全文获取类型
收费全文 | 1061篇 |
免费 | 34篇 |
国内免费 | 14篇 |
专业分类
化学 | 744篇 |
晶体学 | 9篇 |
力学 | 8篇 |
数学 | 143篇 |
物理学 | 205篇 |
出版年
2022年 | 10篇 |
2021年 | 14篇 |
2020年 | 14篇 |
2019年 | 10篇 |
2018年 | 16篇 |
2017年 | 16篇 |
2016年 | 31篇 |
2015年 | 34篇 |
2014年 | 33篇 |
2013年 | 55篇 |
2012年 | 60篇 |
2011年 | 60篇 |
2010年 | 53篇 |
2009年 | 36篇 |
2008年 | 68篇 |
2007年 | 54篇 |
2006年 | 45篇 |
2005年 | 54篇 |
2004年 | 36篇 |
2003年 | 40篇 |
2002年 | 43篇 |
2001年 | 10篇 |
2000年 | 12篇 |
1998年 | 12篇 |
1997年 | 7篇 |
1996年 | 11篇 |
1995年 | 7篇 |
1994年 | 12篇 |
1992年 | 8篇 |
1991年 | 6篇 |
1990年 | 7篇 |
1989年 | 7篇 |
1988年 | 5篇 |
1985年 | 12篇 |
1984年 | 9篇 |
1982年 | 8篇 |
1981年 | 6篇 |
1980年 | 7篇 |
1979年 | 5篇 |
1978年 | 5篇 |
1976年 | 6篇 |
1975年 | 9篇 |
1973年 | 6篇 |
1972年 | 5篇 |
1959年 | 12篇 |
1958年 | 23篇 |
1957年 | 16篇 |
1956年 | 14篇 |
1955年 | 11篇 |
1954年 | 18篇 |
排序方式: 共有1109条查询结果,搜索用时 15 毫秒
51.
Arrival time distributions of product ions reveal isomeric ratio of deprotonated molecules in ion mobility–mass spectrometry of hyaluronan‐derived oligosaccharides 下载免费PDF全文
Martina Hermannová Andreea‐Maria Iordache Kristína Slováková Vladimír Havlíček Helena Pelantová Karel Lemr 《Journal of mass spectrometry : JMS》2015,50(6):854-863
Hyaluronic acid is a naturally occurring linear polysaccharide with substantial medical potential. In this work, discrimination of tyramine‐based hyaluronan derivatives was accessed by ion mobility–mass spectrometry of deprotonated molecules and nuclear magnetic resonance spectroscopy. As the product ion mass spectra did not allow for direct isomer discrimination in mixture, the reductive labeling of oligosaccharides as well as stable isotope labeling was performed. The ion mobility separation of parent ions together with the characteristic fragmentation for reduced isomers providing unique product ions allowed us to identify isomers present in a mixture and determine their mutual isomeric ratio. The determination used simple recalculation of arrival time distribution areas of unique ions to areas of deprotonated molecules. Mass spectrometry data were confirmed by nuclear magnetic resonance spectroscopy. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
52.
Summary The addition of dienes to the system [(Cp2TiCl)2] LiAlH4toluene changes the system so that the complex [Cp2TiAlH4] is quantitatively formed instead of a titanocene hydride — aluminium hydride cluster. The complex [Cp2TiAlH4] is further converted into 3-allyltitanocene derivatives ([Cp2TiA]) if the diene structure is suitable for formation of stable [Cp2TiA] compounds and if the equilibrium [Cp2TiAlH4]+diene[Cp2TiA]+A1H3 is shifted towards the formation of [Cp2TiA] by the excess of diene. All the compounds [Cp2TiA] exhibit high-resolution e.s.r. spectra at g=1.993, showing interaction of the unpaired electron with the cyclopentadienyl and 3-allyl protons. The e.s.r. spectra clearly reveal the presence of alkyl substituents atsyn-1,3-positions of 3-allyl ligand, and show a triplet of multiplets for (3-allyl)titanocene, doublets of multiplets for (1-alkyl-3-allyl)titanocenes and single multiplets for (1,3-dialkyl-3-allyl)-titanocenes. thermal isomerization of (1,3-dimethyl-3-allyl)-titanocene and (1-methyl-3-ethyl-3-allyl)titanocene, hitherto considered as the stable Cp2TiA compounds, into (1-alkyl-3-allyl)titanocenes was confirmed by e.s.r. and electronic absorption spectroscopy as well as by chemical means. 相似文献
53.
Jeremy P. Scott Deborah C. Hammond Elizabeth M. Beck Karel M.J. Brands Antony J. Davies Ulf-H. Dolling Derek J. Kennedy 《Tetrahedron letters》2004,45(17):3345-3348
The efficient preparation of 4-aryl-4-phenylsulfonyl cyclohexanones, containing a quaternary sulfone-bearing carbon centre, is described. Their synthesis proceeds in 38-78% overall yield by way of three steps: (i) sulfinate alkylation; (ii) methylenation; and (iii) regioselective Diels-Alder condensation with 2-trimethylsiloxybutadiene. The scope and limitations of the one-pot Mannich-type methylenation described were examined. 相似文献
54.
Michal Karady Ondřej Novák Aleš Horna Miroslav Strnad Karel Doležal 《Electroanalysis》2011,23(12):2898-2905
On‐line LC‐EC/ESI‐MS has been established as a fast and simple method to mimic some types of oxidation reaction of various drugs and to study the formation and structure of the resulting products. This technique has been applied to a 2,6,9‐trisubstituted purine, R‐roscovitine, which is known to be an inhibitor of some cyclin‐dependent kinases (CDKs) and a potential anticancer drug. Oxidation of R‐roscovitine in an electrochemical cell (EC), operated under various conditions, resulted in appearance of 6 major products. These were further analyzed by high‐resolution mass spectrometry, their structures were elucidated by accurate mass measurement and compared to previously identified R‐roscovitine in vitro/in vivo metabolites. Although none of the observed products was structurally identical to those identified previously in vitro/in vivo, all of them, except for the methoxylated products, resembled similarity due to appearing through the same reaction type. R‐roscovitine in the EC cell underwent N‐dealkylation of the isopropyl moiety, hydroxylation of the aromatic side‐chain, dihydroxylation, methoxylation and dimer formation. The hydroxylation product was identified as Olomoucine II, a R‐roscovitine derivative, which displays 10‐times higher CDK‐inhibiting activity than R‐roscovitine and the occurrence of which, as R‐roscovitine product, has not yet been observed in vitro/in vivo. 相似文献
55.
The dynamics of gel isoelectric focusing were studied by using amphoteric low-molecular-mass colored substances (isoelectric point markers). The polyacrylamide gel in slab format was in direct contact with the electrodes. In addition to isoelectric focusing with a pH gradient composed of synthetic carrier ampholytes, pH gradients created by simple buffers of acetic acid, 2-(N-morpholino)ethanesulfonic acid, histidine and N,N,N',N'-tetramethylethylenediamine were applied. The progress of the electrofocusing process was monitored by a charge-coupled device camera and video recording. The gradient profile and dynamics were approximated from the positions of isoelectric point markers, which were focused both on boundaries between individual zones of simple buffers and within the zones themselves. The obtained animated records enabled the observation of the entire real focusing run within fractions of a minute, which is useful both for the understanding and optimization of the focusing. 相似文献
56.
Karel Strnský Tom Jursík Antonín Vítek Jií Skoepa 《Journal of separation science》1992,15(11):730-740
A method has been developed for calculating more accurate and reproducible equivalent chain length (ECL) values of 33 straight-chain fatty acids (FA), with various positions and numbers of cis double bonds, chromatographed on DB-Wax and DB-1 columns. The dependence of ECL values on the position and the number of double bonds is described, as is a method of utilizing these relationships for the characterization of FA by gas chromatography. 相似文献
57.
Spindler Diane D. Wyman Charles E. Grohmann Karel 《Applied biochemistry and biotechnology》1991,(1):773-786
Four promising woody crops (Populusmaximowiczii x nigra (NE388), P.trichocarpa x deltoides (Nll), P.tremuloides, and SweetgumLiquidambar styraciflua) were pretreated by dilute sulfuric acid and evaluated in the simultaneous saccharification and fermentation (SSF) process
for ethanol production. The yeastSaccharomyces cerevisiae was used in the fermentations alone, and in mixed cultures with β -glucosidase producingBrettanomyces dausenii. Commercial Genencor 150L cellulase enyme was either employed alone or supplemented with β- glucosidase. All SSFs were run at 37 …C for 8 d and compared to saccharifications at 45…C under the same enzyme loadings.S. cerevisiae alone achieved the highest ethanol yields and rates of hydrolysis at the higher enzyme loadings, whereas the mixed culture
performed better at the lower enzyme loadings without β -glucosidase supplementation. The best overall rates of fermentation
(3 d) and final theoretical ethanol yields (86–90%) were achieved with P.maximowiczii x nigra (NE388) and SweetgumLiquidambar styraciflua, followed by P.tremuloides and P.trichocarpa xdeltoides (N1l) with slightly slower rates and lower yields. Although there were some differences in SSF performance, all these pretreated
woody crops show promise as substrates for ethanol production. 相似文献
58.
59.
Vladimíra Novotná Věra Hamplová Miroslav Kašpar Milada Glogarová Karel Knížek Siegmar Diele 《Liquid crystals》2013,40(8):967-975
New mesogens composed of achiral bent molecules with thermally stable ester linkages, and laterally substituted by a methoxy group symmetrically near the central benzene ring, were synthesized. Texture, calorimetric, electro‐optical, X‐ray and dielectric measurements were performed. In most of studied compounds the antiferroelectric B2 phase was found on cooling from the isotropic phase, followed by the B7 phase at lower temperatures. Undulation of layers in the B7 phase was confirmed by precise synchrotron studies. 相似文献
60.
Vladimír Setni
ka Marie Urbanov Statis Pataridis Vladimír Krl Karel Volka 《Tetrahedron: Asymmetry》2002,13(24):2661-2666
A novel approach to study the sol-gel phase transition of a brucine–porphyrin based gelator, which uses vibrational circular dichroism (VCD) spectroscopy, is described. The gelation process leading to highly ordered chiral supramolecular assemblies was investigated in various solvents at the different temperatures and concentrations. The VCD spectra sensitively reveal the specific parts of molecule whose configuration is influenced by a sol-gel phase transition and chiral supramolecular aggregation and therefore indicate the parts of the molecule responsible for the chiral self-assembly formation. Temperature stability of the organogel studied is discussed on the basis of the VCD and IR absorption spectra. The scanning electron microscopy was used to visualize the structure of brucine–porphyrin conjugate in the gel phase. 相似文献