全文获取类型
收费全文 | 98篇 |
免费 | 3篇 |
专业分类
化学 | 83篇 |
力学 | 10篇 |
数学 | 5篇 |
物理学 | 3篇 |
出版年
2020年 | 3篇 |
2019年 | 1篇 |
2018年 | 3篇 |
2017年 | 2篇 |
2016年 | 9篇 |
2015年 | 2篇 |
2014年 | 4篇 |
2013年 | 9篇 |
2012年 | 9篇 |
2011年 | 7篇 |
2010年 | 4篇 |
2009年 | 7篇 |
2008年 | 2篇 |
2007年 | 1篇 |
2005年 | 3篇 |
2004年 | 3篇 |
2002年 | 1篇 |
2000年 | 2篇 |
1998年 | 1篇 |
1997年 | 2篇 |
1996年 | 1篇 |
1995年 | 1篇 |
1985年 | 1篇 |
1984年 | 12篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1976年 | 1篇 |
1968年 | 1篇 |
1963年 | 1篇 |
排序方式: 共有101条查询结果,搜索用时 15 毫秒
1.
Titanium - catalyzed dimerization of cycloheptatriene affords pentacyclo[7.5.0.02,8.05,14.07,11]tetradeca-3,12-diene, , and pentacyclo[8.4.0.03,7.04,14.06,11]tetradeca-8,12-diene, . By heating, is converted quantitatively into . 相似文献
2.
Vivekananda S Sadílek M Chen X Turecek F 《Journal of the American Society for Mass Spectrometry》2004,15(7):1055-1067
Collisional neutralization of several isomeric C(4)H(7)O(2) cations is used to generate radicals that share some structural features with transient species that are thought to be produced by radiolysis of 2-deoxyribose. The title 2-hydroxyoxolan-2-yl radical (1) undergoes nearly complete dissociation when produced by femtosecond electron transfer from thermal organic electron donors dimethyl disulfide and N,N-dimethylaniline in the gas phase. Product analysis, isotope labeling ((2)H and (18)O), and potential energy surface mapping by ab initio calculations at the G2(MP2) and B3-PMP2 levels of theory and in combination with Rice-Ramsperger-Kassel-Marcus (RRKM) kinetic calculations are used to assign the major and some minor pathways for 1 dissociations. The major (approximately 90%) pathway is initiated by cleavage of the ring C-5[bond]O bond in 1 and proceeds to form ethylene and *CH(2)COOH as main products, whereas loss of a hydrogen atom forms 4-hexenoic acid as a minor product. Loss of the OH hydrogen atom forming butyrolactone (2, approximately 9%) and cleavage of the C-3[bond]C-4 bonds (<1%) in 1 are other minor pathways. The major source of excitation in 1 is by Franck-Condon effects that cause substantial differences between the adiabatic and vertical ionization of 1 (5.40 and 6.89 eV, respectively) and vertical recombination in the precursor ion 1(+) (4.46 eV). (+)NR(+) mass spectra distinguish radical 1 from isomeric radicals 2-oxo-(1H)oxolanium (3), 1,3-dioxan-2-yl (9), and 1,3-dioxan-4-yl (10) that were generated separately from their corresponding ion precursors. 相似文献
3.
We present sets of real 3- symbols which correspond to explicitly given irreducible matrix representations for the two double group hierarchies T* C
3
*
and T* C
2
*
. They fit into the formalism exposed in a previous paper [1] on the general theory of 3- symbols and coupling coefficients and illustrate much of the discussion in a subsequent one [2] treating the particular properties of the double groups. 相似文献
4.
Yue Liu Dr. Andy Dang Dr. Jan Urban Prof. Dr. František Tureček 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(20):7846-7851
Adenosine radicals tagged with a fixed-charge group were generated in the gas phase and structurally characterized by tandem mass spectrometry, deuterium labeling, and UV/Vis action spectroscopy. Experimental results in combination with Born–Oppenheimer molecular dynamics, ab initio, and excited-state calculations led to unambiguous assignment of adenosine radicals as N-7 hydrogen atom adducts. The charge-tagged radicals were found to be electronically equivalent to natural DNA nucleoside radicals. 相似文献
5.
Bitar D. Ture Savadkoohi A. Lamarque C.-H. Gourdon E. Collet M. 《Nonlinear dynamics》2020,99(2):1433-1450
Nonlinear Dynamics - The present research work aims to design a passive vibration control based on nonlinear energy pumping. An extended asymptotic approach is introduced based on the invariant... 相似文献
6.
Scott A. Shaffer František Tureček 《Journal of the American Society for Mass Spectrometry》1995,6(11):1004-1018
Neutralization—reionization mass spectrometry is used to generate hypervalent 9-N-4 (ammonium) and 9-O-3 (oxonium) radicals derived from protonated α,ω-bis-(dimethylamino)alkanes and α,ω-dimethoxyalkanes, which exist as cyclic hydrogen-bonded structures in the gas phase. Collisional neutralization with dimethyl disulfide, trimethylamine, and xenon of the hydrogen-bonded onium cations followed by reionization with oxygen results in complete dissociation. Bond cleavages at the hypervalent nitrogen atoms are found to follow the order CH2-N>CH3-N>N-H, which differs from that in the monofunctional hydrogen-n-heptyldimethylammonium radical, which gives CH2-N>N-H>CH3-N. No overall stabilization through hydrogen bonding of the bifunctional hypervalent ammonium and oxonium radicals is observed. Subtle effects of ring size are found that tend to stabilize large ring structures and are attributed to intramolecular hydrogen bonding. 相似文献
7.
Vivekananda S Sadílek M Chen X Adams LE Turecek F 《Journal of the American Society for Mass Spectrometry》2004,15(7):1068-1079
The title radical (1) is generated in the gas-phase by collisional neutralization of carbonyl-protonated oxolan-3-one. A 1.5% fraction of 1 does not dissociate and is detected following reionization as survivor ions. The major dissociation of 1 (approximately 56%) occurs as loss of the hydroxyl H atom forming oxolan-3-one (2). The competing ring cleavages by O[bond]C-2 and C-4[bond]C-5 bond dissociations combined account for approximately 42% of dissociation and result in the formation of formaldehyde and 2-hydroxyallyl radical. Additional ring-cleavage dissociations of 1 resulting in the formation of C(2)H(3)O and C(2)H(4)O cannot be explained as occurring competitively on the doublet ground (X) electronic state of 1, but are energetically accessible from the A and higher electronic states accessed by vertical electron transfer. Exothermic protonation of 2 also produces 3-oxo-(1H)-oxolanium cation (3(+)) which upon collisional neutralization gives hypervalent 3-oxo-(1H)-oxolanium radical (3). The latter dissociates spontaneously by ring opening and expulsion of hydroxy radical. Experiment and calculations suggest that carbohydrate radicals incorporating the 3-hydroxyoxolan-3-yl motif will prefer ring-cleavage dissociations at low internal energies or upon photoexcitation by absorbing light at approximately 590 and approximately 400 nm. 相似文献
8.
Moss CL Chung TW Wyer JA Nielsen SB Hvelplund P Tureček F 《Journal of the American Society for Mass Spectrometry》2011,22(4):731-751
Electron transfer and capture mass spectra of a series of doubly charged ions that were phosphorylated pentapeptides of a
tryptic type (pS,A,A,A,R) showed conspicuous differences in dissociations of charge-reduced ions. Electron transfer from both
gaseous cesium atoms at 100 keV kinetic energies and fluoranthene anion radicals in an ion trap resulted in the loss of a
hydrogen atom, ammonia, and backbone cleavages forming complete series of sequence z ions. Elimination of phosphoric acid was negligible. In contrast, capture of low-energy electrons by doubly charged ions
in a Penning ion trap induced loss of a hydrogen atom followed by elimination of phosphoric acid as the dominant dissociation
channel. Backbone dissociations of charge-reduced ions also occurred but were accompanied by extensive fragmentation of the
primary products. z-Ions that were terminated with a deaminated phosphoserine radical competitively eliminated phosphoric acid and H2PO4 radicals. A mechanism is proposed for this novel dissociation on the basis of a computational analysis of reaction pathways
and transition states. Electronic structure theory calculations in combination with extensive molecular dynamics mapping of
the potential energy surface provided structures for the precursor phosphopeptide dications. Electron attachment produces
a multitude of low lying electronic states in charge-reduced ions that determine their reactivity in backbone dissociations
and H- atom loss. The predominant loss of H atoms in ECD is explained by a distortion of the Rydberg orbital space by the
strong dipolar field of the peptide dication framework. The dipolar field steers the incoming electron to preferentially attach
to the positively charged arginine side chain to form guanidinium radicals and trigger their dissociations. 相似文献
9.
Structures of tert-butylcarbamate ions in the gas-phase and methanol solution were studied for simple secondary and tertiary carbamates as well as for carbamate-containing products and internal standards for lysosomal enzyme assays used in newborn screening of a α-galactosidase A deficiency (Fabry disease), mucopolysaccharidosis I (Hurler disease), and mucopolysaccharidosis II (Hunter disease). The protonation of simple t-butylcarbamates can occur at the carbonyl group, which is the preferred site in the gas phase. Protonation in methanol solution is more favorable if occurring at the carbamate nitrogen atom. The protonation of more complex t-butylcarbamates occurs at amide and carbamate carbonyl groups, and the ions are stabilized by intramolecular hydrogen bonding, which is affected by solvation. Tertiary carbamates containing aminophenol amide groups were calculated to have substantially greater gas-phase basicities than secondary carbamates containing coumarin amide groups. The main diagnostically important ion dissociation by elimination of 2-methylpropene (isobutylene, i-C(4)H(8)) and carbon dioxide is shown by experiment and theory to proceed in two steps. Energy-resolved collision-induced dissociation of the Hurler's disease enzymatic product ion, which is a coumarin-diamine linker-t-butylcarbamate conjugate (3a(+)), indicated separate energy thresholds for the loss of i-C(4)H(8) and CO(2). Computational investigation of the potential energy surface along two presumed reaction pathways indicated kinetic preference for the migration of a t-butyl hydrogen atom to the carbamate carbonyl resulting in the isobutylene loss. The consequent loss of CO(2) required further proton migrations that had to overcome energy barriers. 相似文献
10.
Kadriye Ertekin Ozlem Oter Mustafa Ture Serpil Denizalti Engin Cetinkaya 《Journal of fluorescence》2010,20(2):533-540
In this study, a very sensitive and highly selective irreversible optical chemical sensor (optode) for mercury ions was described.
The sensing scheme was based on the interaction of Hg (II) with a newly synthesized fluoroionophore; chloro phenyl imino propenyl
aniline (CPIPA) in plasticized PVC membrane. The sensor membranes were tested for the determination of mercury ion in aqueous
solutions by batch and flow-through methods. The optodes allow determination of Hg (II) in the working range of 1.0 × 10−9–1.0 × 10−5 M with a detection limit of 4.3 ppb. The sensor exhibited excellent selectivity for Hg (II) with respect to several common
alkali, alkaline earth and transition metal ions. The association constant of the 1:1 complex formation for Hg (II) was found
to be Ka = 1.86 × 105 M−1. The CPIPA exhibited high fluorescence quantum yield, long excitation and emission wavelength and high Stokes’ shift values
in the solid matrix which makes it compatible with solid state optics. 相似文献