全文获取类型
收费全文 | 533篇 |
免费 | 27篇 |
专业分类
化学 | 472篇 |
力学 | 1篇 |
数学 | 44篇 |
物理学 | 43篇 |
出版年
2023年 | 10篇 |
2022年 | 10篇 |
2021年 | 31篇 |
2020年 | 21篇 |
2019年 | 13篇 |
2018年 | 10篇 |
2017年 | 8篇 |
2016年 | 22篇 |
2015年 | 25篇 |
2014年 | 24篇 |
2013年 | 29篇 |
2012年 | 61篇 |
2011年 | 56篇 |
2010年 | 16篇 |
2009年 | 20篇 |
2008年 | 37篇 |
2007年 | 42篇 |
2006年 | 31篇 |
2005年 | 21篇 |
2004年 | 21篇 |
2003年 | 9篇 |
2002年 | 19篇 |
2001年 | 4篇 |
2000年 | 3篇 |
1999年 | 2篇 |
1998年 | 1篇 |
1995年 | 2篇 |
1994年 | 1篇 |
1993年 | 2篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1986年 | 2篇 |
1984年 | 1篇 |
1976年 | 1篇 |
1967年 | 1篇 |
排序方式: 共有560条查询结果,搜索用时 15 毫秒
541.
Recent advances in synthetic chemistry have led to the discovery of "superoxidized" iron centers with valencies Fe(v) and Fe(vi) [K. Meyer et al., J. Am. Chem. Soc., 1999, 121, 4859-4876; J. F. Berry et al., Science, 2006, 312, 1937-1941; F. T. de Oliveira et al., Science, 2007, 315, 835-838.]. Furthermore, in recent years a number of high-valent Fe(iv) species have been found as reaction intermediates in metalloenzymes and have also been characterized in model systems [C. Krebs et al., Acc. Chem. Res., 2007, 40, 484-492; L. Que, Jr, Acc. Chem. Res., 2007, 40, 493-500.]. These species are almost invariably stabilized by a highly basic ligand X(n-) which is either O(2-) or N(3-). The differences in structure and bonding between oxo- and nitrido species as a function of oxidation state and their consequences on the observable spectroscopic properties have never been carefully assessed. Hence, fundamental differences between high-valent iron complexes having either Fe=O or Fe=N multiple bonds have been probed computationally in this work in a series of hypothetical trans-[FeO(NH(3))(4)OH](+/2+/3+) (1-3) and trans-[FeN(NH(3))(4)OH](0/+/2+) (4-6) complexes. All computational properties are permeated by the intrinsically more covalent character of the Fe=N multiple bond as compared to the Fe=O bond. This difference is likely due to differences in Z* between N and O that allow for better orbital overlap to occur in the case of the Fe=N multiple bond. Spin-state energetics were addressed using elaborate multireference ab initio computations that show that all species 1-6 have an intrinsic preference for the low-spin state, except in the case of 1 in which S=1 and S=2 states are very close in energy. In addition to M?ssbauer parameters, g-tensors, zero-field splitting and iron hyperfine couplings, X-ray absorption Fe K pre-edge spectra have been simulated using time-dependent DFT methods for the first time for a series of compounds spanning the high-valent states +4, +5, and +6 for iron. A remarkably good correlation of these simulated pre-edge features with experimental data on isolated high-valent intermediates has been found, allowing us to assign the main pre-edge features to excitations into the empty Fe d(z(2)) orbital, which is able to mix with Fe 4p(z), allowing an efficient mechanism for the intensification of pre-edge features. 相似文献
542.
Riela S Bruno M Formisano C Rigano D Rosselli S Saladino ML Senatore F 《Journal of separation science》2008,31(6-7):1110-1117
The essential oil of Calamintha nepeta has been obtained by solvent-free microwave extraction (SFME) and by classical hydrodistillation (HD). A comparative qualitative-quantitative study on the composition of the oils was carried out. A total of 38 compounds, constituting 97.6% of the oil, were identified in the oil obtained by SFME, whereas 46 compounds, representing 95.4% of the oil, were characterized in the HD oil. SFME-distilled oil is richer in lightly oxygenated monoterpenes (LOM) than HD oil. It also has a higher amount of sesquiterpenes and a lower quantity of hydrocarbon monoterpenes. HD oil seems to be affected by chemical changes more than SFME oil. 相似文献
543.
M Colombo S Mazzucchelli V Collico S Avvakumova L Pandolfi F Corsi F Porta D Prosperi 《Angewandte Chemie (International ed. in English)》2012,51(37):9272-9275
All bound up: A small variant of protein?A was used as a biotemplate for the synthesis and biofunctionalization of gold nanoparticles (AuNPs). These functionalized AuNPs were able to bind to antibodies (green blocks, trastuzumab; TZ) with a defined orientation, thus showing promise as bio-nanoparticle systems suitable for selective cell labeling by membrane-receptor-specific recognition. 相似文献
544.
Zatti S Zoso A Serena E Luni C Cimetta E Elvassore N 《Langmuir : the ACS journal of surfaces and colloids》2012,28(5):2718-2726
Micropatterning techniques and substrate engineering are becoming useful tools to investigate several aspects of cell-cell interaction biology. In this work, we rationally study how different micropatterning geometries can affect myoblast behavior in the early stage of in vitro myogenesis. Soft hydrogels with physiological elastic modulus (E = 15 kPa) were micropatterned in parallel lanes (100, 300, and 500 μm width) resulting in different local and global myoblast densities. Proliferation and differentiation into multinucleated myotubes were evaluated for murine and human myoblasts. Wider lanes showed a decrease in murine myoblast proliferation: (69 ± 8)% in 100 μm wide lanes compared to (39 ± 7)% in 500 μm lanes. Conversely, fusion index increased in wider lanes: from (46 ± 7)% to (66 ± 7)% for murine myoblasts, and from (15 ± 3)% to (36 ± 2)% for human primary myoblasts, using a patterning width of 100 and 500 μm, respectively. These results are consistent with both computational modeling data and conditioned medium experiments, which demonstrated that wider lanes favor the accumulation of endogenous secreted factors. Interestingly, human primary myoblast proliferation is not affected by patterning width, which may be because the high serum content of their culture medium overrides the effect of secreted factors. These data highlight the role of micropatterning in shaping the cellular niche through secreted factor accumulation, and are of paramount importance in rationally understanding myogenesis in vitro for the correct design of in vitro skeletal muscle models. 相似文献
545.
Prof. Arturo Arduini Dr. Rocco Bussolati Prof. Alberto Credi Simone Monaco Prof. Andrea Secchi Dr. Serena Silvi Prof. Margherita Venturi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(50):16203-16213
The development of a pseudorotaxane motif capable of performing unidirectional threading and dethreading processes under control of external stimuli is particularly important for the construction of processive linear motors based on rotaxanes and, at least in principle, it discloses the possibility to access to rotary motors based on catenanes. Here, we report a strategy to obtain the solvent‐controlled unidirectional transit of a molecular axle through a molecular wheel. It is based on the use of appropriately designed molecular components, the essential feature of which is their non‐symmetric structure. Specifically they are an axle containing a central electron‐acceptor 4,4′‐bipyridinium core functionalized with a hexanol chain at one side, and a stilbene unit connected through a C6 chain at the other side, and a heteroditopic tris(phenylureido)‐calix[6]arene wheel. In apolar solvents the axle threads into the wheel from its upper rim and with the end carrying the OH group, giving an oriented pseudorotaxane structure. After a stoppering reaction, which replaces the small hydroxy group with a bulky diphenylacetyl moiety, and replacement of the apolar solvent with a polar one, dethreading occurs through the slippage of the stilbene unit from the lower rim of the wheel, that is, in the same direction of the threading process. The essential role played by the stilbene unit to achieve the unidirectional transit of the axle through the wheel, and to tune the dethreading rate by light is also demonstrated. 相似文献
546.
Kaifer AE Li W Silvi S Sindelar V 《Chemical communications (Cambridge, England)》2012,48(53):6693-6695
Deprotonation of the two terminal COOH groups on a 4,4'-bipyridinium linear derivative leads to a pronounced slow down on the kinetics of threading and unthreading by the cucurbit[7]uril host. 相似文献
547.
Serena Doria 《Annals of Operations Research》2012,195(1):33-48
A model of coherent upper conditional prevision for bounded random variables is proposed in a metric space. It is defined
by the Choquet integral with respect to Hausdorff outer measure if the conditioning event has positive and finite Hausdorff
outer measure in its Hausdorff dimension. Otherwise, when the conditioning event has Hausdorff outer measure equal to zero
or infinity in its Hausdorff dimension, it is defined by a 0–1 valued finitely, but not countably, additive probability. If
the conditioning event has positive and finite Hausdorff outer measure in its Hausdorff dimension it is proven that a coherent
upper conditional prevision is uniquely represented by the Choquet integral with respect to the upper conditional probability
defined by Hausdorff outer measure if and only if it is monotone, comonotonically additive, submodular and continuous from
below. 相似文献
548.
In the present study, a comparison between a disposable electrochemical DNA biosensor and a Vibrio fischeri-based luminescent sensor for the detection of toxicants in water samples was made.In order to realize this study, a disposable electrochemical DNA biosensor has been reported. The DNA biosensor is assembled by immobilizing double stranded Calf Thymus DNA onto the surface of a disposable carbon screen-printed electrode. The oxidation signal of the guanine base, obtained by a square wave voltammetric scan, is used as analytical signal to detect the DNA damage; the presence of low molecular weight compounds with affinity for nucleic acids is measured by their effect on the guanine oxidation peak.Wastewater samples provided during First European Interlaboratory Exercise on water toxicity in the course of the project SWIFT-WFD were analyzed, and biosensor results were compared with a currently used toxicity test ToxAlert®100 based on the bioluminescence inhibition of Vibrio fischeri. This test have been used because is rapid, easy handling and cost effectively responses for the toxicity assessment in real water samples.The results showed a promising correlation between two tests used for the detection of toxic compounds in water samples. 相似文献
549.
Microemulsion EKC (MEEKC) was used for the determination of ketorolac and its three impurities. The microemulsion system was optimized, for the first time in the literature, using a multivariate strategy involving a mixture design. A 13-run experimental plan covering an experimental domain defined by the components aqueous phase (10 mM borate buffer pH 9.2), oil phase (n-heptane) and surfactant/cosurfactant (SDS/n-butanol) was carried out. Good results were obtained with all microemulsions tested considering as responses analysis time and resolution, and according to the desirability function the best microemulsion system was constituted by 90.0% 10 mM borate buffer, 2.0% n-heptane, 8.0% of SDS/n-butanol in 1:2 ratio. Finally, with the aim of reducing analysis time, a response surface study was carried out in the experimental domain defined by the process variables temperature and voltage and the best values were 17 degrees C and -17 kV, respectively. Applying the optimised conditions, a complete resolution among the analytes was obtained in about 3 min using the short-end injection method. The method was validated for both drug substances and drug product and was applied to the quality control of ketorolac in coated tablets. A comparison of MEEKC, MEKC and CEC for assaying ketorolac and its related substances has been made. 相似文献
550.
Taguchi Y Miyake T Margadonna S Kato K Prassides K Iwasa Y 《Journal of the American Chemical Society》2006,128(10):3313-3323
We report on the first synthesis of Li-intercalated manganese-phthalocyanine (MnPc) in the bulk form and on the evolution of the structural and magnetic properties as a function of Li concentration, x. We find that solid beta-MnPc, which comprises rodlike assemblies of individual planar molecules, is best described as a glassy one-dimensional ferromagnet without three-dimensional ordering and that it can be quasi-continuously intercalated with Li up to x = 4, forming an isosymmetrical series of Li(x)[MnPc] phases. Inserted Li+ ions strongly bond to pyrrole-bridging nitrogen atoms of the Pc rings, thereby disrupting the ferromagnetic Mn-N(a)...Mn superexchange pathways. This gradually induces a crossover of the intrachain exchange interactions from ferromagnetic to antiferromagnetic as the doping level, x, increases coupled with a spin-state transition of the Mn2+ ions from intermediate spin, S = 3/2, to high spin, S = 5/2. 相似文献