全文获取类型
收费全文 | 3897篇 |
免费 | 187篇 |
国内免费 | 27篇 |
专业分类
化学 | 2791篇 |
晶体学 | 17篇 |
力学 | 193篇 |
数学 | 559篇 |
物理学 | 551篇 |
出版年
2023年 | 27篇 |
2022年 | 40篇 |
2021年 | 68篇 |
2020年 | 79篇 |
2019年 | 74篇 |
2018年 | 56篇 |
2017年 | 43篇 |
2016年 | 115篇 |
2015年 | 115篇 |
2014年 | 150篇 |
2013年 | 206篇 |
2012年 | 325篇 |
2011年 | 327篇 |
2010年 | 198篇 |
2009年 | 176篇 |
2008年 | 256篇 |
2007年 | 239篇 |
2006年 | 205篇 |
2005年 | 176篇 |
2004年 | 188篇 |
2003年 | 158篇 |
2002年 | 162篇 |
2001年 | 52篇 |
2000年 | 50篇 |
1999年 | 55篇 |
1998年 | 21篇 |
1997年 | 38篇 |
1996年 | 40篇 |
1995年 | 20篇 |
1994年 | 24篇 |
1993年 | 26篇 |
1992年 | 25篇 |
1989年 | 17篇 |
1986年 | 13篇 |
1985年 | 23篇 |
1984年 | 15篇 |
1983年 | 14篇 |
1982年 | 18篇 |
1981年 | 15篇 |
1980年 | 13篇 |
1979年 | 16篇 |
1978年 | 12篇 |
1977年 | 17篇 |
1976年 | 16篇 |
1975年 | 12篇 |
1974年 | 12篇 |
1973年 | 14篇 |
1971年 | 12篇 |
1968年 | 22篇 |
1967年 | 16篇 |
排序方式: 共有4111条查询结果,搜索用时 15 毫秒
31.
Philippe Guerry Philippe Blanco Heinz Brodbeck Olivier Pasteris Reinhard Neier 《Helvetica chimica acta》1991,74(1):163-178
1-Methoxycarbonyl-Substituted 2,3-Dihydropyridin-4(1H)-one(= Methyl 1,2,3,4-Tetrahydro-4-oxopyridine-1-carboxylate) as Chromophore for Photochemical [2 + 2]-Cycloadditions With olefins having an electron-acceptor as well as with olefins having an electron-donor substituent, 1-methoxycarbonyl-substituted dihydropyridinone 12 undergoes [2 + 2] cycloaddition in good preparative yields. The photochemical cycloaddition is highly regioselective. For preparative purposes, the ring junction can be equilibrated to the thermodynamically more stable cis-junction. Only the ‘endo’/‘exo’ selectivity at the C-atom bearing the olefin substituent cannot be controlled. The photodimerization of 12 is the only side reaction. Using a slight excess of the olefin, the photodimerization can be suppressed. The protecting group at the N-atom of the dihydropyridinone can be varied in order to introduce an internal sensitizer, as shown with 1-acyl-substituted compound 29 , which underwent the cycloaddition process even with sunlight. 相似文献
32.
Since it was first isolated, the oil extracted from seeds of neem (Azadirachtin indica A juss) has been extensively studied in terms of its efficacy as an insecticide. Several industrial formulations are produced as emulsifiable solutions containing a stated titer of the active ingredient azadirachtin-A (AZ-A). The work reported here is the characterization of a formulation of this insecticide marketed under the name of Neem-azal T/S and kinetic studies of the major active ingredient of this formulation. We initially performed liquid–liquid extraction to isolate the neem oil from other ingredients in the commercial mixture. This was followed by a purification using flash chromatography and semi-preparative chromatography, leading to 13C NMR identification of structures such as azadirachtin-A, azadirachtin-B, and azadirachtin-H. The neem extract was also characterized by HPLC–MS using two ionization sources, APCI (atmospheric pressure chemical ionization) and ESI (electrospray ionization) in positive and negative ion modes of detection. This led to the identification of other compounds present in the extract—azadirachtin-D, azadirachtin-I, deacetylnimbin, deacetylsalannin, nimbin, and salannin. The comparative study of data gathered by use of the two ionization sources is discussed and shows that the ESI source enables the largest number of structures to be identified. In a second part, kinetic changes in the main product (AZ-A) were studied under precise conditions of pH (2, 4, 6, and 8), temperature (40 to 70 °C), and light (UV, dark room and in daylight). This enabled us to determine the degradation kinetics of the product (AZ-A) over time. The activation energy of the molecule (75±9 kJ mol–1) was determined by examining thermal stability in the range 40 to 70 °C. The degradation products of this compound were identified by use of HPLC–MS and HPLC–MS–MS. The results enabled proposal of a chemical degradation reaction route for AZ-A under different conditions of pH and temperature. The data show that at room temperature and pH between 4 and 5 the product degrades into two preferential forms that are hydrolyzed to a single product over time and as a function of pH change. 相似文献
33.
Abstract— Studies of purine absorption and emission in seven solvents differing greatly in dielectric constant and hydrogen bonding potential, reveal a variety of solvent effects. For example, the resolution of structure in the absorption spectrum, the position and/or intensity of the X2 absorption band, the intensity of fluorescence, the magnitude of the long wave-lenth tail, and the position of the X1 absorption band are differentially affected—in the order listed—by the solvents tested. Even though it is possible to correlate the extent of decrease in the n-π* tail with increasing solvent dielectric constant, probably alterations in all of these spectroscopic parameters depend most critically upon the ability of the various solvents to form hydrogen bonds with the hydrogen on N9 and/for with the non-bonding electrons on the purine nitrogens: it is tentatively concluded that the probability of hydrogen bonding is directly correlated with the electronegativity of the aza nitrogens (N7 > N3 > N1). In solvents like isopropanol not all of the non-bonding electrons must be solvated maximally in most purine molecules since there is appreciable fluorescence under conditions where a long wavelength tail is readily observed in the absorption spectrum (alternatively some noa-bonding electrons may not te relevant to fluorescence quenching.) Decreases in fluorescence yield are associated with red shifts in the fluorescence maximum, and in the solvents of highest polarity the fluorescence yield is again small indicating that glycerol and water can enhance radiationless tunneling—presumably by altering Franck-Condon configurations and/or improving electronic-vibrational coupling between solute and solvent. The quantum yield is uniform throughout the atsorption band for a given solvent, but studies in aqueous buffers varying from pH 1 to 11 show that the fluorescence yield is greater for charged than for neutral molecules. Further, the fluorescence excitation peak is red shifted in powders. Since phosphorescence is the predominant emission at 777deg;K and increases in fluorescence can be correlated with the presumed solvation of non-bonding electrons, the singlet excited state of lowest energy in ‘unperturbed’ purine must be n-π* in nature. The shape of the phosphorescence band and the decay lifetime of ? 1 sec at 77°K lead to the conclusion that the emitting triplet is a π-π* state. The eight vibrational structures in phosphorescence emission can be readily grouped into two progressions: there is an average separation of about 1300 cm-1 between peaks within a given progression, and the two sets are mutually displaced by about 500 cm-l. Individual vibrational peaks are favoured in different solvents and the whole band may be shifted up to 500 cm-l. Even larger shifts are observed in charged purine molecules and in powders (up to 3000 cm-l) and the presumed 0–0 band is not observed. 相似文献
34.
Bossée A Afonso C Fournier F Tasseau O Pepe C Bellier B Tabet JC 《Journal of mass spectrometry : JMS》2004,39(8):903-912
Peptide metallation with Cu2+ was explored in the negative ESI mode using an ion trap mass spectrometer. Under these conditions, the [(M-3H) + CuII]- species formed were investigated under low-energy collision-induced dissociation conditions. MS2 experiments indicate a very different behavior of CuII metallated complexes compared with [M-H]- species. CuII induces an easy loss of CO2 and specific side-chain cleavages (by radical losses) at the C-terminal residue, as observed previously by prompt 'in source' dissociation experiments. The loss of CO2 yields an unstable carbylide that leads to further dissociations involving the migration of a proton or a hydrogen radical (through the reduction of CuII). Multistage MS3 experiments were carried out to rationalize this behavior. Fragmentation pathways are proposed in order to explain the product ions observed. The side-chain radical loss at the C-terminus was demonstrated to be a consecutive process. Finally, evidence is provided that the specific side-chain cleavages can be used for the differentiation of Leu/Ile and Gln/Lys residues when they are located at the C-terminus. The existence of a zwitterionic form in the case of the anionic YGGFK-CuII complex is proposed. 相似文献
35.
36.
Boron was analysed in ore and glass samples by prompt proton spectrometry, using deuterons of 2.7 MeV to coincide with a region
where the excitation function of the10B(d, p)11B reaction did not vary appreciably with energy.
Targets of approximately 300 μg/cm2 thick of powdered samples were prepared by centrifugation. Concentrations down to 0.2% were determined. Possible interference
by other elements, particularly nitrogen, magnesium and titanium, was investigated. 相似文献
37.
Jean M. J. Tronchet Bernard Gentile Alain P. Bonenfant Olivier R. Martin 《Helvetica chimica acta》1979,62(3):696-699
Further examples of O-isopropylidenaldehydosugars in the furanose series Formyl-bearing furanose derivatives 1–3 (α-D -xylo or α-D -erythro configurations) and 5–8 (configurations α-D -ribo, α-D -lyxo, β-L -threo and D -arabino) have been prepared by classical synthetic steps and their properties mainly spectroscopic, reported. The coupling constant between the formyl and the vicinal proton is always small. Like other members of the series, these new aldehydosugars constitute very useful and flexible synthetic intermediates. 相似文献
38.
Olivier Busnel 《Tetrahedron letters》2007,48(33):5767-5770
The preparation of new Nβ-Fmoc-protected aza-β3-amino acids (aza-β3-aa) with proteinogenic side chains as well as their Nβ-Fmoc, Nβ-Cbz or Nβ-Boc aza-β3-amino esters (from Pro, Asn, Asp, Glu, Gln) by successive nucleophilic substitutions will be described. 相似文献
39.
M. J. Musmar M. Robert Willcott Gary E. Martin Robert T. Gampe Masatomo Iwao Milton L. Lee Ralph E. Hurd Leroy F. Johnson Raymond N. Castle 《Journal of heterocyclic chemistry》1983,20(6):1661-1669
Development of successively higher field nmr spectrometers has facilitated the study of increasingly more complex molecules, although smaller molecules such as phenanthro[3,4-b]thiophene still offer very substantial assignment problems because of the highly congested nature of their 1H- and 13C-nmr spectra. Assignments of such spectra, if they are to be unequivocal, frequently require the utilization of two-dimensional nmr spectroscopic techniques. Total assignments of the 1H- and 13C-nmr spectra of phenanthro[3,4-b]thiophene are reported. Assignments were based on a conventional high resolution 500 MHz 1H-nmr spectrum, autocorrelated two-dimensional 1H-nmr spectra (COSY), two-dimensional 1H-13C chemical shift correlation spectra and a modified version of autocorrelated 13C-13C double quantum coherence two-dimensional nmr spectroscopy. From NOE measurements, a separation of 1.99 Å between H1 and H11 was computed, suggesting that phenanthro[3,4-b]thiophene has a pronounced helical conformation in solution. 相似文献
40.
[reaction: see text] The use of hydroxamic acids as templates for Lewis acid catalyzed enantioselective Diels-Alder reactions has been examined. A very simple chiral Lewis acid, prepared by mixing optically pure binaphthol with 3 equiv of trimethylaluminum, catalyzes the [4 + 2] cycloaddition of N-hydroxy-N-phenylacrylamide with cyclopentadiene at 0 degrees C in high yield (>96%) and with a fairly good level of enantioselectivity (91% ee). Facile conversion of the products to the corresponding alcohols or aldehydes makes the hydroxamic acid intermediates particularly useful. 相似文献