全文获取类型
收费全文 | 4040篇 |
免费 | 98篇 |
国内免费 | 13篇 |
专业分类
化学 | 2665篇 |
晶体学 | 39篇 |
力学 | 55篇 |
数学 | 850篇 |
物理学 | 542篇 |
出版年
2020年 | 61篇 |
2019年 | 51篇 |
2017年 | 34篇 |
2016年 | 59篇 |
2015年 | 84篇 |
2014年 | 72篇 |
2013年 | 123篇 |
2012年 | 141篇 |
2011年 | 140篇 |
2010年 | 116篇 |
2009年 | 103篇 |
2008年 | 174篇 |
2007年 | 163篇 |
2006年 | 134篇 |
2005年 | 151篇 |
2004年 | 120篇 |
2003年 | 95篇 |
2002年 | 77篇 |
2001年 | 43篇 |
2000年 | 57篇 |
1999年 | 44篇 |
1998年 | 39篇 |
1997年 | 38篇 |
1996年 | 35篇 |
1995年 | 40篇 |
1994年 | 41篇 |
1993年 | 51篇 |
1992年 | 49篇 |
1991年 | 34篇 |
1989年 | 36篇 |
1988年 | 42篇 |
1987年 | 47篇 |
1985年 | 53篇 |
1984年 | 62篇 |
1983年 | 40篇 |
1982年 | 30篇 |
1981年 | 43篇 |
1980年 | 53篇 |
1979年 | 34篇 |
1978年 | 37篇 |
1977年 | 36篇 |
1976年 | 29篇 |
1975年 | 33篇 |
1974年 | 33篇 |
1956年 | 40篇 |
1934年 | 33篇 |
1932年 | 37篇 |
1931年 | 29篇 |
1930年 | 30篇 |
1926年 | 28篇 |
排序方式: 共有4151条查询结果,搜索用时 15 毫秒
121.
Dana Kubies Jaroslav Š?udla Rudolf Puffr Antonín Sikora Josef Baldrian Jana Ková?ová Miroslav Šlouf František Rypá?ek 《European Polymer Journal》2006,42(4):888-899
Poly(ε-caprolactone) (PCL) masterbatches with the intercalated and the exfoliated morphology were prepared by ring opening polymerization of ε-caprolactone in the presence of organomodified montmorillonite (MMT) Cloisite 30B. Poly(l-lactide) (PLLA) nanocomposites with Cloisite 30B or PCL masterbatches were prepared by melt blending. The effects of the silicate type, MMT content and the nanocomposite morphology on thermal and mechanical properties of PLLA nanocomposites were examined. The montmorillonite particles in PLLA/Cloisite 30B and PLLA/intercalated masterbatch nanocomposites were intercalated. In contrary to expectations, the exfoliated silicate layers of exfoliated masterbatch were not transferred into the PLLA matrix. Due to a low miscibility of PCL and PLLA, MMT remained in the phase-separated masterbatch domains. The stress-strain characteristics of PLLA nanocomposites, Young modulus E, yield stress σy and yield strain εy, decreased with increasing MMT concentration, which is associated with the increase in PCL content. The expected stiffening effect of MMT was low due to a low aspect ratio of its particles and was obscured by both plastifying effects of PCL and low PLLA crystallinity. Interestingly, in contrast to the neat PLLA, ductility was enhanced in all PLLA/Cloisite 30B materials and in PLLA/masterbatch nanocomposites with low MMT concentrations. 相似文献
122.
Josef Scharf Karl Schlögl Michael Widhalm Johann Lex Werner Tückmantel Emanuel Vogel Franz Pertlik 《Monatshefte für Chemie / Chemical Monthly》1986,117(2):255-267
2,7-Dibromo-1,6-methano[10]anulene (3) and 2,9-Dibromo-syn-1,6:8,13-diimino[14]anulene (9) were quantitatively separated into their enantiomers by chromatography on triacetylcellulose (TAC) in ethanol. X-ray structure analysis (Bijvoet technique) established the chiralities (+)(R)-3 and (+)(S)-9 for the dextrorotatory enantiomers.Comparison of the CD spectra allowed the configurational assignment to further optically active [10] and [14] anulenes which were also accessible by chromatography onTAC. Conversion of (+)(R)-2-bromo-1,6-methano[10]anulene (2) into the corresponding methylester (–)-4 confirmed its previously proposed chirality (–)(R).2,7-Dibromo-1,6-oxido[10]anulene (7) and 2,9-dibromo-syn-diimino[14]anulene (9) are in contrast to the 2,9-dibromo-syn-dioxido[14]anulene (10) optically stable until 250°C. Consequently their inversion barriers are higher than 42 kcal (176 kJ) mol–1.The CD spectra of mono and disubstituted anulenes (with C1 and C2 symmetry, resp.) are compared: For the [10]anulenes theCotton effect around 330 nm seems to be specific for their configuration with a positive effect indicating (S)-chirality and vice versa. Some regularities concerning the chromatographic resolutions are discussed.
Stereochemie planar chialer Verbindungen, 10. Mitt.: Röntgenkristallstruktur und absolute Chiralität überbrückter [10]- und [14] Anulene
Zusammenfassung 2,7-Dibrom-1,6-methano[10]anulen (3) und 2,9-Dibrom-syn-1,6:8,13-diimino[14]anulen (9) wurden durch Chromatographie an Triacetylcellulose (TAC) in Ethanol quantitativ in ihre Enantiomeren getrennt. Röntgenstruktur-analyse (Bijvoet-Technik) bewies für die rechtsdrehenden Enantiomeren die Chiralität (+)(R)-3 bzw. (+)(S)-9.Ein Vergleich der CD-Spektren ermöglichte die Konfigurationszuordnung weiterer optisch aktiver [10]- und [14]Anulene, die gleichfalls durch Chromato-graphie anTAC erhalten worden waren. Umwandlung von (+)(R)-2-Brom-1,6-methano[10]anulen (2) in den entsprechenden Methylester (–)-4 bestätigte dessen schon früher vorgeschlagene Chiralität (–)(R).Dibrom-1,6-oxido[10]anulen (7) und Dibrom-diimino[14]anulen (9) sind im Gegensatz zum Dioxido[14]anulen (10) bis 250°C optisch stabil. Ihre Inver-sionsbarrieren liegen somit über 42 kcal (176kJ) mol–1.Die CD-Spektren von mono- und disubstituierten Anulenen (mit C1 bzw. C2-Symmetrie) werden verglichen: Für die [10]Anulene scheint derCottoneffekt um 330 nm konfigurationsspezifisch zu sein, wobei ein positiver Effekt (S)-Chiralität anzeigt — und vice versa. Einige Regelmäßigkeiten bezüglich der chromatographischen Enantiomerentrennung werden diskutiert.相似文献
123.
A method is described for the potentiometric titration of milligram quantities of the uranium(IV) ion in the presence of iron. This is accomplished by complexing the iron with 1.10-phcnanthroline. The uranium can then be titrated with standard ceric sulfate without interference from the iron. 相似文献
124.
Covalent attachment of solvent-sensitive fluorescent dyes to proteins is a powerful tool for studying protein conformational changes, ligand binding, or posttranslational modifications. We report here new merocyanine dyes that make possible the quantitation of such protein activities in individual living cells. The quantum yield of the new dyes is sharply dependent on solvent polarity or viscosity, enabling them to report changes in their protein environment. This is combined with other stringent requirements needed in a live cell imaging dye, including appropriate photophysical properties (excitation >590 nm, high fluorescence quantum yield, high extinction coefficient), good photostability, minimal aggregation in water, and excellent water solubility. The dyes were derivatized with iodoacetamide and succinimidyl ester side chains for site-selective covalent attachment to proteins. A novel biosensor of Cdc42 activation made with one of the new dyes showed a 3-fold increase in fluorescence intensity in response to GTP-binding by Cdc42. The dyes reported here should be useful in the preparation of live cell biosensors for a diverse range of protein activities. 相似文献
125.
Jiří Horský Josef Pitha 《Journal of inclusion phenomena and macrocyclic chemistry》1994,18(3):291-300
The stability constants were measured of inclusion complexes formed from aromatic amino acids and their oligopeptides with - and-cyclodextrin, hydroxypropyl-cyclodextrin, and partially methylated-cyclodextrin. The method of competitive spectrophotometry withp-nitrophenol as a competing reagent was used, and measurements were made at pH 7.4-Cyclodextrin formed complexes of higher stability than the other hosts. The stability of complexes of oligopeptides containing L-phenylalanine was invariably higher than that of L-phenylalanine itself. A model for interaction of proteins with cyclodextrins is proposed, in which the most stable complexes are formed when the native functional form of proteins is unfolded and the nonpolar residues that are buried inside the structure are exposed to water. The complexation of the unfolded structure favors its formation; thus thermal denaturation of proteins is easier in the presence of cyclodextrins. On the other hand, this complexation prevents the intermolecular association of unfolded structures by noncovalent hydrophobic bonding between the exposed nonpolar residues; furthermore, the unfolded complexed forms may revert to the native functional form. This prevention of intermolecular association may explain the stabilizing effect of cyclodextrins on solutions of proteins: a return to the native form is achieved more easily from the complexed, unfolded form than from the unfolded, aggregated forms.Dedicated to Professor József Szejtli. 相似文献
126.
Wind JJ Papp L Happel M Hahn K Andriole EJ Poutsma JC 《Journal of the American Society for Mass Spectrometry》2005,16(7):1151-1161
A new version of the single-reference-extended kinetic method is presented in which direct entropy correction is incorporated. Results of calibration experiments with the monodentate base pyridine and the bidentate base ethylenediamine are presented for which the method provides proton affinities in excellent agreement with published values and reasonable predictions for the protonation entropies. The method is then used to determine the proton affinity and protonation entropy of the non-protein amino acid beta-oxalylaminoalanine (BOAA). The PA of BOAA is found to be 933.1 +/- 7.8 kJ/mol and a prediction for the protonation entropy of -39 J mol(-1) K(-1) is also obtained, indicating a significant degree of intramolecular hydrogen bonding in the protonated form. These results are supported by hybrid density functional theory calculations at the B3LYP/6-311++G**//B3LYP/6-31+G* level. They indicate that the preferred site of protonation is the alpha-nitrogen atom (PA = 935.0 kJ/mol) and that protonated BOAA has a strong hydrogen bond between the hydrogen on the alpha-amino group and one of the carbonyl oxygen atoms on the side chain. 相似文献
127.
Max Winter Karl H. Schulte-Elte Alain Velluz Josef Limacher Wilhelm Pickenhagen Günther Ohloff 《Helvetica chimica acta》1979,62(1):131-134
Aroma Constituents of the Purple Passion Fruit. Two New Edulan Derivatives The isolation of (2R*, 4S*, 4aS*, 8aS*)-4,4a-epoxy-4,4a-dihydroedulan ( 1 ), and (2R*, 3S*, 8aS*)-3-hydroxyedulan ( 2 ), two new constituents of the purple passion-fruit (Passiflora edulis SIMS ), is reported. Racemic epoxide 1 was synthesized by oxidation of edulan 6 with peracidic acid, and racemate of alcohol 2 was obtained by reduction of ketone 7 , one of the chromic acid oxidation-products of edulan 6 . 相似文献
128.
Contributions to the Chemistry of Phosphorus. 143. Li4P26 and Na4P26, the First Salts with Hexacosaphosphid(4?) Ions The hexacosaphosphides Li4P26 ( 1 ) and Na4P26 ( 2 ) are formed besides other polyphosphides in the reaction of white phosphorus with lithium dihydrogenphosphide or sodium. 1 also results from the decomposition of Li2HP7 in tetrahydrofuran at room temperature and can be obtained pure as a crystalline solvent adduct Li4P26 · 16 THF. According to 2D?31P-NMR spectroscopic investigations the P264? ion is a conjucto-phosphane of two P7(5)?-and two P9(3)?-unit groups with structures analogous to norbornane and deltacyclane, respectively. 相似文献
129.
Klaus Grasshoff und Harry Hahn 《Fresenius' Journal of Analytical Chemistry》1962,186(1):147-153
Zusammenfassung Es wird eine polarographische Methode zur Bestimmung von Molybdän in Stahl beschrieben. Als Trägerelektrolyt wird 0,1 m Citronensäure verwendet. Bei pH 2 treten zwei Stufen mit einem Halbstufenpotential von –0,27 und –0,65 V auf. Der Diffusionsstrom bzw. Spitzenstrom beider Stufen ist gut ausgebildet und gut reproduzierbar. Eisen sowie die üblichen in Stählen vorkommenden Elemente stören die Bestimmung nicht. Die Brauchbarkeit und die Genauigkeit der Methode wird an vier verschiedenen Legierungen mit Gehalten von 0,3–1,3% Molybdän demonstriert.V. Mitteilung: Grasshoff, K., u. H. Hahn: diese Z. 186, 132 (1962).Wir danken der Deutschen Forschungsgemeinschaft sowie dem Fonds der Chemischen Industrie für die Unterstützung dieser Arbeit. 相似文献
130.
H. Schumann F. H. Grlitz F. E. Hahn J. Pickardt Changtao Qian Zuowei Xie 《无机化学与普通化学杂志》1992,609(3):131-138
The partial hydrolysis of [O(CH2CH2C5H4)2]Y(C5H4CH3) 1 , [O(CH2CH2C5H4)2]Y(C5H5) 3 , and [O(CH2CH2C5H4)2]Ho(C5H4CH3) 5 results in the formation of [O(CH2CH2CH2C5H4)2Y(μ-OH)2]2 2 , (C5H5)3Y(OH2) 9 and (MeC5H4)3Ho(OH2) 11 . The new compounds have been characterized by elemental analyses, IR and NMR spectra. The X-ray structural analyses shows 2 to be monoclinic, space group P21/n with a = 1146.0(3), b= 1046.6(3), c = 1514.9(3) pm, β = 94.83(2)°. The molecular structure shows bridging hydroxyl groups with a mean distance Y? O = 223.8(3) pm. 11 crystallizes in the cubic space group 14 3d with a = 1847.9(3)pm with Z = 16 molecules per unit cell. The molecules posses symmetry C3-3, the coordination is trigonal pyramidal with three methylcyclopentadienyl anions and one water molecule as ligands. The distance Ho? O is 231 pm. 相似文献