全文获取类型
收费全文 | 1982篇 |
免费 | 84篇 |
国内免费 | 16篇 |
专业分类
化学 | 1498篇 |
晶体学 | 28篇 |
力学 | 41篇 |
数学 | 272篇 |
物理学 | 243篇 |
出版年
2023年 | 9篇 |
2022年 | 17篇 |
2021年 | 38篇 |
2020年 | 27篇 |
2019年 | 46篇 |
2018年 | 28篇 |
2017年 | 30篇 |
2016年 | 58篇 |
2015年 | 53篇 |
2014年 | 79篇 |
2013年 | 122篇 |
2012年 | 151篇 |
2011年 | 139篇 |
2010年 | 104篇 |
2009年 | 74篇 |
2008年 | 130篇 |
2007年 | 153篇 |
2006年 | 124篇 |
2005年 | 125篇 |
2004年 | 107篇 |
2003年 | 90篇 |
2002年 | 76篇 |
2001年 | 31篇 |
2000年 | 44篇 |
1999年 | 23篇 |
1998年 | 16篇 |
1997年 | 19篇 |
1996年 | 26篇 |
1995年 | 9篇 |
1994年 | 13篇 |
1993年 | 9篇 |
1992年 | 19篇 |
1991年 | 11篇 |
1990年 | 6篇 |
1989年 | 4篇 |
1988年 | 11篇 |
1987年 | 3篇 |
1986年 | 12篇 |
1985年 | 9篇 |
1984年 | 9篇 |
1983年 | 5篇 |
1982年 | 5篇 |
1981年 | 10篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1977年 | 1篇 |
1975年 | 3篇 |
1972年 | 1篇 |
1969年 | 1篇 |
排序方式: 共有2082条查询结果,搜索用时 281 毫秒
41.
Katiuska Araujo Marinela Colina Román Mazurek José Delgado Hilda Ledo Elizabeth Gutierrez Lenín Herrera 《Fresenius' Journal of Analytical Chemistry》1996,355(3-4):319-320
The mercury concentrations in wastewater and sewage sludge of a stabilization pond system have been evaluated. The system is built by three parallel facultative ponds followed by two systems of three maturation ponds in series. The samples of wastewater and sludge were digested using nitric acid and placed into a Parr-type bomb for 4 h at 110° C. Mercury was measured by Cold Vapour Atomic Absorption Spectrometry (CV-AAS) at 253.7 nm with sodium tetrahydroborate as reductant. The methodologies were checked with an USEPA quality control sample, a standard reference material from NIST and with another method of mineralization (cold mineralization) showing good results. Concentrations of mercury in wastewater between 1.47 ± 0.75 gl–1 have been found at the entrance of the system and 0.74 ± 0.0 gl–1 at the exit, while in sludge the results were between 0.29 ± 0.12 gkg–1 in the facultative pond and 0.04 ± 0.02 gkg–1 in the second maturation pond (exit). 相似文献
42.
J. U. Delgado J. L. S. Carvalho L. Tauhata 《Journal of Radioanalytical and Nuclear Chemistry》1993,173(1):179-184
Methods to determine U, Th, and other constituent elements in mineral matrices through Instrumental Neutron Activation Analysis (INAA), have been widely utilized due to their capability to extract a large quantity of information from small samples. In the present work, an experimental methodology based on INAA associated to the cluster statistics technique was used to determine the uranium concentration and its correlation with other elements present in the mineral phosphorites from the northeast region of Brazil. Data for 22 elements including rare-earth elements are presented. A good correlation between uranium and rare-earth elements is observed. For the transition metals, correlation with uranium was not noted. 相似文献
43.
Santiago Conde Carlos Corral Jaime Lissavetzky 《Journal of heterocyclic chemistry》1985,22(2):301-304
A study on the oximation of a number of 2-acetylthiophenes in order to ascertain the validity of contradictory results previously described is reported. The fact that the steric hindrance is smaller in 2-acetylthiophenes unsubstituted at position-3 than in acetylbenzenes allows in these cases the formation of Z oximes, which even can predominate on the E oximes in the case of a + M substitution at position-5. In the paper is also shown that the E/Z ratio of 2-acetylthiophene oximes can be deduced from the 1H-nmr spectrum of the crude oxime mixture. 相似文献
44.
45.
46.
Molecular-dynamics simulations for linear quadrupole liquids are presented. The study is carried out for two different molecular lengths at constant density and a number of temperatures and quadrupole moments. All the simulated thermodynamic states correspond to the condensed phases and some of them show typical features of a solid structure. Furthermore, a change on the preferred intermolecular orientation in the liquid phase is observed from a shifted parallel molecular arrangement to a perpendicular orientation as the quadrupole raises. This change depends on the quadrupole moment as well as on the molecular length and is put in relation with the solid structure of different "diatomic" molecules such as nitrogen, ethane, and acetylene. The appearance of a plastic solid phase at low quadrupole moment and density is also justified. A thoroughly discussion about the availability of classical perturbation theories for this kind of systems is presented. 相似文献
47.
Ian PatersonOscar Delgado 《Tetrahedron letters》2003,44(49):8877-8882
A series of novel structural analogues of the potent microtubule-stabilizing anticancer agent discodermolide were synthesised, with modifications in the C16-C20 region to create new oxygenated H-bonding donor/acceptor sites for tubulin binding. By starting from an advanced C9-C24 intermediate, fully synthetic discodermolide analogues, incorporating either an additional hydroxyl group 3, an oxetane 4 or a cyclic carbonate 5, were obtained in 10 or 11 steps by using a versatile aldol construction of the C6-C7 bond. 相似文献
48.
Isobaric vapor–liquid equilibrium (VLE) data of the reactive quaternary system ethanol (1) + water (2) + ethyl lactate (3) + lactic acid (4) have been determined experimentally. Additionally, the reaction equilibrium constant was calculated for each VLE experimental data. The experimental VLE data were correlated using the UNIQUAC equation to describe the chemical and phase equilibria simultaneously. For some of the non-reactive binary systems, UNIQUAC binary interaction parameters were obtained from the literature. The rest of the binary UNIQUAC parameters were obtained by correlating the experimental quaternary VLE data obtained in this work. A maximum pressure azeotrope at high water concentration for the binary reactive system ethyl lactate + water has been calculated. 相似文献
49.
Avelina Arnanz Consuelo Moreno Allan J. Lough Salomé Delgado 《Journal of organometallic chemistry》2004,689(20):3218-3231
The reaction between 2,5-bis(trimethylsilylethynyl)thiophene and Co2(CO)8 or Co2(CO)6(X), (X = dppa, dppm), gave rise to the formation of substituted ethynylcobalt complexes containing one or two Co2(CO)6 or Co2(CO)4(X) units, 2-[Co2(CO)4(X){μ2-η2-(SiMe3)C2}]-5-(Me3SiCC)C4H2S (X = 2CO (1), dppa (3) or dppm (4)) and 2,5-[Co2(CO)4(X){μ2-η2-SiMe3C2}]2C4H2S (X = 2CO (2), dppa (5) or dppm (6)). Desilylation of the non-metallated and metallated alkynes in 3, 4 and 6 occurred on treatment with KOH and tetrabutylammonium fluoride to give 2-[Co2(CO)4(μ-X){μ2-η2-SiMe3C2}]-5-(CCH)C4H2S (X = dppa (7), dppm (8)) and 2,5-[Co2(CO)4(μ-dppm){μ2-η2-HC2}]2C4H2S (9), respectively. Crystals of 6 suitable for single-crystal X-ray diffraction were grown and the molecular structure of this compound is discussed. A comparative electrochemical study of all these complexes is presented by means of the cyclic and square-wave voltammetry techniques. 相似文献
50.
Morales D Pérez J Riera L Riera V Miguel D Mosquera ME García-Granda S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(17):4132-4143
Reactions of the complex [MoCl(eta(3)-C(3)H(4)-Me-2)(CO)(2)(phen)] (1) (phen=1,10-phenanthroline) with potassium arylamides were used to synthesize the amido complexes [Mo(N(R)Ar)(eta(3)-C(3)H(4)-Me-2)(CO)(2)(phen)] (R=H, Ar=Ph, 2 a; R=H, Ar=p-tolyl, 2 b; R=Me, Ar=Ph; 2 c). For 2 b the Mo-N(amido) bond length (2.105(4) A) is consistent with it being a single bond, with which the metal attains an 18-electron configuration. The reaction of 2 b with HOTf affords the amino complex [Mo(eta(3)-C(3)H(4)-Me-2)(NH(2)(p-tol))(CO)(2)(phen)]OTf (3-OTf). Treatment of 3-OTf with nBuLi or KN(SiMe(3))(2) regenerates 2 b. The new amido complexes react with CS(2), arylisothiocyanates and maleic anhydride. A single product corresponding to the formal insertion of the electrophile into the Mo-N(amido) bond is obtained in each case. For maleic anhydride, ring opening accompanied the formation of the insertion product. The reaction of 2 b with maleimide affords [Mo(eta(3)-C(3)H(4)-Me-2)[NC(O)CH=CHC(O)](CO)(2)(phen)] (7), which results from simple acid-base metathesis. The reaction of 2 b with (p-tol)NCO affords [[Mo(eta(3)-C(3)H(4)-Me-2)(CO)(2)(phen)](2)(eta(2)-MoO(4))] (8), which corresponds to oxidation of one third of the metal atoms to Mo(VI). Complex 8 was also obtained in the reactions of 2 b with CO(2) or the lactide 3,6-dimethyl-1,4-dioxane-2,5-dione. The structures of the compounds 2 b, 3-OTf, [Mo(eta(3)-C(3)H(4)-Me-2)[SC(S)(N(H)Ph)](CO)(2)(phen)] (4), [Mo(eta(3)-C(3)H(4)-Me-2)[SC(N(p-tol))(NH(p-tol))](CO)(2)(phen)] (5 a), and [Mo(eta(3)-C(3)H(4)-Me-2)[OC(O)CH=CHC(O)(NH(p-tol))](CO)(2)(phen)] (6), 7, and 8 (both the free complex and its N,N'-di(p-tolyl)urea adduct) were determined by X-ray diffraction. 相似文献