全文获取类型
收费全文 | 81503篇 |
免费 | 8116篇 |
国内免费 | 13333篇 |
专业分类
化学 | 67190篇 |
晶体学 | 2184篇 |
力学 | 2192篇 |
综合类 | 731篇 |
数学 | 11381篇 |
物理学 | 19274篇 |
出版年
2024年 | 165篇 |
2023年 | 1271篇 |
2022年 | 2258篇 |
2021年 | 2628篇 |
2020年 | 2933篇 |
2019年 | 2767篇 |
2018年 | 2364篇 |
2017年 | 2904篇 |
2016年 | 3013篇 |
2015年 | 2661篇 |
2014年 | 3501篇 |
2013年 | 6947篇 |
2012年 | 4855篇 |
2011年 | 5359篇 |
2010年 | 4554篇 |
2009年 | 5681篇 |
2008年 | 5314篇 |
2007年 | 5295篇 |
2006年 | 4966篇 |
2005年 | 4343篇 |
2004年 | 4213篇 |
2003年 | 3431篇 |
2002年 | 3369篇 |
2001年 | 2449篇 |
2000年 | 2212篇 |
1999年 | 1797篇 |
1998年 | 1556篇 |
1997年 | 1307篇 |
1996年 | 1225篇 |
1995年 | 1198篇 |
1994年 | 1075篇 |
1993年 | 813篇 |
1992年 | 795篇 |
1991年 | 562篇 |
1990年 | 398篇 |
1989年 | 363篇 |
1988年 | 344篇 |
1987年 | 245篇 |
1986年 | 189篇 |
1985年 | 195篇 |
1984年 | 182篇 |
1983年 | 66篇 |
1982年 | 144篇 |
1981年 | 190篇 |
1980年 | 170篇 |
1979年 | 167篇 |
1978年 | 128篇 |
1977年 | 119篇 |
1976年 | 91篇 |
1973年 | 55篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
891.
The Fermi and Coulomb holes of the 21
S state of the helium isoelectronic sequence are investigated. Several interesting differences between the results obtained and those which might be expected on the basis of the corresponding 23
S state are pointed out and discussed. 相似文献
892.
首次研究了碳化钨负载S2 O2 -8 ZrO2 (PSZ)固体超强酸催化剂 (WC PSZ)上正戊烷的反应情况及影响催化剂活性的各种因素 ,并用GC MS ,XRD ,BET等手段分析了正戊烷反应产物和催化剂的物理化学性质等 .结果表明 :WC PSZ对正戊烷具有异构化和裂解的双重催化作用 .PSZ在负载适量碳化钨后对正戊烷反应的活性和选择性显著提高 ,显示出优于Pt PSZ催化剂的效果 ,碳化钨的负载量为 2 0 %的效果最佳 .适当的焙烧、活化和反应温度等条件是取得良好反应效果的关键 相似文献
893.
V. V. Dovlatyan K. A. Eliazyan V. A. Pivazyan A. P. Engoyan 《Chemistry of Heterocyclic Compounds》2003,39(9):1238-1241
We have carried out solvolysis of the previously described ethyl esters of 3-methyl(aryl)-4-methyl-2-thioxothiazoline-5-carboxylic acids, leading to the corresponding acids without breaking down the heterocycle. We synthesized a series of novel esters from the latter by treatment with dimethyl sulfate or reactive halides. Of these, only in the case of the ethyl ester of 3,4-dimethyl-2-thioxothiazoline-5-carboxylic acid did we obtain the hydrazinolysis product (the hydrazide), from which we synthesized novel hydrazones by treatment with aldehydes and ketones. 相似文献
894.
Toru Egawa Yukari Kachi Tsuguhide Takeshima Hiroshi Takeuchi Shigehiro Konaka 《Journal of Molecular Structure》2003,658(3):241-251
The molecular structure and conformation of carvone, a compound with a minty odor, were investigated by means of gas electron diffraction supported by theoretical calculations. Electron diffraction patterns were recorded by heating the nozzle up to 128 °C to obtain enough scattering intensity. The infrared spectrum was also measured by using an absorption cell with a path length of 10 m. The obtained molecular scattering intensities were analyzed with the aid of theoretical calculations and infrared spectroscopy. It was revealed that the experimental data are well reproduced by assuming that carvone consists of a mixture of three conformers that have the isopropenyl group in the equatorial position and mutually differ in the torsional angle around the single bond connecting the ring and the isopropenyl group. It was also found that the puckering amplitude of the ring of carvone is close to those of menthol and isomenthol, a minty compound and its nonminty isomer. The determined structural parameters (rg and ∠α) of the most abundant conformer of carvone are as follows: 〈r(C-C)〉=1.520(3) Å; 〈r(CC)〉=1.360(5) Å; r(CO)=1.225(5) Å; 〈r(C-H)〉=1.104(4)Å; 〈∠CC-C〉=121.1(5)°; 〈∠C-C-C〉=110.4(5)°; ∠C-CO-C=117.1(14)°; 〈∠C-C-H〉=111.1(13)°. Angle brackets denote average values and parenthesized values are the estimated limits of error (3σ) referring to the last significant digit. 相似文献
895.
Summary Electronic structure of hydrogen nitryl HNO2, a yet not identified entity, and the path of its possible isomerization totrans-HONO have been investigated byab initio SCF and MRD-CI computations using the 6-31G** basis set. HNO2 isC
2v
-symmetric and its ground state (1
A
1) is less stable thantrans-HONO by 66 kJ/mol (with the SCF vibrational zero-point energy correction). The lowest two excited singlet states (1
A
2 and1
B
1) are nearly degenerate, their vertical excitation energies being predicted to be 4.8 eV. The isomerization path is traced by the CASSCF procedure and the activation barrier height is evaluated by the CI treatment. HNO2 in its ground state isomerizes totrans-HONO by maintaining the planar (C
s-symmetric) structure. The activation energy is calculated to be 171 kJ/mol, which is clearly lower than the calculated H-N bond energy (253 kJ/mol). The transition state seems to be more adequately described as an interacting system of proton and the nitrite anion rather than as a pair of two fragment radicals. 相似文献
896.
Summary The -carbonyl substituted vinylphosphonates6–9 were synthesized from the -dicarbonyl compounds2–5 and the methylenbisphosphonate1 by a Horner-Emmons reaction in different yields.
Synthese von Phosphonocarbonylverbindungen durch Horner-Emmons-Reaktion von Methylenbisphosphonsäuretetraethylester
Zusammenfassung Es wurden die -carbonylsubstituierten Vinylphosphonate6–9 mittels Horner-Emmons-Reaktion aus den -Dicarbonylverbindungen2–5 und Methylenbisphosphonat1 in verschiedenen Ausbeuten hergestellt.相似文献
897.
Summary The halogenation of derivatives of 2-aminophenol with N-chloro- and N-bromosuccinimides at ambient temperatures in acetic acid was studied. With the necessary compounds available, a reexamination of the thermolytic rearrangement of 2-halophenyl azides to 2-aminophenols and other products was undertaken. It is certain that the rearrangement of 4-halophenyl azides to 2-aminophenols occurs but the products identified in this study differ significantly from those reported previously by Suschitzky et al. (1963, 1966).
Neuuntersuchung der thermolytischen Umlagerung von 4-Halogenphenylaziden zu 2-Aminophenolen und anderen Produkten
Zusammenfassung Es wurde die Halogenierung von 2-Aminophenol-Derivaten mit N-Chlor- und N-Bromsuccinimid bei Raumtemperatur in Essigsäure untersucht. Mit den zur Verfügung stehenden Verbindungen konnte eine Neuuntersuchung der thermolytischen Umlagerung von 4-Halogenphenylaziden zu 2-Aminophenolen und anderen Produkten unternommen werden. Diese Umlagerung findet sicherlich statt, allerdings differieren die dabei beobachteten Produkte signifikant von denen, die Suschitzky et al. 1963 und 1966 beschrieben.相似文献
898.
M. M. Krayushkin M. A. Kalik L. G. Vorontsova E. Yu. Zvezdina M. G. Kurella 《Russian Chemical Bulletin》1993,42(7):1204-1208
9-Methyl-3,3a,4,5-tetrahydro-6H-thieno[2,3-b]thiocino[4,5-c]isoxazole and 9-hydroxyimino-2-methyl-7-methylene-6, 7,8,9-tetrahydro-5H-thieno[2,3-b]thiocine have been prepared for the first time by the oxidation of 2--alkenylthio-3-thiophenecarbaldoximes with NaOCl. X-ray structural investigations of thieno[2,3-b]thiocine and 2-homomethallylthio-5-methyl-3-thiophenecarbaldoxime have been carried out.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1262–1266, July, 1993. 相似文献
899.
Constanti Magda Giralt Jaume Bordons Albert Norris Paul R. 《Applied biochemistry and biotechnology》1992,(1):767-776
The growth and oxygen consumption of a variety of thermophilic, acidophilic bacteria in the presence of thiophene-2-carboxylate
(T2C) and dibenzothiophene (DBT) have been determined. T2C was extremely toxic to the acidophiles in comparison with neutrophiles,
but appeared to be degraded by a heterotrophicSulfolobus- like thermophile. DBT proved to be unstable at high temperatures, even in the absence of bacteria, and was not a substrate for
the thermophiles. 相似文献
900.
Titanium dioxide (TiO2) thin films have been prepared on indium doped tin oxide (ITO) glass by sol-gel dip-coating method. Properties of the films
were determined as a function of heat-treatment by X-ray diffraction, scanning electron microscopy and photoelectrochemical
tests. The films heat-treated at higher temperatures show better crystallinity and photoresponse. The microscopic structure
on the film after heat-treatment is attributed to the incorporation of organic polymer into the precursor solution. The performance
of the electrodes treated at different temperature on photoelectrocatalytic degradation of methyl orange was investigated.
The effect of applied potential and the ability of the electrode to be repeatedly used in photoelectrocatalytic degradation
were also evaluated. 相似文献