全文获取类型
收费全文 | 1348篇 |
免费 | 26篇 |
国内免费 | 7篇 |
专业分类
化学 | 694篇 |
晶体学 | 17篇 |
力学 | 83篇 |
综合类 | 2篇 |
数学 | 304篇 |
物理学 | 281篇 |
出版年
2022年 | 13篇 |
2021年 | 20篇 |
2020年 | 17篇 |
2019年 | 13篇 |
2018年 | 24篇 |
2017年 | 21篇 |
2016年 | 30篇 |
2015年 | 26篇 |
2014年 | 32篇 |
2013年 | 58篇 |
2012年 | 48篇 |
2011年 | 59篇 |
2010年 | 57篇 |
2009年 | 43篇 |
2008年 | 53篇 |
2007年 | 60篇 |
2006年 | 54篇 |
2005年 | 49篇 |
2004年 | 41篇 |
2003年 | 35篇 |
2002年 | 43篇 |
2001年 | 29篇 |
2000年 | 33篇 |
1999年 | 17篇 |
1998年 | 24篇 |
1997年 | 18篇 |
1996年 | 20篇 |
1995年 | 25篇 |
1994年 | 25篇 |
1993年 | 12篇 |
1992年 | 15篇 |
1991年 | 17篇 |
1990年 | 19篇 |
1987年 | 12篇 |
1986年 | 10篇 |
1985年 | 15篇 |
1984年 | 16篇 |
1983年 | 12篇 |
1982年 | 15篇 |
1981年 | 14篇 |
1979年 | 11篇 |
1978年 | 14篇 |
1975年 | 13篇 |
1974年 | 14篇 |
1973年 | 10篇 |
1972年 | 11篇 |
1970年 | 10篇 |
1969年 | 13篇 |
1968年 | 10篇 |
1916年 | 10篇 |
排序方式: 共有1381条查询结果,搜索用时 71 毫秒
101.
A. Andreone A. Di Chiara G. Peluso U. Scotti di Uccio F. Tafuri A. Barone G. Pepe F. Fontana 《Il Nuovo Cimento D》1990,12(6):863-868
Summary Some of the main anomalies in conductance characteristics of high-T
C tunnel junctions are considered. Mainly, the extreme, depression of gap structures, the presence of conductance peaks in
corrispondence to the counterelectrode gap, and ?zero-bias anomalies? will be examined. The possibility of application of
the proximity McMillan model to describe the behaviour in conductance of high-T
C junctions is considered. Discussion and preliminary comparison with experimental data on YBCO junctions are also reported. 相似文献
102.
The enantioselective synthesis of 3(S)-hydroxy polygodial and its acetyl derivative is described. The construction of the 3-hydroxy drimane skeleton was based on the titanium-catalyzed radical cyclization of (10S)-10, 11-epoxy-farnesyl acetate. Only underivatized 3(S)-hydroxy polygodial showed activity in assays on VR1 vanilloid receptor in HEK cells transfected with the human VR1. 相似文献
103.
Göbel MC Gregori G Guo X Maier J 《Physical chemistry chemical physics : PCCP》2010,12(42):14351-14361
Thin films of CeO(2) (both nominally pure and 10 mol% gadolinium-doped) grown via pulsed-laser deposition were studied. The electrical conductivity of the samples was measured as a function of thickness, temperature and oxygen partial pressure (pO(2)) using impedance spectroscopy. As expected, undoped CeO(2) exhibits electronic conductivity (with activation energy between 1.4 and 1.6 eV) whereas the highly doped samples are oxygen vacancy conductors (activation energy around 0.7 eV for epitaxial films). In order to investigate the influence of the nature of the substrate the thin films were grown on two different substrates, Al(2)O(3) (0001) and SiO(2) (0001), and compared. While the films grown on SiO(2) exhibit a microstructure characterized by columnar grains, the films grown on Al(2)O(3) are epitaxial. Notably, for films on both substrates the conductivity and activation energy vary with film thickness and exhibit remarkable differences when the films on different substrates are compared. In the case of the polycrystalline films (SiO(2) substrate), the space charge layer effects of the grain boundaries dominate over the substrate-film interface effect. In the case of the epitaxial films (Al(2)O(3) substrate), a small interface effect, probably due to a space charge layer or structural strain, is observed. 相似文献
104.
L. Elviri F. Speroni M. Careri A. Mangia L. Sanità di Toppi M. Zottini 《Journal of chromatography. A》2010,1217(25):4120-4126
Reversed-phase liquid chromatography (RPLC) and electrospray (ESI)-linear ion trap (LIT) mass spectrometry was applied to the direct characterization of in vivo S-nitrosylated (SNO) phytochelatins (PCs) expressed in cadmium-stressed Arabidopsis thaliana cells. Cys-nitrosylation is under discussion as in vivo redox-based post-translational modification of proteins and peptides in plants in which the –NO group is involved as signal molecule in different biological functions. The gas-phase ion chemistry of in vivo and in vitro generated SNO-PCs was compared with the aim of evaluating NO binding stability and improving MS knowledge about peptide nitrosation. Using RPLC separation and ESI-LIT-MS, mono-nitrosylated PCs were identified in in vivo cadmium treated A. thaliana cells without derivatization. The in vivo binding of the NO group to PC2, PC3 and PC4 resulted to occur selectively on only one cystein residue. The fragmentation pathway energies of the in vitro GSNO-generated NO-PCs with respect to the in vivo NO-PCs were investigated, suggesting the presence of a different internal stability for these molecules. By carrying out MS2 experiments on these quasi-symmetric peptides, the different stability degree of the NO group was demonstrated to be correlated with the PC chain length. In addition, the data obtained highlight a putative role of the adjacent Glu/Cys motif in the gas-phase stability of the NO-containing molecule. 相似文献
105.
El-Ghayoury A Mézière C Simonov S Zorina L Cobián M Canadell E Rovira C Náfrádi B Sipos B Forró L Batail P 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(47):14051-14059
We report on the acid ethylenedithiotetrathiafulvaleneamidoglycine (EDT-TTF-CO-NH-CH(2)-CO(2)H; 1; EDT-TTF=ethylenedithiotetrathiafulvalene) and the 1:1 adduct [(EDT-TTF)(·+)-CO-NH-CH(2)-(CO(2))(-)][(EDT-TTF)-CO-NH-CH(2)-(CO(2)H)]·CH(3)OH (2), a new type of hydrogen-bonded, 1:1 acid/zwitterion hybrid embrace of redox peptidics into a two-dimensional architecture, an example of a system deliberately fashioned so that oxidation of π-conjugated cores toward the radical-cation form would interfere with the activity of the appended ionizable residues in the presence of a templating base during crystal growth. First-principles calculations demonstrate that, notwithstanding preconceived ideas, a metallic state is more stable than the hole-localized alternatives for a neat 1:1 neutral acid/zwitterion hybrid. The inhomogeneous Coulomb field associated with proton-shared, interstacks O-H···O hydrogen bonds between the ionizable residues distributed on both sides of the two-dimensional π-conjugated framework leads, however, to a weak hole localization responsible for the activated but high conductivity of 1 S cm(-1). This situation is reminiscent of the role of the environment on electron transfer in tetraheme cytochrome c, in which the protonation state of a heme propionate becomes paramount, or ion-gated transport phenomena in biology. These observations open rather intriguing opportunities for the construction of electronic systems at the interface of chemistry and biology. 相似文献
106.
Umberto Casellato Rodolfo Graziani Giuseppe Maccarrone Angel J. di Bilio 《Journal of chemical crystallography》1986,16(5):695-702
cis-Diaquabis(2,2-bipyridyl)chromium(III) nitrate crystallizes in the mono-clinic system, space groupP21/c, witha=16.102(6),b=10.792(5),c=15.076(6) Å,=112.90(5)°, andZ=4. The saltlike structure was determined from X-ray crystallography and refined toR=7.5% for 3342 observed reflections. The Cr atom is octahedrally surrounded by twocis water molecules and by two chelated 2,2-bypiridyl ligands forming two nearly orthogonal planes. Selected bond distances are: Cr-O, 2.00(1) and 1.98(1) Å, Cr-N, 2.04 Å (mean). 相似文献
107.
Parracino A Gajula GP di Gennaro AK Neves-Petersen MT Rafaelsen J Petersen SB 《Journal of fluorescence》2011,21(2):663-672
Medical interest in nanotechnology originates from a belief that nanoscale therapeutic devices can be constructed and directed
towards its target inside the human body. Such nanodevices can be engineered by coupling superparamagnetic nanoparticle to
biomedically active proteins. We hereby report the immobilization of a PhEst, a S-formylglutathione hydrolase from the psychrophilic
P. haloplanktis TAC125 onto the gold coated surface of modified superparamagnetic core-shell nanoparticles (Fe3O4@Au). The synthesis of the nanoparticles is also reported. S-formylglutathione hydrolases constitute a family of ubiquitous
enzymes which play a key role in formaldehyde detoxification both in prokaryotes and eukaryotes. PhEst was originally annotated
as a putative feruloyl esterase, an enzyme that releases ferulic acid (an antioxidant reactive towards free radicals such
as reactive oxygen species) from polysaccharides esters. Dynamic light scattering, scanning electron microscopy with energy
dispersive X-ray spectroscopy, UV–visible absorption spectroscopy, fluorescence spectroscopy, magnetic separation technique
and enzyme catalytic assay confirmed the chemical composition of the gold covered superparamagnetic nanoparticles, the binding
and activity of the enzyme onto the nanoparticles. Activity data in U/ml confirmed that the immobilized enzyme is approximately
2 times more active than the free enzyme in solution. Such particles can be directed with external magnetic fields for bio-separation
and focused towards a medical target for therapeutical as well as bio-sensor applications. 相似文献
108.
Rita Giuliano Claudio Macci Barbara Pacchiarotti 《Journal of Mathematical Analysis and Applications》2014
In this paper we study some sequences of weighted means of continuous real valued Gaussian processes. More precisely we consider suitable generalizations of both arithmetic and logarithmic means of a Gaussian process with covariance function which satisfies either an exponential decay condition or a power decay condition. Our aim is to provide limits of variances of functionals of such weighted means which allow the application of some large deviation results in the literature. 相似文献
109.
Mohamed Saïdi 《Mathematische Zeitschrift》2014,277(1-2):361-372
We show the existence of group-theoretic sections of the “étale-by-geometrically abelian” quotient of the arithmetic fundamental group of hyperbolic curves over $p$ -adic local fields relative to a proper and flat model which are non-geometric, i.e., which do not arise from rational points. 相似文献
110.
Giuliano Alagona Caterina Ghio Alessandro Giolitti Susanna Monti 《Theoretical chemistry accounts》1999,101(1-3):143-150
Several histidine-tryptophan complexes (either stacked or T-shaped), derived from the crystal structures available in the
Brookhaven Protein Data Bank, have been examined with molecular mechanics (MM), using the Tripos force field with Gasteiger-Hückel
charges, whose trend was found to be analogous to the AMBER or CHARMM ones. The MM results were compared to the ab initio
MP2 results, with and without counterpoise (CP) correction, previously obtained using extended basis sets on 5-methylimidazole
and indole as model systems. MM seems to underestimate the interaction energy between the two monomers when compared to the
uncorrected MP2 results, while the agreement is much better after including the CP correction at the MP2 level in all cases.
MM was thus used to qualitatively analyse the dependence of the stacking energy on the ring rotation at a variable distance
and ring centroid displacement for these systems, while keeping the rings in parallel planes. An analogous study was carried
out for a T-shaped adduct.
Received: 24 March 1998 / Accepted: 3 September 1998 / Published online: 1 February 1999 相似文献