全文获取类型
收费全文 | 2358篇 |
免费 | 81篇 |
国内免费 | 9篇 |
专业分类
化学 | 1963篇 |
晶体学 | 12篇 |
力学 | 25篇 |
数学 | 221篇 |
物理学 | 227篇 |
出版年
2023年 | 24篇 |
2022年 | 45篇 |
2021年 | 68篇 |
2020年 | 48篇 |
2019年 | 59篇 |
2018年 | 40篇 |
2017年 | 37篇 |
2016年 | 81篇 |
2015年 | 85篇 |
2014年 | 82篇 |
2013年 | 116篇 |
2012年 | 150篇 |
2011年 | 201篇 |
2010年 | 119篇 |
2009年 | 109篇 |
2008年 | 152篇 |
2007年 | 153篇 |
2006年 | 115篇 |
2005年 | 121篇 |
2004年 | 101篇 |
2003年 | 93篇 |
2002年 | 74篇 |
2001年 | 37篇 |
2000年 | 20篇 |
1999年 | 34篇 |
1998年 | 17篇 |
1997年 | 13篇 |
1996年 | 23篇 |
1995年 | 23篇 |
1994年 | 21篇 |
1993年 | 15篇 |
1992年 | 11篇 |
1991年 | 13篇 |
1990年 | 19篇 |
1989年 | 15篇 |
1988年 | 10篇 |
1987年 | 6篇 |
1986年 | 5篇 |
1985年 | 15篇 |
1984年 | 9篇 |
1983年 | 5篇 |
1982年 | 12篇 |
1980年 | 8篇 |
1979年 | 12篇 |
1978年 | 9篇 |
1976年 | 4篇 |
1975年 | 4篇 |
1974年 | 3篇 |
1970年 | 2篇 |
1967年 | 2篇 |
排序方式: 共有2448条查询结果,搜索用时 15 毫秒
81.
Sandra Grebenteuch Clemens Kanzler Stefan Klaußnitzer Lothar W. Kroh Sascha Rohn 《Molecules (Basel, Switzerland)》2021,26(4)
Lipid oxidation and the resulting volatile organic compounds are the main reasons for a loss of food quality. In addition to typical compounds, such as alkanes, aldehydes and alcohols, methyl ketones like heptan-2-one, are repeatedly described as aroma-active substances in various foods. However, it is not yet clear from which precursors methyl ketones are formed and what influence amino compounds have on the formation mechanism. In this study, the formation of methyl ketones in selected food-relevant fats and oils, as well as in model systems with linoleic acid or pure secondary degradation products (alka-2,4-dienals, alken-2-als, hexanal, and 2-butyloct-2-enal), has been investigated. Elevated temperatures were chosen for simulating processing conditions such as baking, frying, or deep-frying. Up to seven methyl ketones in milk fat, vegetable oils, and selected model systems have been determined using static headspace gas chromatography-mass spectrometry (GC-MS). This study showed that methyl ketones are tertiary lipid oxidation products, as they are derived from secondary degradation products such as deca-2,4-dienal and oct-2-enal. The study further showed that the position of the double bond in the precursor compound determines the chain length of the methyl ketone and that amino compounds promote the formation of methyl ketones to a different degree. These compounds influence the profile of the products formed. As food naturally contains lipids as well as amino compounds, the proposed pathways are relevant for the formation of aroma-active methyl ketones in food. 相似文献
82.
Garcia S Chavez L Lowery TJ Han SI Wemmer DE Pines A 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2007,184(1):72-77
Hyperpolarized xenon associated with ligand derivatized cryptophane-A cages has been developed as a NMR based biosensor. To optimize the detection sensitivity we describe use of xenon exchange between the caged and bulk dissolved xenon as an effective signal amplifier. This approach, somewhat analogous to 'remote detection' described recently, uses the chemical exchange to repeatedly transfer spectroscopic information from caged to bulk xenon, effectively integrating the caged signal. After an optimized integration period, the signal is read out by observation of the bulk magnetization. The spectrum of the caged xenon is reconstructed through use of a variable evolution period before transfer and Fourier analysis of the bulk signal as a function of the evolution time. 相似文献
83.
Granwehr J Harel E Hilty C Garcia S Chavez L Pines A Sen PN Song YQ 《Magnetic resonance imaging》2007,25(4):449-452
Remote detection nuclear magnetic resonance and magnetic resonance imaging can be used to study fluid flow and dispersion in a porous medium from a purely Eulerian point of view (i.e., in a laboratory frame of reference). Information about fluid displacement is obtained on a macroscopic scale in a long-time regime, while local velocity distributions are averaged out. It is shown how these experiments can be described using the common flow propagator formalism and how experimental data can be analyzed to obtain effective porosity, flow velocity inside the porous medium, fluid dispersion and flow tracing of fluid. 相似文献
84.
In this brief review, an overview about recent efforts to simulate the spectroscopic signatures of chiral molecules is given with focus on real time propagation approaches to solve the time-dependent Schrödinger equation. In particular the simulation of electric circular dichroism spectra and vibrational Raman optical activity is discussed. In comparison to linear absorption spectra, where only the response of the electric dipole moment is necessary, the response of the magnetic dipole moment and electric quadrupole moment is more intricate. Issues such as gauge origin dependence, basis set dependence, non-local potentials and the dipole approximation are addressed. 相似文献
85.
Xianwen Lou Sandra M. C. Schoenmakers Joost L. J. van Dongen Miguel Garcia-Iglesias Nicolás M. Casellas Marcos Fernández-Castaño Romera Rint P. Sijbesma E. W. Meijer Anja R. A. Palmans 《Journal of polymer science. Part A, Polymer chemistry》2021,59(12):1151-1161
A comprehensive understanding of the structure, self-assembly mechanism, and dynamics of one-dimensional supramolecular polymers in water is essential for their application as biomaterials. Although a plethora of techniques are available to study the first two properties, there is a paucity in possibilities to study dynamic exchange of monomers between supramolecular polymers in solution. We recently introduced hydrogen/deuterium exchange mass spectrometry (HDX-MS) to characterize the dynamic nature of synthetic supramolecular polymers with only a minimal perturbation of the chemical structure. To further expand the application of this powerful technique some essential experimental aspects have been reaffirmed and the technique has been applied to a diverse library of assemblies. HDX-MS is widely applicable if there are exchangeable hydrogen atoms protected from direct contact with the solvent and if the monomer concentration is sufficiently high to ensure the presence of supramolecular polymers during dilution. In addition, we demonstrate that the kinetic behavior as probed by HDX-MS is influenced by the internal order within the supramolecular polymers and by the self-assembly mechanism. 相似文献
86.
Julian Hofmann Dr. Tiziana Ginex Dr. Alba Espargaró Matthias Scheiner Sandra Gunesch Marc Aragó Prof. Dr. Christian Stigloher Prof. Dr. Raimon Sabaté Prof. Dr. F. Javier Luque Prof. Dr. Michael Decker 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(19):6015-6027
Many (poly-)phenolic natural products, for example, curcumin and taxifolin, have been studied for their activity against specific hallmarks of neurodegeneration, such as amyloid-β 42 (Aβ42) aggregation and neuroinflammation. Due to their drawbacks, arising from poor pharmacokinetics, rapid metabolism, and even instability in aqueous medium, the biological activity of azobenzene compounds carrying a pharmacophoric catechol group, which have been designed as bioisoteres of curcumin has been examined. Molecular simulations reveal the ability of these compounds to form a hydrophobic cluster with Aβ42, which adopts different folds, affecting the propensity to populate fibril-like conformations. Furthermore, the curcumin bioisosteres exceeded the parent compound in activity against Aβ42 aggregation inhibition, glutamate-induced intracellular oxidative stress in HT22 cells, and neuroinflammation in microglial BV-2 cells. The most active compound prevented apoptosis of HT22 cells at a concentration of 2.5 μm (83 % cell survival), whereas curcumin only showed very low protection at 10 μm (21 % cell survival). 相似文献
87.
88.
Application of Novel Zn‐Ferrite Modified Glassy Carbon Paste Electrode as a Sensor for Determination of Cd(II) in Waste Water 下载免费PDF全文
Dalibor M. Stanković Sandra Škrivanj Nenad Savić Aleksandar S. Nikolić Predrag Vulić Dragan D. Manojlović 《Electroanalysis》2014,26(7):1536-1543
This paper describes the preparation of a new sensor based on Zn‐ferrite modified glassy carbon paste electrode and its electrochemical application for the determination of trace Cd(II) ions in waste waters using differential pulse anodic stripping voltammetry (DPASV). Different Zn/Ni ferrite nanoparticles were synthesized and characterized using scanning electron microscopy (SEM) and X‐ray powder diffraction (XRPD). The prepared ferrite nanoparticles were used for the preparation of Zn‐ferrite‐modified glassy carbon paste electrode (ZnMGCPE) for determination of Cd(II) at nanomolar levels in waste water at pH 5. The different parameters such as conditions of preparation, Zn2+/Ni2+/Fe2+ ratio and electrochemical parameters, percentage of modifier, accumulation time, pH and accumulation potential were investigated. Besides, interference measurements were also evaluated under optimized parameters. The best voltammetric response was observed for ZnFe2O4 modifier, when the percentage of modifier was 3 %, accumulation time 9 min, pH of supporting electrolyte 5 and accumulation potential ?1.05 V. Thus prepared electrode displays excellent response to Cd(II) with a detection limit of 0.38 ppb, and selective detection toward Cd(II) was achieved. 相似文献
89.
Weixun Wang Bernard K. Choi Wenyu Li Zhege Lao Anita Y. H. Lee Sandra C. Souza Nathan A. Yates Timothy Kowalski Alessandro Pocai Lucinda H. Cohen 《Journal of the American Society for Mass Spectrometry》2014,25(4):614-625
Stromal cell-derived factor 1α (SDF-1α) or CXCL12 is a small pro-inflammatory chemoattractant cytokine and a substrate of dipeptidyl peptidase IV (DPP-IV). Proteolytic cleavage by DPP-IV inactivates SDF-1α and attenuates its interaction with CXCR4, its cell surface receptor. To enable investigation of suppression of such inactivation with pharmacologic inhibition of DPP-IV, we developed quantitative mass spectrometric methods that differentiate intact SDF-1α from its inactive form. Using top-down strategy in quantification, we demonstrated the unique advantage of keeping SDF-1α’s two disulfide bridges intact in the analysis. To achieve the optimal sensitivity required for quantification of intact and truncated SDF-1α at endogenous levels in blood, we coupled nano-flow tandem mass spectrometry with antibody-based affinity enrichment. The assay has a quantitative range of 20 pmol/L to 20 nmol/L in human plasma as well as in rhesus monkey plasma. With only slight modification, the same assay can be used to quantify SDF-1α in mice. Using two in vivo animal studies as examples, we demonstrated that it was critical to differentiate intact SDF-1α from its truncated form in the analysis of biomarkers for pharmacologic inhibition of DPP-IV activity. These novel methods enable translational research on suppression of SDF-1 inactivation with DPP-IV inhibition and can be applied to relevant clinical samples in the future to yield new insights on change of SDF-1α levels in disease settings and in response to therapeutic interventions. Figure
? 相似文献
90.
The Origin of the Selectivity and Activity of Ruthenium‐Cluster Catalysts for Fuel‐Cell Feed‐Gas Purification: A Gas‐Phase Approach 下载免费PDF全文
Dr. Sandra M. Lang Prof. Dr. Thorsten M. Bernhardt Marjan Krstić Prof. Dr. Vlasta Bonačić‐Koutecký 《Angewandte Chemie (International ed. in English)》2014,53(21):5467-5471
Gas‐phase ruthenium clusters Run+ (n=2–6) are employed as model systems to discover the origin of the outstanding performance of supported sub‐nanometer ruthenium particles in the catalytic CO methanation reaction with relevance to the hydrogen feed‐gas purification for advanced fuel‐cell applications. Using ion‐trap mass spectrometry in conjunction with first‐principles density functional theory calculations three fundamental properties of these clusters are identified which determine the selectivity and catalytic activity: high reactivity toward CO in contrast to inertness in the reaction with CO2; promotion of cooperatively enhanced H2 coadsorption and dissociation on pre‐formed ruthenium carbonyl clusters, that is, no CO poisoning occurs; and the presence of Ru‐atom sites with a low number of metal–metal bonds, which are particularly active for H2 coadsorption and activation. Furthermore, comprehensive theoretical investigations provide mechanistic insight into the CO methanation reaction and discover a reaction route involving the formation of a formyl‐type intermediate. 相似文献