全文获取类型
收费全文 | 826篇 |
免费 | 37篇 |
国内免费 | 2篇 |
专业分类
化学 | 600篇 |
晶体学 | 8篇 |
力学 | 15篇 |
数学 | 133篇 |
物理学 | 109篇 |
出版年
2023年 | 8篇 |
2022年 | 9篇 |
2021年 | 21篇 |
2020年 | 17篇 |
2019年 | 15篇 |
2018年 | 16篇 |
2017年 | 19篇 |
2016年 | 35篇 |
2015年 | 30篇 |
2014年 | 29篇 |
2013年 | 48篇 |
2012年 | 60篇 |
2011年 | 54篇 |
2010年 | 42篇 |
2009年 | 24篇 |
2008年 | 50篇 |
2007年 | 49篇 |
2006年 | 58篇 |
2005年 | 44篇 |
2004年 | 22篇 |
2003年 | 27篇 |
2002年 | 16篇 |
2001年 | 9篇 |
2000年 | 5篇 |
1999年 | 12篇 |
1998年 | 6篇 |
1997年 | 3篇 |
1996年 | 9篇 |
1995年 | 6篇 |
1994年 | 6篇 |
1993年 | 11篇 |
1992年 | 7篇 |
1991年 | 8篇 |
1990年 | 3篇 |
1989年 | 8篇 |
1988年 | 4篇 |
1986年 | 7篇 |
1985年 | 6篇 |
1984年 | 8篇 |
1983年 | 5篇 |
1982年 | 8篇 |
1981年 | 6篇 |
1980年 | 6篇 |
1979年 | 3篇 |
1978年 | 6篇 |
1977年 | 6篇 |
1975年 | 4篇 |
1974年 | 3篇 |
1973年 | 4篇 |
1971年 | 2篇 |
排序方式: 共有865条查询结果,搜索用时 156 毫秒
61.
The oxidative cleavage of the known anti-psoriasis drug 1 to give 2 has been reported previously. Due to the importance of accessing medium-sized ring containing systems via oxidative cleavage, this reaction has been revisited revealing additional information about the structure of 2. Alternative reaction products were identified when the reaction was carried out in the presence of water. The conversion of 1 to 2 has also been carried out using ruthenium tetroxide. A detailed variable temperature NMR and computational study of the restricted rotation of the N-aryl ring in 2 is presented. 相似文献
62.
The ASMS conference on ion spectroscopy brought together at Asilomar on October 16–20, 2009 a large group of mass spectrometrists
working in the area of ion spectroscopy. In this introduction to the field, we provide a brief history, its current state,
and where it is going. Ion spectroscopy of intermediate size molecules began with photoelectron spectroscopy in the 1960s,
while electronic spectroscopy of ions using the photodissociation “action spectroscopic” mode became active in the next decade.
These approaches remained for many years the main source of information about ionization energies, electronic states, and
electronic transitions of ions. In recent years, high-resolution laser techniques coupled with pulsed field ionization and
sample cooling in molecular beams have provided high precision ionization energies and vibrational frequencies of small to
intermediate sized molecules, including a number of radicals. More recently, optical parametric oscillator (OPO) IR lasers
and free electron lasers have been developed and employed to record the IR spectra of molecular ions in either molecular beams
or ion traps. These results, in combination with theoretical ab initio molecular orbital (MO) methods, are providing unprecedented
structural and energetic information about gas-phase ions. 相似文献
63.
Threshold photoelectron photoion coincidence has been used to prepare selected internal energy distributions of nitrosobenzene ions [C(6)H(5)NO(+)]. Dissociation to C(6)H(5)(+) + NO products was measured over a range of internal energies and rate constants from 10(3) to 10(7) s(-1) and fitted with the statistical theory of unimolecular decay. A 0 K dissociative photoionization onset energy of 10.607 ± 0.020 eV was derived by using the simplified statistical adiabatic channel model. The thermochemical network of Active Thermochemical Tables (ATcT) was expanded to include phenyl and phenylium, as well as nitrosobenzene. The current ATcT heats of formation of these three species at 0 K (298.15 K) are 350.6 (337.3) ± 0.6, 1148.7 (1136.8) ± 1.0, and 215.6 (198.6) ± 1.5 kJ mol(-1), respectively. The resulting adiabatic ionization energy of phenyl is 8.272 ± 0.010 eV. The new ATcT thermochemistry for phenyl entails a 0 K (298.15 K) C-H bond dissociation enthalpy of benzene of 465.9 (472.1) ± 0.6 kJ mol(-1). Several related thermochemical quantities from ATcT, including the current enthalpies of formation of benzene, monohalobenzenes, and their ions, as well as interim ATcT values for the constituent atoms, are also given. 相似文献
64.
Zachariasova M Cajka T Godula M Malachova A Veprikova Z Hajslova J 《Rapid communications in mass spectrometry : RCM》2010,24(22):3357-3367
The objective of the presented study was to develop and optimize a simple, high-throughput method for the control of 32 mycotoxins (Fusarium and Alternaria toxins, aflatoxins, ergot alkaloids, ochratoxins, and sterigmatocystin) in beer. Due to the broad range of their physicochemical properties, the sample preparation step was simplified as much as possible to avoid analyte losses. The addition of acetonitrile to beer samples enabled precipitation of abundant matrix components. The clean-up efficiency was controlled by ambient mass spectrometry employing a direct analysis in real time (DART) ion source. For determination of analytes, ultra-high-performance liquid chromatography hyphenated with high-resolution mass spectrometry utilizing an orbitrap (U-HPLC-orbitrapMS) or time-of-flight (TOFMS) technology was used. Because of significantly better detection capabilities of the orbitrap technology, the U-HPLC-orbitrapMS method was chosen as a determinative step and fully validated. To compensate matrix effects, matrix-matched calibration was employed. The lowest calibration levels for most of the target mycotoxins ranged from 1 to 8 μg L(-1) beer and the recoveries of analytes were in range from 86 to 124%. 相似文献
65.
The nucleophilic addition of both silyl ketene acetals and lithium enolates derived from methyl acetate to chiral non-racemic N-(benzyloxyethyl)nitrones has been studied both experimentally and theoretically. Aromatic nitrones showed lower reactivity that aliphatic nitrones and the addition of the silyl ketene acetal led to lower selectivities than the addition of the corresponding lithium enolate. Whereas low selectivity was obtained for the addition of the silyl ketene acetal, only one diastereomer could be detected in all cases for the addition of lithium enolate to aliphatic nitrones. The synthetic utility of the two chiral auxiliaries employed lies in the preparation of enantiomeric compounds. DFT theoretical calculations confirmed the stepwise mechanism for the addition of silyl ketene acetals to nitrones and are in good agreement with the observed experimental results. 相似文献
66.
67.
C. Tomas J.P. Girardeau-Montaut M. Afif M. Romand M. Charbonnier T.M. Duc 《Applied Physics A: Materials Science & Processing》1997,64(5):467-471
3+ :YAG laser with 5th harmonic generator, generating 16 ps duration pulses at 213 nm, with energies up to 0.5 mJ. Experimental results concerning
the action of laser pulses, as well as the effects of residual pressure on the cleanliness of the photocathodes surface are
presented and discussed. Influence of laser pulses and residual pressure on the work function of the metal are also investigated.
Received: 15 April 1996/Accepted: 5 November
1996 相似文献
68.
Tomas de Paulis Nabil El Tayar Pierre-Alain Carrupt Bernard Testa Han van de Waterbeemd 《Helvetica chimica acta》1991,74(2):241-254
A large series of orthopramides (= 2-methoxybenzamides), 6-methoxysalicylamides, and 2,6-dimethoxy-benzamides were examined for their affinity to the dopamine D2 receptor. The binding data were correlated with physicochemical parameters and 13C-NMR chemical shifts using the cross-validated partial least-squares method and multiple linear regression analysis. The results quantitate the influence of electronic factors and lipophilicity to D2 receptor binding. They also show that the N-[(1-ethylpyrroIidin-2-yl)methyl] and N-(1-benzylpiperidin-4-yl) side-chains affect the mode of binding of these compounds. 相似文献
69.
Gluconobacter oxydans bacteria exhibit a unique metabolism for quick and incomplete oxidation of a wide range of different compounds (aldoses, ketoses, mono- and poly-alcohols, etc.). Such biotransformation efficiency with simple biomass production led to the industrial applications of these bacteria in the production of several important commodities. Their respiratory activity can also be successfully studied and used in the field of bioelectrochemistry. The main aim of this review is to present various strategies to improve selectivity of assays using intact/treated cells of G. oxydans, to introduce the application of G. oxydans-based biosensors in selective monitoring of analytes during biotransformation processes and to provide information about utilizable sugars in fermentation media or in biological oxygen demand value determination. The final part of the review describes potential application of G. oxydans cells in the generation of electricity from complex fuels within microbial fuel cells by advanced direct electron transfer route between bacterial cells and electrodes. 相似文献
70.
A tight Heffter array is an matrix with nonzero entries from such that (i) the sum of the elements in each row and each column is 0, and (ii) no element from appears twice. We prove that exist if and only if both m and n are at least 3. If H has the property that all entries are integers of magnitude at most , every row and column sum is 0 over the integers, and H also satisfies ), we call H an integer Heffter array. We show integer Heffter arrays exist if and only if . Finally, an integer Heffter array is shiftable if each row and column contains the same number of positive and negative integers. We show that shiftable integer arrays exists exactly when both are even. 相似文献