全文获取类型
收费全文 | 635篇 |
免费 | 56篇 |
国内免费 | 2篇 |
专业分类
化学 | 514篇 |
晶体学 | 2篇 |
力学 | 19篇 |
数学 | 70篇 |
物理学 | 88篇 |
出版年
2023年 | 17篇 |
2022年 | 11篇 |
2021年 | 14篇 |
2020年 | 25篇 |
2019年 | 22篇 |
2018年 | 14篇 |
2017年 | 10篇 |
2016年 | 36篇 |
2015年 | 30篇 |
2014年 | 23篇 |
2013年 | 45篇 |
2012年 | 46篇 |
2011年 | 57篇 |
2010年 | 33篇 |
2009年 | 17篇 |
2008年 | 45篇 |
2007年 | 50篇 |
2006年 | 34篇 |
2005年 | 49篇 |
2004年 | 28篇 |
2003年 | 22篇 |
2002年 | 14篇 |
2001年 | 10篇 |
2000年 | 4篇 |
1999年 | 2篇 |
1998年 | 6篇 |
1997年 | 2篇 |
1996年 | 5篇 |
1995年 | 2篇 |
1994年 | 2篇 |
1993年 | 3篇 |
1991年 | 2篇 |
1988年 | 2篇 |
1982年 | 1篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1955年 | 3篇 |
1954年 | 3篇 |
1949年 | 1篇 |
排序方式: 共有693条查询结果,搜索用时 15 毫秒
1.
Jeroen J. L. M. Cornelissen W. Sander Graswinckel Alan E. Rowan Nico A. J. M. Sommerdijk Roeland J. M. Nolte 《Journal of polymer science. Part A, Polymer chemistry》2003,41(11):1725-1736
The conformational properties of polymers derived from isocyanodipeptides have been investigated with a combination of model calculations, X‐ray diffraction, and circular dichroism spectroscopy. Depending on the configuration of the side chains, defined arrays of hydrogen bonds along the polymeric backbone are formed. This leads to a well‐defined conformation as, for example, expressed in the formation of lyotropic liquid‐crystalline phases and increased helical stability. Upon the disruption of the hydrogen bonds by a strong acid, a less well‐defined macromolecular conformation is observed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1725–1736, 2003 相似文献
2.
We perform three tests on our proposal to implement diffeomorphism invariance in the non-abelian D0-brane DBI action as a base-point independence constraint between matrix Riemann normal coordinate systems. First, we show that T-duality along an isometry correctly interchanges the potential and kinetic terms in the action. Second, we show that the method to impose base-point independence using an auxiliary dN2-dimensional nonlinear sigma model also works for metrics which are curved along the brane, provided a physical gauge choice is made at the end. Third, we show that without alteration this method is applicable to higher order in velocities. Testing specifically to order 4, we elucidate the range of validity of the symmetrized trace approximation to the non-abelian DBI action. 相似文献
3.
Nynke A. M. Verhaegh Jeroen S. van Duijneveldt Jan K. G. Dhont Henk N. W. Lekkerkerker 《Physica A》1996,230(3-4):409-436
Mixtures of colloidal silica spheres and polydimethylsiloxane in cyclohexane with a colloid-polymer size ratio of about one were found to phase separate into two fluid phases, one which is colloid-rich and one which is colloid-poor. In this work the phase separation kinetics of this fluid-fluid phase separation is studied for different compositions of the colloid-polymer mixtures, and at several degrees of supersaturation, with small angle light scattering and with light microscopy. The small angle light scattering curve exhibits a peak that grows in intensity and that shifts to smaller wave vector with time. The characteristic length scale that is obtained from the scattering peak is of the order of a few μm, in agreement with observations by light microscopy. The domain size increases with time as
, which might be an indication of coarsening by diffusion and coalescence, like in the case of binary liquid mixtures and polymer blends. For sufficiently low degrees of supersaturation the angular scattering intensity curves satisfy dynamical scaling behavior. 相似文献
4.
Nanoscale organization of the pathogen receptor DC-SIGN mapped by single-molecule high-resolution fluorescence microscopy. 总被引:3,自引:0,他引:3
Bärbel I. de Bakker Dr. Frank de Lange Dr. Alessandra Cambi Dr. Jeroen P. Korterik Erik M. H. P. van Dijk Dr. Niek F. van Hulst Prof. Carl G. Figdor Prof. Maria F. Garcia‐Parajo Prof. 《Chemphyschem》2007,8(10):1473-1480
DC-SIGN, a C-type lectin exclusively expressed on dendritic cells (DCs), plays an important role in pathogen recognition by binding with high affinity to a large variety of microorganisms. Recent experimental evidence points to a direct relation between the function of DC-SIGN as a viral receptor and its spatial arrangement on the plasma membrane. We have investigated the nanoscale organization of fluorescently labeled DC-SIGN on intact isolated DCs by means of near-field scanning optical microscopy (NSOM) combined with single-molecule detection. Fluorescence spots of different intensity and size have been directly visualized by optical means with a spatial resolution of less than 100 nm. Intensity- and size-distribution histograms of the DC-SIGN fluorescent spots confirm that approximately 80 % of the receptors are organized in nanosized domains randomly distributed on the cell membrane. Intensity-size correlation analysis revealed remarkable heterogeneity in the molecular packing density of the domains. Furthermore, we have mapped the intermolecular organization within a dense cluster by means of sequential NSOM imaging combined with discrete single-molecule photobleaching. In this way we have determined the spatial coordinates of 13 different individual dyes, with a localization accuracy of 6 nm. Our experimental observations are all consistent with an arrangement of DC-SIGN designed to maximize its chances of binding to a wide range of microorganisms. Our data also illustrate the potential of NSOM as an ultrasensitive, high-resolution technique to probe nanometer-scale organization of molecules on the cell membrane. 相似文献
5.
Band broadening related to laminar flow and spray chamber dead volume is a potential problem in flow injection (FI)-inductively coupled plasma-mass spectrometry (ICP-MS). We studied these two dispersion effects with a sheath flow capillary electrophoresis (CE)-ICP-MS interface. A numerical model was used to simulate advection diffusion processes in the CE-capillary and dispersion in the spray chamber. Experimental results of FI with this CE-ICP-MS interface agree well with numerical modeling results. Dispersion due to laminar flow depends strongly on capillary diameter and analyte diffusion coefficient and to a lesser extent on laminar velocity and capillary length and typically amounts to one order of magnitude peak width increase. Three spray chambers of 5, 20 and 150 ml dead volume showed an increase in band broadening and peak tailing with increasing dead volume. The use of standard Scott-type spray chambers (>90 ml volume) increases peak widths by 5-10 s regardless of injection time. The use of a low dead volume spray chamber is recommended for experiments where resolution is critical. The modeling approach can be extended to the coupling of other flow injection techniques, like micro-LC and nano-LC with ICP-MS. 相似文献
6.
Demmers JA Rijkers DT Haverkamp J Killian JA Heck AJ 《Journal of the American Chemical Society》2002,124(37):11191-11198
In this report, we evaluate the validity of using hydrogen/deuterium exchange in combination with collision-induced dissociation mass spectrometry (CID MS) for the detailed structural and conformational investigation of peptides and proteins. This methodology, in which partly deuterated peptide ions are subjected to collision-induced dissociation in the vacuum of a mass spectrometer, has emerged as a useful tool in structural biology. It may potentially provide quantitatively the extent of deuterium incorporation per individual amino acid in peptides and proteins, thus providing detailed structural information related to protein structure and folding. We report that this general methodology has limitations caused by the fact that the incorporated deuterium atoms migrate prior or during the CID MS analysis. Our data are focused on a variety of transmembrane peptides, incorporated in a lipid bilayer, in which the near-terminal amino acids that anchor at the lipid-water interface are systematically varied. Our findings suggest that, under the experimental conditions we use, the extent of intramolecular hydrogen scrambling is strongly influenced by experimental factors, such as the exact amino acid sequence of the peptide, the nature of the charge carrier, and therefore most likely by the gas-phase structure of the peptide ion. Moreover, the observed scrambling seems to be independent of the nature of the peptide fragment ions (i.e., protonated B and Y' ' ions, and sodiated A and Y' ions). Our results strongly suggest that scrambling may be reduced by using alkali metal cationization instead of protonation in the ionization process. 相似文献
7.
Conventional proteomics makes use of two-dimensional gel electrophoresis followed by mass spectrometric analysis of tryptic fragments derived from in-gel digestion of proteins. Although being a very strong technique capable of separating and visualizing hundreds of proteins, 2D-gel electrophoresis has some well-documented disadvantages as well. More recently, liquid chromatographic-(tandem) mass spectrometric techniques have been developed to overcome some of the shortcomings of 2D-gel electrophoresis. In this review we have described several recent applications of liquid chromatography-(tandem) mass spectrometry in the field of proteomics and especially in the field of membrane proteomics, quantitative proteomics and in the analysis of post-translational modifications. 相似文献
8.
van Apeldoorn AA van Manen HJ Bezemer JM de Bruijn JD van Blitterswijk CA Otto C 《Journal of the American Chemical Society》2004,126(41):13226-13227
Understanding the degradation behavior of polymeric microspheres is crucial for the successful application of such devices in controlled drug delivery. The degradation mechanism of poly(lactic-co-glycolic acid) (PLGA) microspheres inside phagocytic cells is not known, but different models for degradation in aqueous solution have been proposed. We have used confocal Raman spectroscopy and imaging to study the intracellular degradation of PLGA microspheres inside individual macrophages. Our results show that ingested microspheres degrade in a heterogeneous manner, with a more rapid degradation in the center. Comparison of Raman spectra from degrading beads with those of uningested beads reveals that ester hydrolysis occurs throughout the phagocytosed microspheres, with a selective loss of glycolic acid units. Furthermore, we show that PLGA degradation is a cell-mediated process, possibly caused by the low pH of the phagosome and/or the presence of hydrolytic enzymes. In conclusion, we have demonstrated that the chemical composition of degrading polymers inside cells can be probed by Raman spectral imaging. This technique will expand the capabilities of investigating biomaterial degradation in vivo. 相似文献
9.
Jeroen Kuipers 《Mathematical Methods of Operations Research》1993,38(2):131-139
LetN=1,2,...,n be a set of customers andG=(N {0},E) an undirected connected graph with non-negative edge lengths. 0 is the home location of a salesman who visits the customers inN. Each subset
can invite the salesman to visit its members only. The costc(S) of coalitionS is the length of a shortest tour that starts in 0, visits each customer inS at least once and returns to 0. The cooperative cost game defined in this way is called a (symmetric) traveling salesman game (TSG).The core of a TSG can be empty when ¦N¦ 6 and it was proved that it always has a non-empty core when ¦N¦ 4. In this note we shall prove that a TSG always has a non-empty core when ¦N¦=5. 相似文献
10.
de Loos F Reynhout IC Cornelissen JJ Rowan AE Nolte RJ 《Chemical communications (Cambridge, England)》2005,(1):60-62
A series of mono-functionalized metallo-porphyrin polystyrenes have been synthesized using atom transfer radical polymerization and their self-assembling behavior was studied by electron microscopy showing that the polystyrene tail-length influences the aggregate architecture. 相似文献