全文获取类型
收费全文 | 161篇 |
免费 | 7篇 |
专业分类
化学 | 127篇 |
数学 | 13篇 |
物理学 | 28篇 |
出版年
2020年 | 3篇 |
2019年 | 3篇 |
2018年 | 3篇 |
2017年 | 2篇 |
2016年 | 2篇 |
2015年 | 3篇 |
2014年 | 4篇 |
2013年 | 6篇 |
2012年 | 7篇 |
2011年 | 11篇 |
2010年 | 8篇 |
2008年 | 8篇 |
2007年 | 6篇 |
2006年 | 4篇 |
2005年 | 6篇 |
2004年 | 4篇 |
2003年 | 8篇 |
2002年 | 4篇 |
2001年 | 4篇 |
2000年 | 5篇 |
1999年 | 3篇 |
1998年 | 3篇 |
1997年 | 1篇 |
1996年 | 5篇 |
1995年 | 1篇 |
1994年 | 1篇 |
1993年 | 3篇 |
1992年 | 5篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1989年 | 2篇 |
1988年 | 1篇 |
1986年 | 3篇 |
1985年 | 3篇 |
1984年 | 4篇 |
1982年 | 4篇 |
1981年 | 1篇 |
1980年 | 3篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1974年 | 1篇 |
1973年 | 2篇 |
1971年 | 1篇 |
1970年 | 1篇 |
1967年 | 1篇 |
1966年 | 3篇 |
1965年 | 2篇 |
排序方式: 共有168条查询结果,搜索用时 11 毫秒
1.
The results of Monte Carlo simulations of the beta dose rate to enamel are presented. The dose rates are the most comprehensive to date, incorporating the beta spectrum from 21 different radionuclides, all internal conversion and Auger electrons, the majority of the bremsstrahlung radiation, effects due to radon loss in the uranium series, and variations in the moisture content of the sediment. Applications to a new dating technique in archaeology using electron spin resonance and beta-gradient isochrons are discussed. 相似文献
2.
3.
Joseph B. Schlenoff W. Jack Rink Lawrence Seger 《Physica C: Superconductivity and its Applications》1991,180(5-6):387-393
Single crystals and polycrystalline pellets of the high-temperature cuprate superconductor Bi2Sr2Ca1Cu2O8 were doped at room temperature by electrochemical reduction at > 95% Coulombic efficiency using lithium dopant ions in propylene carbonate electrolyte. Cyclic voltammetry and potential step measurements on single crystals suggest an unusual reduction mechanism, with a diffusion coefficient for Li+ in the c-axis direction of bulk superconductor of ca. 3 × 10−11 cm2s−1. Sintered pellets of polycrystalline powder could be doped more rapidly, with an apparent diffusion coefficient of 7 × 10−8 cm2s−1. X-ray susceptibility analysis show extensive disordering occurs on heavy Li doping, with a first-order transition from a crystalline/superconducting to an amorphous/non-superconducting phase. Single, crystals of Bi2Sr2Ca1Cu2O8 exhibited a color change on reduction from metallic gray to golden bronze. The reduced material was highly air-sensitive, forming a hydroxide surface film on exposure to ambient atmosphere. 相似文献
4.
Ferenc Sztaricskai Gyula Batta Zoltan Dinya Istvan F. Pelyvas Pal Herczegh Tamas E. Gunda Istvan Koczka 《Chemistry of Heterocyclic Compounds》1998,34(11):1296-1307
Starting from 3,5-dimethylisoxazole the carboxylic acids I and V, the amino acids VIII (L-) and IX (D-), and the ureido acids X (L-) and XI (D-) were prepared, which were used for the synthesis of the new cephalosporins XVIIb, XXa-c (L-), and XXIb (D-). Thein vitro antibacterial activity of these semi-synthetic antibiotics was studied. The resorption of XVIIb was investigated in mice.Research Group for Antibiotics of the Hungarian Academy of Sciences, H-4010 Debrecen, P.O. Box 70, Hungary. Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1524–1535, November, 1998. 相似文献
5.
An efficient and concise approach to the synthesis of the macrolide core of the cryptophycins has been developed. A novel macrolactonization utilizing a reactive acyl-beta-lactam intermediate incorporates the beta-amino acid moiety within the 16-membered macrolide core. This modular approach, involving a cyanide-initiated acyl-beta-lactam ring opening followed by cyclization, was successfully applied to the total synthesis of cryptophycin-24. The strategy was also used in an efficient synthesis of the 6,6-dimethyl-substituted dechlorocryptophycin-52. In this case, the cyanide-initiated ring opening of the bis-substituted 2-azetidinone followed by macrolactonization was achieved through a catalytic process. 相似文献
6.
Mass-selected gas-phase UV spectra of laser-desorbed molecules at room temperature have been measured via resonance-enhanced multiphoton ionisation (REMPI) and time-of-flight mass selection. The wavelength range of 260 to 320 nm is optimal for detection of polycyclic aromatic hydrocarbons (PAHs) using REMPI-mass spectrometry. A new laser desorption/laser ionisation source has been used which features a compact size and thermal equilibrium of the desorbed molecules. 16 PAHs have been investigated which have been selected by the US Environmental Protection Agency (EPA). These 16 EPA-PAHs are commonly used world-wide to characterise the PAH-load of environmental samples. 相似文献
7.
Pd-catalyzed coupling of the axially constrained, less reactive benzo[a]pyrene bay-region amino benzoates, derived from the tetrahydro and diol epoxides, with C-6 and C-2 halopurine deoxynucleosides offers an efficient approach to the synthesis of the corresponding nucleoside-epoxide adducts. Also reported are the first examples involving the coupling of a 6-chloropurine deoxynucleoside with these amines, a reaction that is difficult by direct halide displacement. Certain mechanistic aspects of this metal-catalyzed C-N bond formation are also discussed. [reaction--see text] 相似文献
8.
A new procedure for the synthesis of peptides on a soluble carrier is described. It relies on gel filtration for the removal of low molecular weight reactants from the peptide-polymer complex after each cycle. The advantages of the method are assessed and the insight into the problematics of the carrier synthesis which it provides are discussed. Finally, the use of a monovalent, soluble carrieer molecule of defined chemistry is proposed. Such a carrier should reduce the problems of carrier synthesis to the purely chemical ones commonly associated with peptide synthesis. 相似文献
9.
Christina Haberhauer-Troyer Marizela Delic Brigitte Gasser Diethard Mattanovich Stephan Hann Gunda Koellensperger 《Analytical and bioanalytical chemistry》2013,405(6):2031-2039
A novel method for the simultaneous quantification of both glutathione (GSH) and its oxidized form glutathione disulfide (GSSG) by hydrophilic interaction chromatography–MS/MS has been developed and is critically discussed. Internal standardization based on isotopically labeled standards for both analytes is an absolute prerequisite for accurate quantification of this redox pair. Hence, a highly efficient and selective miniaturized procedure for the synthesis of isotopically labeled GSSG from commercially available glutathione-(glycine-13C2,15N) was established using H2O2 as oxidant and NaI as catalyst. Moreover, a tool is presented to monitor and hence uncover artifactual GSSG formation due to oxidation of GSH during sample preparation, which is the main source of systematic error in GSSG analysis. For this purpose, we propose to monitor the oxidation product formed by reaction of naturally occurring GSH with the isotopically labeled GSH used as internal standard. For the determination of GSH/GSSG ratios in yeast, different extraction methods based on (1) hot extraction with aqueous, acidic, or organic solvents, (2) mechanical cell lysis, and (3) extraction at subambient temperature were investigated in terms of recovery, extraction efficiency, and artifactual formation of GSSG. Total combined uncertainties of as low as 25–30 % (coverage factor?=?2) for the determination of GSH/GSSG ratios without derivatization were made possible by the addition of the internal standards early in the analytical procedure (before extraction) and immediate analysis of the analytes. 相似文献
10.
Electrochemiluminescence Bioassays with a Water‐Soluble Luminol Derivative Can Outperform Fluorescence Assays 下载免费PDF全文
Michael Mayer Prof. Dr. Shigehiko Takegami Michael Neumeier Simone Rink Prof. Dr. Axel Jacobi von Wangelin Silja Schulte Moritz Vollmer Prof. Dr. Axel G. Griesbeck PD Dr. Axel Duerkop Prof. Dr. Antje J. Baeumner 《Angewandte Chemie (International ed. in English)》2018,57(2):408-411
The most efficient and commonly used electrochemiluminescence (ECL) emitters are luminol, [Ru(bpy)3]2+, and derivatives thereof. Luminol stands out due to its low excitation potential, but applications are limited by its insolubility under physiological conditions. The water‐soluble m‐carboxy luminol was synthesized in 15 % yield and exhibited high solubility under physiological conditions and afforded a four‐fold ECL signal increase (vs. luminol). Entrapment in DNA‐tagged liposomes enabled a DNA assay with a detection limit of 3.2 pmol L?1, which is 150 times lower than the corresponding fluorescence approach. This remarkable sensitivity gain and the low excitation potential establish m‐carboxy luminol as a superior ECL probe with direct relevance to chemiluminescence and enzymatic bioanalytical approaches. 相似文献