全文获取类型
收费全文 | 838篇 |
免费 | 25篇 |
国内免费 | 3篇 |
专业分类
化学 | 581篇 |
晶体学 | 5篇 |
力学 | 8篇 |
数学 | 117篇 |
物理学 | 155篇 |
出版年
2021年 | 5篇 |
2019年 | 5篇 |
2018年 | 9篇 |
2017年 | 6篇 |
2016年 | 19篇 |
2015年 | 13篇 |
2014年 | 19篇 |
2013年 | 31篇 |
2012年 | 50篇 |
2011年 | 72篇 |
2010年 | 41篇 |
2009年 | 26篇 |
2008年 | 46篇 |
2007年 | 55篇 |
2006年 | 44篇 |
2005年 | 34篇 |
2004年 | 34篇 |
2003年 | 30篇 |
2002年 | 35篇 |
2001年 | 21篇 |
2000年 | 12篇 |
1999年 | 10篇 |
1998年 | 10篇 |
1997年 | 10篇 |
1996年 | 16篇 |
1995年 | 14篇 |
1994年 | 13篇 |
1993年 | 12篇 |
1992年 | 19篇 |
1991年 | 8篇 |
1990年 | 11篇 |
1989年 | 5篇 |
1988年 | 3篇 |
1987年 | 14篇 |
1986年 | 6篇 |
1985年 | 11篇 |
1984年 | 9篇 |
1983年 | 7篇 |
1982年 | 6篇 |
1980年 | 6篇 |
1979年 | 4篇 |
1978年 | 4篇 |
1977年 | 5篇 |
1976年 | 5篇 |
1974年 | 4篇 |
1973年 | 5篇 |
1970年 | 4篇 |
1958年 | 5篇 |
1956年 | 3篇 |
1955年 | 3篇 |
排序方式: 共有866条查询结果,搜索用时 31 毫秒
781.
Roithová J Schröder D Loos J Schwarz H Jankowiak HC Berger R Thissen R Dutuit O 《The Journal of chemical physics》2005,122(9):094306
Charge stripping (CS) of the molecular ion of toluene, C(7)H(8) (+)-->C(7)H(8) (2+)+e, is often used as a reference for the determination of second ionization energies in energy-resolved CS experiments. For calibration of the kinetic energy scale, a value of IE(C(7)H(8) (+))=(15.7+/-0.2) eV derived from the appearance energy of the toluene dication upon electron ionization has been accepted generally. Triggered by some recent discrepancies between CS measurements on the one hand and different experimental methods as well as theoretical predictions on the other, we have reinvestigated the photon-induced double ionization of toluene using synchrotron radiation. These photoionization measurements yield phenomenological appearance energies of AE(C(7)H(8) (+))=(8.81+/-0.03) eV for the monocation and AE(C(7)H(8) (2+))=(23.81+/-0.06) eV for the dication. The former is in good agreement with a much more precise spectroscopic value, IE(C(7)H(8))=(8.8276+/-0.0006) eV. Explicit consideration of the Franck-Condon envelopes associated with photoionization to the dication in conjunction with the application of the Wannier law leads to an adiabatic ionization energy IE(a)(C(7)H(8) (+))=(14.8+/-0.1) eV, which is as much as 0.9 eV lower than the previous value derived from electron ionization. Because in many previous CS measurements the transition C(7)H(8) (+)-->C(7)H(8) (2+)+e was used as a reference, the energetics of several gaseous dications might need some readjustment. 相似文献
782.
783.
Wilfried A. Knig Angelika Krüger Detlef Icheln Torsten Runge 《Journal of separation science》1992,15(3):184-189
Using a dual column gas chromatograph equipped with two capillary columns coated with heptakis(6-O-methyl-2,3-di-O-pentyl)-β-cyclodextrin (6-me-2,3-pe-β-CD) and octakis(6-O-methyl-2,3-di-O-pentyl)-γ-cyclodextrin (6-me-2,3-pe-γ-CD), respectively, all important olefinic monoterpene hydrocarbons occurring in essential oils, including α-thujene, α- and β-pinene, camphene, sabinene, α- and β-phellandrene, Δ-3-carene and limonene can be resolved into enantiomers. With the chromatographic system described the characteristic enantiomeric composition of these monoterpene hydrocarbons in essential oils can be determined. 相似文献
784.
Stöckigt J Sheludk Y Unger M Gerasimenko I Warzecha H Stöckigt D 《Journal of chromatography. A》2002,967(1):85-113
Systems for efficient separation of selected alkaloid groups by high performance liquid chromatography (HPLC), capillary electrophoresis (CE) and capillary electrophoresis coupled with electrospray ionisation mass spectrometry (CE-ESI-MS) are described. The optimized HPLC system was applied for the separation of 23 standard indole alkaloids as well as for qualitative and quantitative analyses of crude alkaloid extracts of Rauvolfia serpentina X Rhazya stricta hybrid cell cultures. The developed conditions for CE analysis proved to be efficient for separation of mixtures of standard indole and beta-carboline alkaloids. The described buffer system is also applicable in the combination of CE with electrospray ionisation mass spectrometry. This analytical technique allowed the separation and identification of components of standard indole alkaloid mixture as well as crude extracts of R. serpentina roots, R. serpentina cell suspension cultures and cortex of Aspidosperma quebracho-blanco. The influence of buffer composition and analyte structures on separation is discussed. 相似文献
785.
In order to make analytical measurement results traceable to the SI units in the field of clinical chemistry, an ion chromatographic (IC) measurement procedure has been developed which allows the amount of substance of the four so-called electrolytes Na, K, Mg and Ca as well as that of Li to be determined efficiently in human serum and with high accuracy. The IC measurement procedure was validated using primary measurement procedures confirmed by international comparison measurements and is proposed for use as a transfer standard when comparing measurements with clinical reference laboratories. The solutions used for calibration were gravimetrically prepared from pure substances (salts). Their chemical compositions had been iteratively fitted to those of the samples. The serum samples were mineralized by microwave-assisted digestion. The following relative expanded uncertainties for the average elemental contents were obtained: Li 0.4%, Na 0.14%, K 0.6%, Mg 0.8% and Ca 0.4%. 相似文献
786.
Semialjac M Schröder D Schwarz H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(18):4396-4404
Car-Parrinello molecular dynamics (CPMD) studies of neutral (1) and ionized (1 (+.)) valeramide are performed with the aim of providing a rationalization for the unusual temperature effect on the dissociation pattern of 1(+.) observed in mass spectrometric experiments. According to CPMD simulations of neutral valeramide 1 performed at approximately 500 K, the conformation with the fully relaxed carbon backbone predominates (96 %). Conformational changes involving folding of the carbon backbone into conformers that would allow intramolecular H transfers are predicted not to take place spontaneously at this temperature because of the barrier heights associated with these transitions (3.5 and 6.9 kcal mol(-1)), which cannot be overcome by thermal motion alone. For 1(+.), CPMD simulations performed at approximately 300 K reveal a substantial stability of a conformation in which the carbon backbone is fully relaxed; no reaction is observed even after 7 ps. However, when conformers with already folded carbon-backbones are used as initial geometries in the CPMD simulations, the gamma-hydrogen migration (McLafferty rearrangement resulting in C(3)H(6)) is already completed within 2 ps. For this important process, the free activation energy associated with both a required conformational change and the subsequent H transfer equals 4.5 kcal mol(-1), while for the formally related delta-H shift (which eventually gives rise to the elimination of C(2)H(4)/C(2)H(5.)) it amounts to 7.0 kcal mol(-1). Since the barriers associated with conformational changes are energetically more demanding than those of the corresponding hydrogen transfers, 1(+.) is essentially trapped by conformational barriers and long-lived at approximately 300 K. At elevated temperatures (500 K), the preferred reaction (within 7.3 ps) in the CPMD simulation corresponds to the McLafferty rearrangement. The estimated free activation energy associated with this process amounts to 2.5 kcal mol(-1), while the free activation energy for the delta-H transfer equals 4.4 kcal mol(-1). This relatively small free activation energy for the McLafferty rearrangement might cause dissociation of a substantial fraction of 1(+.) prior to the time-delayed mass selection, which would reduce the C3/C2 ratio in the experiments conducted with metastable ions that have a lifetime in the order of some micros at a source temperature of 500 K. 相似文献
787.
788.
789.
790.