全文获取类型
收费全文 | 1150篇 |
免费 | 15篇 |
国内免费 | 30篇 |
专业分类
化学 | 658篇 |
晶体学 | 1篇 |
力学 | 33篇 |
数学 | 373篇 |
物理学 | 130篇 |
出版年
2020年 | 7篇 |
2018年 | 7篇 |
2016年 | 18篇 |
2015年 | 9篇 |
2014年 | 17篇 |
2013年 | 71篇 |
2012年 | 32篇 |
2011年 | 39篇 |
2010年 | 28篇 |
2009年 | 33篇 |
2008年 | 41篇 |
2007年 | 38篇 |
2006年 | 42篇 |
2005年 | 35篇 |
2004年 | 46篇 |
2003年 | 45篇 |
2002年 | 44篇 |
2001年 | 23篇 |
2000年 | 25篇 |
1999年 | 10篇 |
1998年 | 10篇 |
1997年 | 20篇 |
1996年 | 25篇 |
1995年 | 25篇 |
1993年 | 20篇 |
1992年 | 9篇 |
1991年 | 17篇 |
1990年 | 12篇 |
1989年 | 14篇 |
1988年 | 18篇 |
1987年 | 19篇 |
1986年 | 10篇 |
1985年 | 24篇 |
1984年 | 17篇 |
1983年 | 17篇 |
1982年 | 25篇 |
1981年 | 26篇 |
1980年 | 29篇 |
1979年 | 28篇 |
1978年 | 20篇 |
1977年 | 18篇 |
1976年 | 18篇 |
1975年 | 13篇 |
1974年 | 14篇 |
1973年 | 16篇 |
1972年 | 11篇 |
1971年 | 8篇 |
1970年 | 7篇 |
1967年 | 7篇 |
1966年 | 7篇 |
排序方式: 共有1195条查询结果,搜索用时 15 毫秒
21.
Sternfeld T Thilgen C Hoffman RE Del Rosario Colorado Heras M Diederich F Wudl F Scott LT Mack J Rabinovitz M 《Journal of the American Chemical Society》2002,124(20):5734-5738
Reduction of the two "closed" [6,6] methanofullerenes, [6,6]C(61)H(2) (1) and [6,6]C(71)H(2) (5), to the corresponding hexaanions with lithium metal causes the bridgehead-bridgehead bonds to open, at least partially, and this change gives rise to diamagnetic ring currents in the resulting homoconjugated six-membered rings (6-MRs). These new ring currents shield the overlying hydrogen atoms on the methylene bridge and induce upfield shifts of 1.60 and 0.11 ppm in their (1)H NMR resonances, respectively. Analogous reduction of the already "open" [5,6]methanofullerenes, [5,6]C(61)H(2) (2) and [5,6]C(71)H(2) (3 and 4), only slightly enhances the shielding of the hydrogen atoms over the homoconjugated 6-MRs (upfield shifts of 0.13, 0.68, and 0.14 ppm, respectively) but leads to exceptionally strong diamagnetic ring currents in the homoconjugated five- membered rings (5-MRs), as evidenced by dramatic shielding of the hydrogen atoms situated over them (upfield shift of 5.01, 6.78, and 1.63 ppm, respectively). The strongest shielding is seen for the hydrogen atom sitting over the 5-MR at the pole of C(71)H(2)(6)(-) (delta = -0.255 ppm) indicating that the excess charge density is concentrated at the poles. 相似文献
22.
MM2 Exploration of the conformational space for methylcyclopentane, in contrast to cyclopentanone yields more and flatter minima than known previously. Calculations of cyclopentanes with substituents X = F, Cl, CHMe2, and CMe3 with two stable conformations indicate <2° torsional angle changes with the different substituents. Cyclopentanes bearing not more than 2 substituents can accommodate all groups in pseudoequatorial positions without changing the basic envelope and twist chair geometries significantly. A model for 13C-shift calculation is proposed in which shift increments for the different torsional arrangements are obtained by linear interpolation between corresponding cyclohexane values. After correction for the nonequivalent carbon shifts in the hydrocarbon itself, again using the linear interpolation, a significant improvement of the shift correlations is observed. For disubstituted cyclopentanes these predict the shifts within ± 1.7 ppm with Me, CHMe2, CMe3, Cl, Br and OH as substituents. Configurational assignments are difficult with 1,3-di-substituted cyclopentanes, but straightforward with 1,2-di- and trisubstituted compounds. Thus, due to the presence of smaller torsional angles between, e.g. diequatorial vicinal substituents in the 1,2- cis series as compared to the trans compounds, the latter show deshielding, particularly at C2, by 1–4 ppm. Several epimers are stereo-selectively prepared by suitable ketone reduction and displacement methods. 相似文献
23.
Fred C Cantillana T Henderson AP Golding BT Törnqvist M 《Rapid communications in mass spectrometry : RCM》2004,18(18):2177-2184
Isoprene (2-methylbuta-1,3-diene) is a multi-site carcinogen in rodents. To evaluate the role of the diepoxide metabolite (1,2:3,4-diepoxy-2-methylbutane) in carcinogenesis, measurements of in vivo doses of the diepoxide are needed. The in vivo dose may be inferred from levels of reaction products with hemoglobin (Hb adducts). This report presents in vitro studies of the adduct formation by the diepoxide of isoprene with valinamide and oligopeptides as model compounds of N-terminal valines in hemoglobin (Hb). In the reaction with valinamide it was shown that isoprene diepoxide forms as the main product a ring-closed adduct, which is a pyrrolidine derivative [N,N-(2,3-dihydroxy-2-methyl-1,4-butadiyl)valinamide, MPyr-Val]. The analysis was performed by gas chromatography/mass spectrometry (GC/MS) (EI and PICI) after acetylation. The ring-closed adduct was also identified by liquid chromatography/electrospray ionization mass spectrometry (LC/ESI-MS) as the main product in the reaction between isoprene diepoxide and standard hepta- or (2H8)octapeptides, corresponding to the N-terminal peptides of the alpha-chains in mouse and rat Hb. These peptides, alkylated with isoprene diepoxide, to be used as internal standards and calibration standards for quantification of MPyr-adduct levels in vitro and in vivo, were analyzed with respect to the degree of MPyr-alkylation by two independent methods, amino acid analysis and HPLC-UV; similar results were obtained using these methods. A method for measurement of Hb adducts as modified peptides, used earlier to measure a similar adduct to N-terminal valines in Hb from the diepoxide of 1,3-butadiene, has in the present work been tested for application to isoprene diepoxide. The method is based on tryptic degradation of globin and LC/ESI-MS analysis of N-terminal Pyr-heptapeptides of the Hb alpha-chain enriched by HPLC. MPyr-adduct levels in isoprene diepoxide alkylated hemolysate from mouse erythrocytes incubated with different concentrations of isoprene diepoxide (2 and 10 mM) for 1 h were quantified. The adduct level was about 50 nmol/g alpha-chain Hb per mM x h. From the adduct levels the rate constant of isoprene diepoxide for reaction with N-terminal valine was calculated to be about 1.6 times faster than for diepoxybutane. 相似文献
24.
A study of the extraction of chromium(VI) from aqueous media by ketones was made. Extraction of chromium was found to be most efficient from aqueous hydrochloric acid solutions. A mechanism for the extraction of chromium(VI) from aqueous hydrochloric acid solutions by methyl isobutyl ketone is proposed involving the formation of a receptor in the organic phase, the exchange of the chloride ion of the receptor for the anionic chromium(VI) species of the aqueous phase, and the solvation of the extracted chromium species. The differences in the abilities of various ketones to extract chromium(VI) from aqueous hydrochloric acid solutions, and the differences in the extraction of chromium (VI) from various aqueous acids by methyl isobutyl ketone are attributed to the differences in the formation of receptors. 相似文献
25.
Michael W. Senko Steven C. Beu Fred W. McLafferty 《Journal of the American Society for Mass Spectrometry》1995,6(1):52-56
The recent proliferation of electrospray as an ionization method has greatly increased the ability to perform analyses of large biomolecules by using mass spectrometry. The major advantage of electrospray is the ability to produce multiply charged ions, which brings large molecules down to a mass-to-charge ratio range amenable to most instruments. Multiple charging is also a disadvantage because mass (m) becomes ambiguous unless charge (z) can be assigned. This is typically performed with simple algorithms that use multiple peaks of the same m and different z, but these methods are difficult to apply to complex mixtures and not applicable when only one z appears for each m. The use of mass analyzers with higher resolving powers, like the Fourier transform mass spectrometer, allows resolution of isotopic peaks, providing an internal 1-Da mass scale that can be used for unambiguous charge assignment. Manual assignment of charge state from the isotopic peaks is time consuming and becomes inaccurate when either the signal level or resolving power are low. For these cases, computer algorithms based on pattern recognition techniques have been developed to assist in assignment of charge states to isotopic clusters. These routines provide for more rapid analysis with higher accuracy than available manually. 相似文献
26.
Pyrolysis—mass spectrometry (Py—MS) as a taxonomic tool was applied to a series of atmospheric particulate samples. Seven pure and mixed source samples were individually pyrolyzed at 450°C directly into a mass spectrometer. The resulting spectra were summed and analyzed using an Euclidian Distance calculated from an n-dimensional array of peak intensity values weighted utilizing a Fisher ratioing procedure. The results of this study indicate that Py—MS can be used to distinguish various atmospheric particulate sources. 相似文献
27.
Song -Cheng Sun David E. Reed John K. Cullison Lyman H. Rickard Fred M. Hawkridge 《Mikrochimica acta》1988,96(1-6):97-104
The heterogeneous electron transfer reactions of cytochromec occurring at platinum, gold and mercury electrodes are shown to be quasi-reversible. In each case the electrodes have not been modified and the cytochromec samples are native. This work extends previous work and demonstrates that biological molecule electron transfer reactions can be studied at clean metal surfaces to gain fundamental knowledge of the mechanisms of these reactions. 相似文献
28.
Extraction and characterization of adenovirus 总被引:5,自引:0,他引:5
Mirza UA Liu YH Tang JT Porter F Bondoc L Chen G Pramanik BN Nagabhushan TL 《Journal of the American Society for Mass Spectrometry》2000,11(4):356-361
A new methodology for the extraction and characterization of proteins from Coomassie-stained sodium dodecylsulfate polyacrylamide gel electrophoresis using matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) has been described. The utility of this methodology was demonstrated in the characterization of adenovirus proteins. The key steps in the extraction and destaining process involve washing the excised band with a combination of solvents that include 10% acetic acid, acetonitrile, methanol, and formic acid:water:isopropanol mixture. By using this procedure, we determined adenovirus proteins with molecular weights ranging from 10,000 to 110,000 Da by MALDI-MS, obtaining a detection limit of approximately 6 pmol. Parallel experiments were successfully carried out to analyze adenovirus proteins from Cu-stained gels. It was observed that increase in laser intensity resulted in significant improvements in the quality of MALDI mass spectra for the analysis of inefficiently destained proteins from Cu-stained gels. 相似文献
29.
The kinetics of the reduction of Eu3+ and Cr3+ at mercury electrodes have been studied in various mixed perchlorate electrolytes containing iodide, bromide, and p-toluene-sulfonate as adsorbing anions. Specific adsorption data were obtained by means of the constant ionic strength approach due to Hurwitz and Parsons. The rate enhancements observed in the presence of the first two (monatomic) anions were in good agreement with the predictions of the simple Frumkin model only when the experimental, rather than calculated diffuse-layer capacitances were employed in the data analysis. It was demonstrated that the effects of ion-pairing and ligand-bridging of the reactants with the adsorbing anions were negligible under the experimental conditions chosen. From experiments with these systems and also with weakly adsorbing chloride electrolytes it was concluded that ion-pairing did not enhance the electrochemical reactivity of either Eu3+ or Cr3+. The value of the analyses described in separating various contributions to the catalytic effects of adsorbing anions is emphasized. 相似文献
30.
Cheeseman M Feuillet FJ Johnson AL Bull SD 《Chemical communications (Cambridge, England)》2005,(18):2372-2374
A new way of combining chiral auxiliaries and substrate-directable reactions for asymmetric synthesis is described that employs a three-step sequence of aldol-cyclopropanation-retro-aldol reactions for the stereoselective synthesis of enantiopure cyclopropane carboxaldehydes. 相似文献