionization detection for quantitative analyses. So-called “modified closeable sampling columns” are used as batch-reactor in thermal desorption experiments. Desorbed vapours can be introduced on capillary columns without sample discrimination and without a disturbing lost of resolution. In this manner a lot of individual polycyclic aromatic hydrocarbons were determinated in waste wood samples, especially in railway sleepers. 相似文献