全文获取类型
收费全文 | 660篇 |
免费 | 16篇 |
国内免费 | 3篇 |
专业分类
化学 | 505篇 |
晶体学 | 6篇 |
力学 | 6篇 |
数学 | 109篇 |
物理学 | 53篇 |
出版年
2023年 | 2篇 |
2022年 | 5篇 |
2021年 | 8篇 |
2020年 | 12篇 |
2019年 | 14篇 |
2018年 | 6篇 |
2017年 | 9篇 |
2016年 | 10篇 |
2015年 | 16篇 |
2014年 | 15篇 |
2013年 | 30篇 |
2012年 | 31篇 |
2011年 | 44篇 |
2010年 | 25篇 |
2009年 | 25篇 |
2008年 | 40篇 |
2007年 | 38篇 |
2006年 | 33篇 |
2005年 | 37篇 |
2004年 | 27篇 |
2003年 | 28篇 |
2002年 | 35篇 |
2001年 | 11篇 |
2000年 | 13篇 |
1999年 | 5篇 |
1998年 | 8篇 |
1997年 | 10篇 |
1996年 | 19篇 |
1995年 | 5篇 |
1994年 | 4篇 |
1993年 | 10篇 |
1992年 | 6篇 |
1991年 | 5篇 |
1990年 | 6篇 |
1989年 | 6篇 |
1987年 | 5篇 |
1986年 | 7篇 |
1985年 | 12篇 |
1984年 | 2篇 |
1983年 | 4篇 |
1982年 | 7篇 |
1981年 | 9篇 |
1980年 | 8篇 |
1978年 | 6篇 |
1977年 | 6篇 |
1976年 | 6篇 |
1973年 | 4篇 |
1971年 | 1篇 |
1970年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有679条查询结果,搜索用时 15 毫秒
101.
Douglas Iafrate Castelhano Juliana de Almeida Carlos Henrique de Paiva Pinheiro Rodnei Bertazzoli Christiane de Arruda Rodrigues 《Journal of Solid State Electrochemistry》2018,22(8):2445-2455
Although TiO2 anatase phase has been widely chosen as the main photocatalyst, it presents high electron/hole recombination rate. However, today, what is sought is a semiconductor material with enhanced photocatalytic activity with higher photon to electron conversion efficiency by introduction of electrons trap dopants. In this paper, TiO2 nanotubes arrays obtained by anodization of Ti substrates were decorated with Ru via electrodeposition, and their photo-response was investigated. First, voltammetric experiments were performed to elucidate the route of Ru reduction on the TiO2 surface and to select the range of potentials for Ru deposition. The reduction potentials were used for controlling the amount of Ru distributed all over the surface. Although Ru was electrodeposited at potentials over the range from ??0.025 to ??0.188 V vs. Ag/AgCl, the deposition of 3.7 mC cm?2 at ??0.100 V for 30 min resulted in a tenfold greater photocurrent when compared to the recorded photocurrent for the undecorated TiO2 nanotubes array. Next, Ru-decorated TiO2 nanotubes with a length of 323?±?18 nm and inner and outer diameters of 91 and 104 nm, respectively, were characterized using SEM-WDS, SEM-FEG, XRD, and XPS. UV-Vis-NIR diffuse reflectance spectroscopy and photoluminescence (PL) measurements, which revealed a maximum PL emission at 445 nm, showed that for the array of Ru-decorated TiO2 nanotubes, the electron-hole recombination may be effectively inhibited by the presence of ruthenium electrodeposited, which can make this photocatalyst even more attractive for environmental applications. The performances of the TiO2 and Ru-decorated TiO2 catalysts were compared in heterogeneous photocatalysis experiments for color removal of an azo-dye, which presented a pseudo-first-order rate constant more than twofold greater for the Ru-decorated TiO2 catalysts. 相似文献
102.
The representation theory of the generalized deformed oscillator algebras (GDOA's) is developed. GDOA's are generated by the four operators {1, a, a
, N}. Their commutators and Hermiticity properties are those of the boson oscillator algebra, except for [a, a
]
q
= G(N), where [a, b]
q
= ab – q ba and G(N) is a Hermitian, analytic function. The unitary irreductible representations are obtained by means of a Casimir operator C and the semi-positive operator a
a. They may belong to one out of four classes: bounded from below (BFB), bounded from above (BFA), finite-dimentional (FD), unbounded (UB). Some examples of these different types of unirreps are given. 相似文献
103.
We define trees generated by bi-infinite sequences, calculate their walk-invariant distribution and the speed of a biased random walk. We compare a simple random walk on a tree generated by a bi-infinite sequence with a simple random walk on an augmented Galton-Watson tree. We find that comparable simple random walks require the augmented Galton-Watson tree to be larger than the corresponding tree generated by a bi-infinite sequence. This is due to an inequality for random variables with values in [1, [ involving harmonic, geometric and arithmetic mean. 相似文献
104.
A rearrangement in basic medium of the natural endoperoxide G3-factor extracted from Eucalyptus grandis is described. Evidence to support a 1,2-dioxetane intermediate that decomposes with weak luminescence emission (quantum yield) is presented. 相似文献
105.
Chabre YM Contino-Pépin C Placide V Shiao TC Roy R 《The Journal of organic chemistry》2008,73(14):5602-5605
A new family of glycodendrimer scaffolds containing 12 and 18 peripheral alpha-d-mannopyranosidic units has been synthesized by Cu(I)-catalyzed [1,3]-dipolar cycloadditions using sulfurated dendritic scaffolds bearing alkyne functionalities and novel TRIS derivatives. 相似文献
106.
Zampella A Sepe V Luciano P Bellotta F Monti MC D'Auria MV Jepsen T Petek S Adeline MT Laprévôte O Aubertin AM Debitus C Poupat C Ahond A 《The Journal of organic chemistry》2008,73(14):5319-5327
A new anti-HIV cyclodepsipeptide, homophymine A, was isolated from a New Caledonian collection of the marine sponge Homophymia sp. The structure of homophymine A was determined by interpretation of spectroscopic data, acid hydrolysis, and LC-MS analysis. Homophymine A contains 11 amino acid residues and an amide-linked 3-hydroxy-2,4,6-trimethyloctanoic acid moiety. Along with four D-, two L-, and one N-methyl amino acids, it also contains four unusual amino acid residues: (2S,3S,4R)-3,4-diMe-Gln, (2R,3R,4S)-4-amino-2,3-dihydroxy-1,7-heptandioic acid, L-ThrOMe, and (2R,3R,4R)-2-amino-3-hydroxy-4,5-dimethylhexanoic acid. In a cell-based XTT assay, homophymine A exhibited cytoprotective activity against HIV-1 infection with a IC50 of 75 nM. 相似文献
107.
Godin JP Breuillé D Obled C Papet I Schierbeek H Hopfgartner G Fay LB 《Journal of mass spectrometry : JMS》2008,43(10):1334-1343
On-line gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) is commonly used to measure isotopic ratios at natural abundance as well as for tracer studies in nutritional and medical research. However, high-precision (13)C isotopic enrichment can also be measured by liquid chromatography-isotope ratio mass spectrometry (LC-IRMS). Indeed, LC-IRMS can be used, as shown by the new method reported here, to obtain a baseline separation and to measure (13)C isotopic enrichment of underivatised amino acids (Asp, Thr-Ser, Glu, Pro, Gly, Ala, Cys and Val). In case of Val, at natural abundance, the SD(delta(13)C) reported with this method was found to be below 1 per thousand . Another key feature of the new LC-IRMS method reported in this paper is the comparison of the LC-IRMS approach with the conventional GC-C-IRMS determination. To perform this comparative study, isotopic enrichments were measured from underivatised Val and its N(O, S)-ethoxycarbonyl ethyl ester derivative. Between 0.0 and 1.0 molar percent excess (MPE) (delta(13)C= -12.3 to 150.8 per thousand), the calculated root-mean-square (rms) of SD was 0.38 and 0.46 per thousand and the calculated rms of accuracy was 0.023 and 0.005 MPE, respectively, for GC-C-IRMS and LC-IRMS. Both systems measured accurately low isotopic enrichments (0.002 atom percent excess (APE)) with an SD (APE) of 0.0004. To correlate the relative (delta(13)C) and absolute (atom%, APE and MPE) isotopic enrichment of Val measured by the GC-C-IRMS and LC-IRMS devices, mathematical equations showing the slope and intercept of the curves were established and validated with experimental data between 0.0 to 2.3 MPE. Finally, both GC-C-IRMS and LC-IRMS instruments were also used to assess isotopic enrichment of protein-bound (13)C-Val in tibial epiphysis in a tracer study performed in rats. Isotopic enrichments measured by LC-IRMS and GC-C-IRMS were not statistically different (p>0.05). The results of this work indicate that the LC-IRMS was successful for high-precision (13)C isotopic measurements in tracer studies giving (13)C isotopic enrichment similar to the GC-C-IRMS but without the step of GC derivatisation. Therefore, for clinical studies requiring high-precision isotopic measurement, the LC-IRMS is the method of choice to measure the isotopic ratio. 相似文献
108.
Sigrid Blömeke Anja Felbrich Christiane Müller Gabriele Kaiser Rainer Lehmann 《ZDM》2008,40(5):719-734
Teacher-education research lacks a common theoretical basis, which prevents a convincing development of instruments and makes it difficult to connect studies to each other. Our paper models how to measure effective teacher education in the context of the current state of knowledge in the field. First, we conceptualize the central criterion of effective teacher education: “professional competence of future teachers”. Second, individual, institutional, and systemic factors are modeled that may influence the acquisition of this competence during teacher education. In doing this, we turn round the perspective taken by Cochran-Smith and Zeichner (Studying teacher education. The report of the AERA panel on research and teacher education. Lawrence Erlbaum, Mahwah 2005), who mainly take an educational-sociological perspective by focusing on characteristics of teacher education and looking for their effects. In contrast, we take an educational-psychological perspective by focusing on professional competence of teachers and examining influences on this. Challenges connected to an assessment of teacher-education outcomes are discussed as well. 相似文献
109.
da Silva Júnior EN de Souza MC Pinto AV Pinto Mdo C Nogueira CM Ferreira VF Azeredo RB 《Magnetic resonance in chemistry : MRC》2008,46(12):1158-1162
Six new nor-beta-lapachones have been synthesized from reaction of 3-bromo-nor-beta-lapachone with arylamines. These derivatives have potent anticancer properties against several cell lines. Here, we report complete unambiguous assignments of (1)H and (13)C chemical shifts of the new compounds. The assignments were made using a combination of one- and two-dimensional NMR techniques ((1)H, (13)C, (1)H-(1)H COSY, (1)H-(13)C HSQC, and (1)H-(13)C HMBC). 相似文献
110.
Riedinger C Endicott JA Kemp SJ Smyth LA Watson A Valeur E Golding BT Griffin RJ Hardcastle IR Noble ME McDonnell JM 《Journal of the American Chemical Society》2008,130(47):16038-16044
In this study we present a method for defining the binding modes of a set of structurally related isoindolinone inhibitors of the MDM2-p53 interaction. This approach derives the location and orientation of isoindolinone binding, based on an analysis of the patterns of magnitude and direction of chemical shift perturbations for a series of inhibitors of the MDM2-p53 interaction. The MDM2-p53 complex is an attractive target for therapeutic intervention in cancer cells with intact tumor suppressor p53, as it offers the possibility of releasing p53 by blocking the MDM2-p53 binding site with a small molecule antagonist to promote apoptosis. Isoindolinones are a novel class of MDM2-antagonists of moderate affinity, which still require the development of more potent candidates for clinical applications. As the applicability of conventional structural methods to this system is limited by a number of fundamental factors, the exploitation of the information contained in chemical shift perturbations has offered a useful route to obtaining structural information to guide the development of more potent compounds. For a set of 12 structurally related isoindolinones, the data suggests 4 different orientations of binding, caused by subtle changes in the chemical structure of the inhibitors. 相似文献