全文获取类型
收费全文 | 286篇 |
免费 | 6篇 |
专业分类
化学 | 128篇 |
晶体学 | 1篇 |
力学 | 39篇 |
数学 | 23篇 |
物理学 | 101篇 |
出版年
2017年 | 4篇 |
2016年 | 3篇 |
2015年 | 6篇 |
2014年 | 5篇 |
2013年 | 12篇 |
2012年 | 10篇 |
2011年 | 20篇 |
2010年 | 11篇 |
2009年 | 5篇 |
2008年 | 14篇 |
2007年 | 12篇 |
2006年 | 10篇 |
2005年 | 13篇 |
2004年 | 6篇 |
2003年 | 8篇 |
2002年 | 8篇 |
2001年 | 14篇 |
2000年 | 13篇 |
1999年 | 14篇 |
1998年 | 3篇 |
1997年 | 2篇 |
1996年 | 13篇 |
1995年 | 3篇 |
1994年 | 8篇 |
1993年 | 2篇 |
1992年 | 4篇 |
1991年 | 8篇 |
1990年 | 3篇 |
1989年 | 1篇 |
1988年 | 3篇 |
1987年 | 4篇 |
1986年 | 3篇 |
1985年 | 2篇 |
1984年 | 5篇 |
1982年 | 2篇 |
1981年 | 4篇 |
1980年 | 3篇 |
1979年 | 1篇 |
1978年 | 6篇 |
1977年 | 1篇 |
1976年 | 3篇 |
1975年 | 2篇 |
1973年 | 2篇 |
1970年 | 2篇 |
1969年 | 1篇 |
1968年 | 2篇 |
1967年 | 3篇 |
1955年 | 1篇 |
1933年 | 2篇 |
1932年 | 2篇 |
排序方式: 共有292条查询结果,搜索用时 15 毫秒
81.
Tseitlin M Quine RW Rinard GA Eaton SS Eaton GR 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2011,213(1):119-125
A digital EPR spectrometer was constructed by replacing the traditional bridge with an arbitrary waveform generator (AWG) to produce excitation patterns and a high-speed digitizer for direct detection of the spin system response at the carrier frequency. Digital down-conversion produced baseband signals in quadrature with very precise orthogonality. Real-time resonator tuning was performed by monitoring the Fourier transforms of signals reflected from the resonator during frequency sweeps generated by the AWG. The capabilities of the system were demonstrated by rapid magnetic field scans at 256 MHz carrier frequency, and FID and spin echo experiments at 1 and 10 GHz carrier frequencies. For the rapid scan experiments the leakage through a cross-loop resonator was compensated by adjusting the amplitude and phase of a sinusoid at the carrier frequency that was generated with another AWG channel. 相似文献
82.
Tseitlin M Eaton SS Eaton GR 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2011,209(2):277-281
Selection of the amplitude of magnetic field modulation for continuous wave electron paramagnetic resonance (EPR) often is a trade-off between sensitivity and resolution. Increasing the modulation amplitude improves the signal-to-noise ratio, S/N, at the expense of broadening the signal. Combining information from multiple harmonics of the field-modulated signal is proposed as a method to obtain the first derivative spectrum with minimal broadening and improved signal-to-noise. The harmonics are obtained by digital phase-sensitive detection of the signal at the modulation frequency and its integer multiples. Reconstruction of the first-derivative EPR line is done in the Fourier conjugate domain where each harmonic can be represented as the product of the Fourier transform of the 1st derivative signal with an analytical function. The analytical function for each harmonic can be viewed as a filter. The Fourier transform of the 1st derivative spectrum can be calculated from all available harmonics by solving an optimization problem with the goal of maximizing the S/N. Inverse Fourier transformation of the result produces the 1st derivative EPR line in the magnetic field domain. The use of modulation amplitude greater than linewidth improves the S/N, but does not broaden the reconstructed spectrum. The method works for an arbitrary EPR line shape, but is limited to the case when magnetization instantaneously follows the modulation field, which is known as the adiabatic approximation. 相似文献
83.
Basran J Efimov I Chauhan N Thackray SJ Krupa JL Eaton G Griffith GA Mowat CG Handa S Raven EL 《Journal of the American Chemical Society》2011,133(40):16251-16257
Heme dioxygenases catalyze the oxidation of L-tryptophan to N-formylkynurenine (NFK), the first and rate-limiting step in tryptophan catabolism. Although recent progress has been made on early stages in the mechanism, there is currently no experimental data on the mechanism of product (NFK) formation. In this work, we have used mass spectrometry to examine product formation in a number of dioxygenases. In addition to NFK formation (m/z = 237), the data identify a species (m/z = 221) that is consistent with insertion of a single atom of oxygen into the substrate during O(2)-driven turnover. The fragmentation pattern for this m/z = 221 species is consistent with a cyclic amino acetal structure; independent chemical synthesis of the 3a-hydroxypyrroloindole-2-carboxylic acid compound is in agreement with this assignment. Labeling experiments with (18)O(2) confirm the origin of the oxygen atom as arising from O(2)-dependent turnover. These data suggest that the dioxygenases use a ring-opening mechanism during NFK formation, rather than Criegee or dioxetane mechanisms as previously proposed. 相似文献
84.
Richard Gilardi Clifford George Jerome Karle Philip E. Eaton Munagala Rao 《Journal of heterocyclic chemistry》1993,30(5):1389-1391
Despite the angular strain associated with the assembly of small rings, 1,2-diisocyanatocubane reacts with trimethylsilyl azide under mild conditions to form a hexacyclic ring assembly that contains an imidazolidone ring fused to one edge of cubane. This compound was identified as an azidocarbonyl-substituted cubanourea by means of X-ray crystal structure analysis of the nitro-derivative, the energetic compound N-azidocarbonyl-N1-nitrocubanourea. 相似文献
85.
Three-dimensional spectral-spatial-spatial images are presented for a sample containing six different species in seven compartments. EPR spectra used to construct these images were obtained by the normal CW methods and by electron spin echo detection. Images of the sample when viewed from these two different perspectives are contrasted. 相似文献
86.
The aim of this work is the study of longitudinal field relaxation for organic radicals in the gas or vapour phase, for which
the technique of Muon Spin Relaxation proves to be uniquely suitable. Following on from the first such study of the muonium
substituted ethyl radical in gaseous ethene [1], the present work represents the beginning of a systematic study of species
of various molecular symmetries and still higher molecular weight, with a view to investigating their collisional dynamics.
Preliminary data for the muonium substituted cyclohexadienyl radical in benzene vapour, and the results of tests for radical
formation in acetylene and carbon monoxide, are presented. 相似文献
87.
88.
Alkynes as Linchpins for the Additive Annulation of Biphenyls: Convergent Construction of Functionalized Fused Helicenes 下载免费PDF全文
Dr. Rana K. Mohamed Dr. Sayantan Mondal Joseph V. Guerrera Teresa M. Eaton Prof. Thomas E. Albrecht‐Schmitt Prof. Michael Shatruk Prof. Igor V. Alabugin 《Angewandte Chemie (International ed. in English)》2016,55(39):12054-12058
A new approach to fused helicenes is reported, where varied substituents are readily incorporated in the extended aromatic frame. From the alkynyl precursor, the final helical compounds are obtained under mild conditions in a two‐step process, in which the final C?C bond is formed via a photochemical cyclization/ dehydroiodination sequence. The distortion of the π‐system from planarity leads to unusual packing in the solid state. Computational analysis reveals that substituent incorporation perturbs geometries and electronic structures of these nonplanar aromatics. 相似文献
89.
Gucciardi A Cogo PE Traldi U Eaton S Darch T Simonato M Ori C Carnielli VP 《Rapid communications in mass spectrometry : RCM》2008,22(13):2097-2103
Deuterium (2H) in water and urine can be measured by off-line and, more recently, on-line techniques using isotope ratio mass spectrometry (IRMS). We describe a new simple on-line pyrolysis method for the analysis of 2H/1H in water and urine samples by continuous flow IRMS, normally used for 2H/1H measurements in organic compounds. A deactivated column connected the split injector to a high-temperature conversion reactor (TC HD), and 0.5 microL of sample was injected. Accuracy and precision were determined with Vienna Standard Mean Ocean Water (VSMOW), Standard Light Antarctic Precipitation (SLAP), and Greenland Ice Sheet Precipitation (GISP). The range of linearity was measured with a calibration curve of enriched water from 0 up to 0.1 atom percent excess (APE) (i.e. -72 up to 6323 delta per mil (deltaD per thousand)) with a precision of <5 per thousand and accuracy ranging between 1 and 55 per thousand. Blinded reanalysis of urine samples by an equilibration device (Gas Bench) and by a dedicated pyrolysis system (TC/EA) was performed and results compared by the Bland-Altman test. Enrichments ranged between 600 and 2400 per thousand deltaD(VSMOW) with a precision of +/-5 per thousand. Urine enrichments described by our method were strongly correlated with values obtained by Gas Bench and TC/EA (p < 0.0001). There was a significant memory effect that was reduced by injecting the sample 15 times and discarding the first 10 injections, together with accurate furnace conditioning and appropriate cleaning of the syringe. Data indicate that the method is accurate, and that it can be used for water and urine deuterium determination when a Gas Bench or TC/EA instrument is not available and the amount of sample is limited. 相似文献
90.