全文获取类型
收费全文 | 3487篇 |
免费 | 90篇 |
国内免费 | 9篇 |
专业分类
化学 | 2436篇 |
晶体学 | 17篇 |
力学 | 58篇 |
数学 | 341篇 |
物理学 | 734篇 |
出版年
2020年 | 51篇 |
2019年 | 36篇 |
2016年 | 53篇 |
2015年 | 65篇 |
2014年 | 67篇 |
2013年 | 116篇 |
2012年 | 136篇 |
2011年 | 130篇 |
2010年 | 85篇 |
2009年 | 105篇 |
2008年 | 137篇 |
2007年 | 129篇 |
2006年 | 145篇 |
2005年 | 118篇 |
2004年 | 107篇 |
2003年 | 87篇 |
2002年 | 95篇 |
2001年 | 105篇 |
2000年 | 93篇 |
1999年 | 51篇 |
1998年 | 51篇 |
1997年 | 39篇 |
1996年 | 62篇 |
1995年 | 41篇 |
1994年 | 59篇 |
1993年 | 50篇 |
1992年 | 65篇 |
1991年 | 44篇 |
1990年 | 45篇 |
1989年 | 38篇 |
1988年 | 36篇 |
1987年 | 46篇 |
1986年 | 36篇 |
1985年 | 41篇 |
1984年 | 37篇 |
1983年 | 41篇 |
1982年 | 49篇 |
1981年 | 31篇 |
1979年 | 39篇 |
1978年 | 39篇 |
1977年 | 34篇 |
1976年 | 30篇 |
1975年 | 32篇 |
1973年 | 28篇 |
1972年 | 24篇 |
1971年 | 28篇 |
1969年 | 30篇 |
1968年 | 27篇 |
1967年 | 30篇 |
1966年 | 25篇 |
排序方式: 共有3586条查询结果,搜索用时 987 毫秒
101.
Solid-state 2H NMR spectroscopy is a well-established and versatile method to study molecular orientation and dynamics in selectively deuterated samples. Herein, we introduce a 2D 2H double-quantum (DQ) NMR experiment performed under fast magic-angle spinning with a slight offset of the magic angle (OMAS). The experiment combines 2H chemical-shift resolution with DQ-filtered quasistatic 2H line shapes. In this way, it is possible to separate 2H resonances and to independently determine 2H quadrupole couplings at multiple sites. While 2H chemical shifts are resolved in the 2H DQ dimension, the quadrupole parameters can be obtained from characteristic line shapes which are reintroduced in the second dimension by the magic-angle offset. The 2D 2H DQ OMAS experiment is demonstrated on L-histidine which was deuterated at multiple sites by recrystallisation from D2O. 相似文献
102.
We report on the catalytic effects by alkali-metal ions in the ethanolysis of p-nitrophenyl diphenyl phosphate, in continuation of our studies on alkali-metal ion catalysis and inhibition in nucleophilic displacement reactions at carbon, phosphorus and sulfur centres. The following selectivity order of catalytic reactivity was observed for nucleophilic displacement at the phosphorus center with p-nitrophenoxide as leaving group: Li+ > Na+ > K+ > Cs+. A minor reaction pathway with phenoxide leaving was also found. The kobs data have been dissected into reaction pathways by free ions (kEtO) and by ion pairs (kMOEt), with the latter being dominant, in a 4-membered transition-state. Further analysis is given in terms of initial-state and transition-state stabilization by the alkali-metal ions in terms of the Eisenman model (electrostatic interaction vs. desolvation). Results of ab-initio MO calculations are presented based on interaction between M+ and a model bipyramidal phosphorane intermediate and compared with the sulfurane analogue. 相似文献
103.
A method for separation and chemical identification of products formed in nuclear reactions or nuclear decay is to slow down the recoil products in a gas and to transport them to a trap, where a detecting system is arranged. The sources for the recoil products are252Cf and224Ra. As transport phase we used nitrogen or argon and added chemical reagents such as methyl and ethyl radicals, chlorine, oxygen, carbon monoxide or methane. The chemical additives lead to selective and fast separation of certain elements. As examples the results of two experiments are presented:224Ra with ethyl radicals, and252Cf with chlorine-oxygen-nitrogen mixtures. The registration of the recoil products at the trap was measured as a function of temperature, pressure and composition of the reactive gas. 相似文献
104.
A two-step protocol for the first chemoselective cleavage of 2-hydroxy acid amides has been developed. Mesylation of the model substrate 2-(hydroxypropionylamino)-4-methylpentanoic acid methyl ester (11) followed by treatment with N-ethylthiourea (13) allows cleavage of 2-hydroxy acid amides under smooth conditions. Successful application of this methodology to the open-chain transesterification product 15 (methylester) of the cyclic heptadepsipeptide HUN-7293, a potent inhibitor of inducible cell adhesion molecule expression, delivered the corresponding hexapeptide 18 with unprotected N-terminus in 70-75% yield. This result demonstrates that the protocol developed even works in the presence of an ester and several methylated and unmethylated amide bonds. Finally, a sequence of ligation of methyl D-dehydroglutaminate (20) to the C-terminus of the saponification product 21, followed by the degradation protocol and ring closure, allowed chemical "point mutation" at the DGCN site affording the aza analogue of HUN-7293 (24) in 15% overall yield. To the best of our knowledge this is the first report on chemoselective cleavage of 2-hydroxy acid amides. 相似文献
105.
N. Pilz P. Hoffmann K. H. Lieser W. Dams K. H. Nelges 《Fresenius' Journal of Analytical Chemistry》1989,335(7):695-697
Summary A non-destructive method and an experimental set-up are described by which the Pu content in UO2/PuO2 mixed oxide (MOX) pellets and in fuel rods, respectively, can be determined. The K-lines of Pu are excited by external -radiation (192Ir) and measured by a high-purity Ge detector. A calibration curve is presented and the detection limits are plotted as function of the time of measuring.
Dedicated to Prof. Dr. G. Tölg on the occasion of his 60th birthday 相似文献
Zerstörungsfreie bestimmung von plutonium in kernbrennstoff-stäben und -pellets
Dedicated to Prof. Dr. G. Tölg on the occasion of his 60th birthday 相似文献
106.
Ernst Schaumann Erwin Kausch Karl-Heinz Klaska Rolf Klaska Otto Jarchow 《Journal of heterocyclic chemistry》1977,14(5):857-860
The crystal and molecular structures of the cycloadduct from isopropyl[α-(dimethylthio-carbamoyl)isopropyl]carbodiimide and methyl isothiocyanate were determined by single-crystal X-ray methods. The product was established to be 2-(1-isopropyl-3,5-dimethyl-4,6-dithioxo-hexahydro-1,3,5-triazine-2-ylidenamino)-N,N-dimethylthioisoburyramide, in which contrary to expectations based on hybridisation the heterocyclic ring adopts a boat conformation. 相似文献
107.
W. A. Schönfeldt P. H. Mokler D. H. H. Hoffmann A. Warczak 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1986,4(2):161-176
For 3.6 MeV/u Sm q+ projectiles a hump in the projectile (L l +L α) x-ray emission cross section is seen as a function of charge stateq for highq with 46≦q≦52 (closed incomingL shell). This hump is attributed to the Resonant electron Transfer from the Xe target atom with simultaneous Excitation of anL 3-shell electron to theM shell. The cross section for thisL 3-shell RTE process has values up to 2·10?19 cm2, which is seen in single spectra already. To verify the existence of theL-shell RTE process for the studied collision system, extensive calculations have been carried out. Especially theL 3-shell fluorescence yield for the radiative stabilization process in the highly-charged projectile has been considered. Our calculatedq-dependent cross sections for the RTE process support the given interpretation. 相似文献
108.
1,3-Dimethylated hydrocarbon segments occur frequently as structural elements in polyketide natural products. The (13)C NMR chemical shifts of a series of model compounds containing such segments can be well reproduced by a combination of molecular mechanics and SOS-DFPT/IGLO calculations. (13)C NMR chemical shifts are calculated on MM3 geometries and are Boltzmann weighted according to the MM3 energies. On the basis of the resulting thermally averaged chemical shifts, all diastereomers of the model compounds can be unequivocally distinguished. Significant differences in chemical shifts occur at methyl groups and methylene groups that are adjacent to a single stereogenic center. The method is applied to predict the relative configuration of two stereocenters in the side chains of two natural products, sambutoxin and the bradykinin inhibitor L-755,897. 相似文献
109.
Efforts are described to design simple, fully flexible but conformationally preorganised omega-hydroxy-nonanoic acids that could serve as the conformation controlling unit in analogues of the potent protein-kinase C activator aplysiatoxin. Such analogues are macrodilactones incorporating the designed omega-hydroxy-nonanoic acid and 3,4-dihydroxy-pentanoic acid, which contains the pharmacophoric groups. The design process (replacement of CH(2) groups by an oxygen atom, annelation of a six-membered ring and placement of alkyl substituents) of the omega-hydroxy-nonanoic acids was monitored by force-field calculations. In the end of this process simple analogues of aplysiatoxin are proposed in which the proper disposition of the pharmacophoric groups is secured by a conformationally flexible but preorganised template structure as part of the macrodilactone ring. 相似文献
110.
Summary A simple procedure for the determination of salicylanilide and paratoluene sulphonamide in paints has been worked out. Salicylanilide is determined by ethanol extraction and subsequent measuring of the UV-absorption spectrum, and also by determining the nitrogen content according to Kjeldahl. For the determination of para-toluene sulphonamide three different methods are employed, viz., the Kjeldahl determination of the nitrogen content, the determination of the sulphur content by burning the sample in an oxygen flask and subsequent determination of sulphate, and also by measuring the UV-absorption spectrum, the last method being only a semi-quantitative check.
Part II: Hoffmann, E., B. Bursztyn, and A. Saracz: Z. analyt. Chem. 207, 432 (1965). 相似文献
Zusammenfassung Ein einfaches Verfahren zur Bestimmung von Salicylanilid und p-Toluolsulfonamid in Anstrichfarben wird beschrieben. Die Salicylanilidbestimmung erfolgt durch Äthanolextraktion und anschließende Messung des UV-Absorptionsspektrums sowie durch Stickstoffbestimmung nach Kjeldahl. Zur Bestimmung von p-Toluolsulfonamid dient ebenfalls die Stickstoffbestimmung nach Kjeldahl, sowie die Schwefelbestimmung durch Verbrennung in Sauerstoff mit anschließender Sulfatbestimmung und auch die UV-Absorptionsspektrometrie, letztere jedoch nur als halb quantitative Kontrollmethode.
Part II: Hoffmann, E., B. Bursztyn, and A. Saracz: Z. analyt. Chem. 207, 432 (1965). 相似文献