全文获取类型
收费全文 | 43941篇 |
免费 | 1831篇 |
国内免费 | 1470篇 |
专业分类
化学 | 31572篇 |
晶体学 | 349篇 |
力学 | 825篇 |
综合类 | 10篇 |
数学 | 6080篇 |
物理学 | 8406篇 |
出版年
2023年 | 316篇 |
2022年 | 566篇 |
2021年 | 778篇 |
2020年 | 723篇 |
2019年 | 726篇 |
2018年 | 824篇 |
2017年 | 810篇 |
2016年 | 1576篇 |
2015年 | 1292篇 |
2014年 | 1367篇 |
2013年 | 2906篇 |
2012年 | 3180篇 |
2011年 | 3463篇 |
2010年 | 1983篇 |
2009年 | 2050篇 |
2008年 | 2705篇 |
2007年 | 2636篇 |
2006年 | 2368篇 |
2005年 | 2235篇 |
2004年 | 2245篇 |
2003年 | 1648篇 |
2002年 | 1524篇 |
2001年 | 939篇 |
2000年 | 806篇 |
1999年 | 607篇 |
1998年 | 512篇 |
1997年 | 414篇 |
1996年 | 504篇 |
1995年 | 380篇 |
1994年 | 323篇 |
1993年 | 382篇 |
1992年 | 340篇 |
1991年 | 241篇 |
1990年 | 240篇 |
1989年 | 187篇 |
1988年 | 179篇 |
1987年 | 178篇 |
1986年 | 169篇 |
1985年 | 268篇 |
1984年 | 246篇 |
1983年 | 175篇 |
1982年 | 170篇 |
1981年 | 157篇 |
1980年 | 132篇 |
1979年 | 133篇 |
1978年 | 106篇 |
1977年 | 103篇 |
1976年 | 98篇 |
1975年 | 97篇 |
1973年 | 101篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
911.
J. O. Jílek V. Seidlová E. Svátek M. Protiva 《Monatshefte für Chemie / Chemical Monthly》1965,96(1):182-207
Zusammenfassung Im Rahmen der Suche nach neuen neurotropen und psychotropen Substanzen, besonders nach antidepressiv wirkenden Psychopharmaka, wurde eine systematische präparative Arbeit in den Gruppen der 10-substituierten Derivate des 10,11-Dihydrodibenzo[a,d]cycloheptens (I) und des 10,11-Dihydrodibenzo[b,f]-thiepins (II) unternommen. Im ersten Fall war die Ausgangssubstanz das Keton XIV, das mit üblichen Methoden zum basischen Äther XVI, zu Aminen und Derivaten XVIII–XXII und schließlich in dieMannich-Base XXVI übergeführt wurde. DieBeckmannsche Umlagerung des Oxims XVII eröffnete den Weg zu Derivaten eines neuen Systems, des 5,6,7,12-Tetrahydrodibenz[b,e]azocins (Verbindungen XXVIII, XXX und XXXI). Auch im zweiten Fall bildete das entsprechende Keton (XXXVIII) die Schlüsselsubstanz, die einerseits zu Aminen mit der Aminogruppe in der Seitenkette (XXXIX, XL, XLII, LV, LVI), anderseits zu Aminen mit der direkt am Skelett haftenden Aminogruppe (XLIV–LIII) umgesetzt wurde. Außer den angeführten Aminen wurde in allen drei Gruppen eine Reihe von neutralen Verbindungen hergestellt (Zwischenprodukte und Nebenprodukte), deren Struktur meistens mit Hilfe der Spektren geklärt wurde. Die vorläufigen Ergebnisse der pharmakologischen Prüfung einiger Produkte deuten interessante Wirksamkeit an, besonders vom Standpunkt der erwarteten neurotropen und psychotropen Eigenschaften aus.
mit technischer Hilfe von
Herrn Professor Dr.Hermann Bretschneider zum 60. Geburtstag gewidmet
4. Mitt.:J. O. Jílek, K. Pelz, D. Pavlíková undM. Protiva, Coll. Czechoslov. Chem. Commun.30, im Druck (1965). 相似文献
In the effort to find new neurotropic and psychotropic substances a systematic chemical study was undertaken in the groups of the 10-substituted derivatives of 10,11-dihydrodibenzo[a,d]-cycloheptene (I) and 10,11-dihydrodibenzo[b,f]thiepine (II). In the first case the ketone XIV was transformed by usual methods into the basic ether XVI, to the amines and derivatives XVIII–XXII, and to theMannich base XXVI. TheBeckmann rearrangement of the oxime XVII opened the way to derivatives of a new system — 5,6,7,12-tetrahydrodibenz[b,e]azocine (compounds XXVIII, XXX and XXXI). In the second case (derivatives of II) the syntheses started from the ketone XXXVIII and two series of amines were prepared: with the amino group in the side chain (XXXIX, XL, XLII, LV, LVI) and with the amino group attached directly to the skeleton (XLIV–LIII). In addition to the amines several neutral compounds in either group were synthesized (intermediates and byproducts), the structure of which was elucidated mainly by means of the spectra. Preliminary results of the pharmacological testing show a rather important degree of activity of some substances, especially in the line of the expected neurotropic and psychotropic properties.
mit technischer Hilfe von
Herrn Professor Dr.Hermann Bretschneider zum 60. Geburtstag gewidmet
4. Mitt.:J. O. Jílek, K. Pelz, D. Pavlíková undM. Protiva, Coll. Czechoslov. Chem. Commun.30, im Druck (1965). 相似文献
912.
Alkaloids such as cinchonidine, quinine and N-methylephedrine have been N-alkylated using polymeric benzyl halides or co-polymerized and then N-alkylated, thus affording a series of polymer-supported chiral ammonium salts which have been employed as phase-transfer catalysts in the asymmetric benzylation of an N-(diphenylmethylene)glycine ester. These new polymeric catalysts can be easily recovered by simple filtration after the reaction and reused. The best ee's were achieved when Merrifield resin-anchored cinchonidinium ammonium salts were employed. 相似文献
913.
Íñigo X. García-Zubiri Gustavo González-Gaitano Miguel Sánchez Josér; Ramón Isasi 《Journal of inclusion phenomena and macrocyclic chemistry》2004,49(3-4):291-302
The inclusion complexes of β-cyclodextrin (β-CD) with naphthalene and some of its derivatives in the solid state have been studied by infrared spectroscopy. Digital subtraction, deconvolution and curve fitting have been used to investigate the interactions between the naphthalene derivatives andβ-CD. Several preparation methods for the solid dispersions have been tested, using FTIR as an effective tool to evaluate the interactions at the molecular level. The effects of temperature and humidity on the spectra have been also analyzed. A carbonyl moiety in the guest molecule can increase the stability of the complex by establishing specific interactions with the hydroxyl groups of the CD cavity rims. The stability of the complexes is higher for 2-naphthylacetate than that for 1-naphthyl acetate, andso is the degree of association of its carbonyl groups. On the other hand, 2-acetylnaphthaleneforms very stable inclusioncomplexes although its carbonyl groups appear to be significantly less associated. 相似文献
914.
Platas-Iglesias C Esteban-Gómez D Enríquez-Pérez T Avecilla F de Blas A Rodríguez-Blas T 《Inorganic chemistry》2005,44(7):2224-2233
Compounds of formula [Pb(L2)(NCS)2] (1) and [Pb(L4)(SCN)2] (2) (where L2 is the lariat crown ether N,N'-bis(3-aminobenzyl)-4,13-diaza-18-crown-6 and L4 is the Schiff-base lariat crown ether N,N'-bis(3-(salicylaldimino)benzyl)-4,13-diaza-18-crown-6) were isolated and structurally characterized by X-ray diffraction analyses. The X-ray crystal structures of both compounds show the metal ion coordinated to the six donor atoms of the crown moiety, leaving the corresponding pendant arms uncoordinated. The coordination sphere of lead(II) is completed by two thiocyanate groups that coordinate either through their nitrogen (1) or sulfur (2) atoms. The organic receptor adopts a syn conformation in 1, while in 2 it shows an anti conformation. To rationalize these unexpected different conformations of the L2 and L4 receptors in compounds 1 and 2, as well as the different binding modes found for the thiocyanate ligands, we have carried out theoretical calculations at the DFT (B3LYP) level. These calculations predict the syn conformation being the most stable in both 1 and 2 complexes. So, the anti conformation found for 2 in the solid state is tentatively attributed to the presence of intermolecular pi-pi interactions between phenol rings, for which the dihedral angle between the least-squares planes of both rings amounts to 2.6 degrees and the distance between the center of both rings is 3.766 A. On the other hand, the analysis of the electronic structure has revealed that the Pb-ligand bonds present highly ionic character in this family of compounds. They also suggest a greater transfer of electron density from the NCS- ligands when they coordinate through the less electronegative S atom. The Pb-SCN covalent bond formation mainly occurs due to an effective overlap of the occupied 3p z orbitals of the S atoms and the unoccupied 6p z AO of the Pb atom, while the Pb-NCS bonding interaction is primarily due to the overlap of the 6s and 7s AO of Pb with sp(1.10) hybrids of the N donor atoms. Our electronic structure calculations can rationalize the different coordination of the thiocyanate groups in compounds 1 and 2: the simultaneous formation of two Pb-SCN bonds is more favorable for S-Pb-S angles close to 180 degrees , for which the overlap between the occupied 3p z orbitals of the S atoms and the unoccupied 6 pz AO of the Pb atom is maximized. 相似文献
915.
Alibés R Bayón P de March P Figueredo M Font J García-García E González-Gálvez D 《Organic letters》2005,7(22):5107-5109
[reaction: see text] A highly versatile approach to the enantioselective synthesis of securinega alkaloids is presented. Crucial steps are a palladium-catalyzed enantioselective imide alkylation, a vinylogous Mannich reaction, and a ring-closing metathesis process. Through this strategy, the synthesis of (-)-norsecurinine has been accomplished in nine steps and 11% overall yield. 相似文献
916.
Sponer JE Spacková N Kulhanek P Leszczynski J Sponer J 《The journal of physical chemistry. A》2005,109(10):2292-2301
Large RNA molecules exhibit an astonishing variability of base-pairing patterns, while many of the RNA base-pairing families have no counterparts in DNA. The cis Watson-Crick/sugar edge (cis WC/SE) RNA base pairing is investigated by ab initio quantum chemical calculations. A detailed structural and energetic characterization of all 13 crystallographically detected members of this family is provided by means of B3LYP/6-31G and RIMP2/aug-cc-pVDZ calculations. Further, a prediction is made for the remaining 3 cis WC/SE base pairs which are yet to be seen in the experiments. The interaction energy calculations point at the key role of the 2'-OH group in stabilizing the sugar-base contact and predict all 16 cis WC/SE base-pairing patterns to be nearly isoenergetic. The perfect correlation of the main geometrical parameters in the gas-phase optimized and X-ray structures shows that the principle of isosteric substitutions in RNA is rooted from the intrinsic structural similarity of the isolated base pairs. The present quantum chemical calculations for the first time analyze base pairs involving the ribose 2'-OH group and unambiguously correlate the structural information known from experiments with the energetics of interactions. The calculations further show that the relative importance and absolute value of the dispersion energy in the cis WC/SE base pairs are enhanced compared to the standard base pairs. This may by an important factor contributing to the strength of such interactions when RNA folds in its polar environment. The calculations further demonstrate that the Cornell et al. force field commonly used in molecular modeling and simulations provides satisfactory performance for this type of RNA interactions. 相似文献
917.
J. Kučera J. Kučera A. R. Byrne A. R. Byrne J. Mizera J. Mizera M. Lučaníková M. Lučaníková Z. Řanda Z. Řanda 《Journal of Radioanalytical and Nuclear Chemistry》2006,269(2):251-257
Summary Radiochemical neutron activation procedures using liquid-liquid extraction with tetraphenylarsonium chloride in chloroform
from 1M HCl and solid extraction with ALIQUAT 336 incorporated in a polyacrylonitrile binding matrix from 0.1M HCl were developed
for accurate determination of rhenium in biological and environmental samples at the sub-ng . g-1 level. Concentrations of Re in the range of 0.1 to 2.4 ng . g-1 were determined in several botanical reference materials (RM), while in a RM of road dust a value of ~10 ng . g-1 was found. Significantly elevated values of Re, up to 90 ng . g-1 were found in seaweed (brown algae). Results for Re in the brown algae Fucus vesiculosus in which elevated 99Tc values had previously been determined suggested possible competition between Re and Tc in the accumulation process. 相似文献
918.
Infant formula and powdered milk samples were suspended in a medium containing 20% ethanol, 0.65% nitric acid, 6% hydrogen peroxide and 0.1% ammonium dihydrogenphosphate and directly introduced in the electrothermal atomizer. Liquid milk samples were diluted with this suspension solution. The build-up of carbonaceous residues inside the atomizer was avoided by using a combination of hydrogen peroxide and nitric acid. Fast programs were used to simplify the heating cycles. Calibration was carried out using aqueous standards and the detection limits for copper and zinc were found to be 70 and 15 pg, respectively. The metal contents of several milk samples obtained by direct introduction of the samples agree with those obtained by means of a conventional procedure based on the total dissolution of the samples. The reliability of the methods was also confirmed by analyzing three certified reference materials. The free and protein binding fractions were measured by ultrafiltration membrane permeability of the milk samples. 相似文献
919.
I. I. Chernobaev M. N. Yakubovich A. I. Tripol’skií N. V. Pavlenko V. L. Struzhko 《Theoretical and Experimental Chemistry》1997,33(1):38-40
Methane is formed in the Fischer-Tropsch synthesis under real conditions both through intermediates leading to chain propagation
and by hydrogenation of surface carbon.
L. V. Pisarzhevskii Institute of Physical Chemistry, National Academy of Sciences of Ukraine, Prospekt Nauki 31, 252039 Kiev,
Ukraine. Translated from Teoreticheskaya i éksperimental’naya Khimiya, No. 1, pp. 41–43, January–February, 1996. 相似文献
920.
We have studied the operational conditions which allow the synthesis gas to hydrocarbon transformation in only one step using Pd supported over an amorphous silica-alumina catalyst. The increase of temperature, pressure and time factor favors carbon monoxide conversion. Methanol synthesis reaction can be considered as the limiting step of the overall process. The product distribution is governed by the reaction medium (type and distribution of active sites and the presence of hydrogen). 相似文献