全文获取类型
收费全文 | 31477篇 |
免费 | 1041篇 |
国内免费 | 664篇 |
专业分类
化学 | 7861篇 |
晶体学 | 351篇 |
力学 | 687篇 |
综合类 | 83篇 |
数学 | 15218篇 |
物理学 | 8982篇 |
出版年
2023年 | 153篇 |
2022年 | 275篇 |
2021年 | 229篇 |
2020年 | 221篇 |
2019年 | 722篇 |
2018年 | 537篇 |
2017年 | 438篇 |
2016年 | 302篇 |
2015年 | 320篇 |
2014年 | 508篇 |
2013年 | 1670篇 |
2012年 | 811篇 |
2011年 | 1532篇 |
2010年 | 1073篇 |
2009年 | 1406篇 |
2008年 | 1593篇 |
2007年 | 1539篇 |
2006年 | 1386篇 |
2005年 | 930篇 |
2004年 | 1251篇 |
2003年 | 1399篇 |
2002年 | 1889篇 |
2001年 | 1861篇 |
2000年 | 1721篇 |
1999年 | 1900篇 |
1998年 | 1612篇 |
1997年 | 1000篇 |
1996年 | 576篇 |
1995年 | 391篇 |
1994年 | 349篇 |
1993年 | 233篇 |
1992年 | 187篇 |
1991年 | 146篇 |
1990年 | 221篇 |
1989年 | 200篇 |
1988年 | 136篇 |
1987年 | 125篇 |
1986年 | 160篇 |
1985年 | 249篇 |
1984年 | 235篇 |
1983年 | 113篇 |
1982年 | 184篇 |
1981年 | 275篇 |
1980年 | 266篇 |
1979年 | 142篇 |
1978年 | 200篇 |
1977年 | 130篇 |
1976年 | 92篇 |
1975年 | 90篇 |
1974年 | 82篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
911.
B. Natalini R. Sardella E. Camaioni S. Natalini R. Pellicciari 《Chromatographia》2006,64(5-6):343-349
With the aim of optimizing the chromatographic process by avoiding any preliminary derivatizing step, we examined the chromatographic behaviour of a selected set of unconjugated bile acids looking at the dominant factors that affect the performances of three different stationary phases: RP-8, RP-18 and RP-18 Base Deactivated (RP-18-BD). Accordingly to its structural peculiarity, the RP-18-BD column combined with a specific mobile phase has proved to be the most suitable one, in enhancing both separation factor α and resolution R
S
within the selected set of analytes. Pronounced changes in the chromatographic profiles by only slightly changing the mobile phase composition (pH, buffer concentration, percentage and kind of organic modifier) prompted us to achieve satisfactory results in the separation and resolution of the selected set of bile acids.Presented at: CE in the Biotechnology & Pharmaceutical Industries: 7th symposium on the practical applications for the analysis of proteins, nucleotides and small molecules, Montreal, Canada, August 12–16, 2005.An erratum to this article can be found at 相似文献
912.
We report on a luminescent phenomenon in Dy3+-doped SrSiO3 long-lasting phosphor. After irradiation by a 254-nm UV lamp for 5 min, the Dy3+-doped SrSiO3 phosphor emits white light-emitting long-lasting phosphorescence for more than 1 h even after the irradiation source has been removed. Photoluminescence, long-lasting phosphorescence and thermoluminescence (TL) spectra are used to explain this phenomenon. Photoluminescence spectra reveal that the white light-emitting long-lasting phosphorescence originated from the two mixtures of Dy3+ characteristic luminescence, the 480-nm blue emission (4F9/2→6H15/2) and the 572-nm yellow emission (4F9/2→6H13/2). TL spectra shows that the introduction of Dy3+ ions into the SrSiO3 host produces a highly dense trapping level at 377 K (0.59 eV), which is responsible for the long-lasting phosphorescence at room temperature. A possible mechanism of the long-lasting phosphorescence based on the experimental results is proposed. It is considered that the long-lasting phosphorescence is due to persistent energy transfer from the electron traps to the Dy3+ ions, which creates the persistent luminescence of Dy3+ to produce the white light-emitting long-lasting phosphorescence. 相似文献
913.
K. M. Valikhanov M. G. Levkovich A. K. Tashmukhamedova 《Chemistry of Natural Compounds》2001,37(4):361-363
New derivatives of dibenzo-18-crown-6 were prepared by condensing 4,4(5)-dibenzo-18-crown-6-dicarboxylic acid dichloride with salsolidine and salsoline. The structures of these compounds were proved by PMR and IR spectral methods. 相似文献
914.
Celestino Angeli Renzo Cimiraglia Maurizio Persico Alessandro Toniolo 《Theoretical chemistry accounts》1997,98(1):57-63
We discuss the “three class” approximation to full multireference perturbation CI, which greatly reduces the computational
effort by restricting the summation of diagrams to determinants belonging to a subspace of the zero-order space. In the framework
of the CIPSI algorithm, we propose a new extrapolation procedure allowing recovery of the full “two class” results. The new
procedure is applied to complete active spaces (CAS) and to individually selected zero-order spaces. Comparison with a full
two class calculation on a CAS shows a reduction of computer time of one or two orders of magnitude in the tests presented
here, with an accuracy in the order of 0.1 kcal/mol. Our procedure can thus compete with the CASPT2 algorithm, specifically
conceived to deal with CAS. In the case of selected zero-order spaces, the speed-up is less dramatic but the method still
retains its advantages.
Received: 12 June 1997 / Accepted: 31 July 1997 相似文献
915.
The reaction of alkali metal hexacyanoferrate(II/III) with (CH2)6N4 (hexamethylenetetramine, abbreviated HMT) in an acidic medium yielded crystalline compounds of stoichiometries HK2[Fe111(CN)6]·2HMT·4H2O, H2K2[Fe11(CN)6]·2HMT·4H2O, and HNa2[Fe111(CN)6]· 2HMT·5H2O. Their crystal structures are based on a packing of three molecular components: neutral and/orprotonated HMT, hexacyanoferrate, and an alkali metal ion-water cluster. The resulting three-dimensional supramolecular framework is constructed from the coordination of the alkali metal ion by aqua ligands as well as [Fe(CN)6]{n–} and HMT units, and further stabilization is achieved by hydrogen bonding between water molecules and the noncoordinated nitrogen atoms of HMT and hexacyanoferrate. 相似文献
916.
Despite the continuing dominance of trifluoroacetic acid (TFA) as the anionic ion-pairing reagent of choice for peptide separations by reversed-phase high-performance liquid chromatography (RP-HPLC), we believe that a step-by-step approach to re-examining the relative efficacy of TFA compared to other ion-pairing reagents is worthwhile, particularly for the design of separation protocols for complex peptide mixtures, e.g., in proteomics applications. Thus, we applied RP-HPLC in the presence of different concentrations of anionic ion-pairing reagents - phosphoric acid, TFA, pentafluoropropionic acid (PFPA) and heptafluorobutyric acid (HFBA)--to a mixture of three groups of four 10-residue peptides, these groups containing peptides of +1, +3 or +5 net charge. Overall separation of the 12-peptide mixture improved with increasing reagent hydrophobicity (phosphate- < TFA- < PFPA- < HFBA-) and/or concentration of the anion, with reagent hydrophobicity having a considerably more pronounced effect than reagent concentration. HFBA, in particular, achieved an excellent separation at a concentration of just 10 mM, whereby the peptides were separated by charged groups (+1 < +3 < +5) and hydrophobicity within these groups. There was an essentially equal effect of reagent hydrophobicity and concentration on each positive charge of the peptides, a useful observation for prediction of the effect of varying counterion concentration hydrophobicity and/or concentration during optimization of peptide purification protocols. Peak widths were greater for the more highly charged peptides, although these could be decreased significantly by raising the acid concentration; concomitantly, peptide resolution increased with increasing concentration of ion-pairing reagent. 相似文献
917.
A series of superabsorbent hydrogels were prepared from carrageenan and partially neutralized acrylic acid by gamma irradiation at room temperature. The gel fraction, swelling kinetics and the equilibrium degree of swelling (EDS) of the hydrogels were studied. It was found that the incorporation of even 1% carrageenan (sodium salt) increases the EDS of the hydrogels from 320 to 800 g/g. Thermal analysis were carried out to determine the amount of free water and bound water in the hydrogels. Under optimum conditions, poly(acrylic acid)–carrageenan hydrogels with high gel fraction (80%) and very high EDS (800 g/g) were prepared gamma radiolytically from aqueous solution containing 15% partially neutralized acrylic acid and 1–5% carrageenan. The hydrogels were also found to be sensitive to the pH and the ionic strength of the medium. 相似文献
918.
Till?R?hrich Bassam?Abu Thaher Nico?Manicone Hans-Hartwig?OttoEmail author 《Monatshefte für Chemie / Chemical Monthly》2004,135(8):979-999
Summary. (RS)-2-tert-Butyldimethylsilyl-1,2-thiazetidine-3-acetic acid 1,1-dioxide prepared from (RS)-S-benzyl--homocysteine was condensed via DCC/NHS with various L-amino acid esters or dipeptide esters yielding N-silylated -sultam peptides. A -sultam active ester was isolated as an intermediate. Desilylation with TBAF in THF yielded stable N-unsubstituted products, and deprotection of the benzyl esters was achieved by catalytic hydrogenation. (S)-S-Benzyl--homocysteine was obtained by fractional crystallization of the brucine salt of the racemate and transformed into benzyl (S)-1,2-thiazetidine-3-acetate, which was on the other hand synthesized by an enantiospecific route from -benzyl Boc-L-aspartate. Some -sultam peptides were prepared from the (S)-enantiomer, and finally some -sultam peptides containing D-Ala units were obtained. 相似文献
919.
Samuel Melaku Ilse Gelaude Frank Vanhaecke Luc Moens Richard Dams 《Mikrochimica acta》2003,142(1-2):7-12
Microwave digestion reduction-aeration and pyrolysis combined with cold vapour atomic absorption and cold vapour atomic fluorescence
are compared for the determination of total mercury in several biological and environmental matrices. The biological samples
were digested in a mixture of HNO3/H2O2, the environmental samples in a mixture of HNO3/HClO4. After reduction with SnCl2, the mercury was collected by two-stage gold amalgamation. After microwave digestion reduction-aeration, detection limits
of 1.4 ng g−1 and 0.6 ng g−1 were obtained for cold vapour atomic absorption spectrometry (CVAAS) and cold vapour atomic fluorescence spectrometry (CVAFS),
respectively, for 250 mg of environmental samples. For biological samples (500 mg) the detection limits were 0.7 ng g−1 (CVAAS) and 0.4 ng g−1 (CVAFS). After pyrolysis, detection limits of 3.5 ng g−1 and 1.6 ng g−1 for CVAAS and CVAFS, respectively, were obtained for a 10 mg sample. Pyrolysis can only be applied when the organic content
of the sample is not too high. Accurate results were obtained for 8 certified reference materials of both environmental and
biological origin. In addition, a real sludge sample was analysed.
Author for correspondence. E-mail: richard.dams@rug.ac.be
Received September 18, 2002; accepted December 3, 2002
Published online May 5, 2003 相似文献
920.
Dhananjay B. Kendre 《Tetrahedron》2007,63(45):11000-11004
A convenient route was successfully developed for the synthesis of novel heterocycles such as pyrazolo[3,4-h][1,6]naphthyridine and dipyrazolo[3,4-b:3,4-d]pyridine (DPP) from pyrazolo[3,4-b]pyridine in good yield. The DPP derivatives synthesized were further studied for their fluorescence properties. 相似文献