全文获取类型
收费全文 | 1476篇 |
免费 | 34篇 |
国内免费 | 11篇 |
专业分类
化学 | 890篇 |
晶体学 | 8篇 |
力学 | 30篇 |
数学 | 285篇 |
物理学 | 308篇 |
出版年
2021年 | 16篇 |
2020年 | 26篇 |
2019年 | 19篇 |
2018年 | 18篇 |
2017年 | 11篇 |
2016年 | 32篇 |
2015年 | 18篇 |
2014年 | 36篇 |
2013年 | 55篇 |
2012年 | 75篇 |
2011年 | 92篇 |
2010年 | 60篇 |
2009年 | 42篇 |
2008年 | 86篇 |
2007年 | 65篇 |
2006年 | 71篇 |
2005年 | 72篇 |
2004年 | 65篇 |
2003年 | 61篇 |
2002年 | 53篇 |
2001年 | 24篇 |
2000年 | 18篇 |
1999年 | 20篇 |
1998年 | 12篇 |
1997年 | 16篇 |
1996年 | 18篇 |
1994年 | 9篇 |
1993年 | 22篇 |
1992年 | 31篇 |
1991年 | 8篇 |
1990年 | 13篇 |
1989年 | 12篇 |
1988年 | 13篇 |
1987年 | 13篇 |
1986年 | 12篇 |
1985年 | 14篇 |
1984年 | 12篇 |
1983年 | 13篇 |
1982年 | 19篇 |
1981年 | 16篇 |
1980年 | 16篇 |
1979年 | 20篇 |
1978年 | 16篇 |
1977年 | 18篇 |
1976年 | 12篇 |
1975年 | 13篇 |
1974年 | 22篇 |
1973年 | 23篇 |
1972年 | 9篇 |
1954年 | 9篇 |
排序方式: 共有1521条查询结果,搜索用时 593 毫秒
81.
Ditte C. Andersen Ida Skovrind Marlene Louise Christensen Charlotte H. Jensen Søren P. Sheikh 《Analytical and bioanalytical chemistry》2013,405(29):9585-9591
Stem cell therapy has opened up the possibility of treating numerous degenerating diseases. However, we are still merely at the stage of identifying appropriate sources of stem cells and exploring their full differentiation potential. Thus, tracking the stem cells upon in vivo engraftment and during in vitro co-culture is very important and is an area of research embracing many pitfalls. 5-Ethynyl-2′-deoxyuridine (EdU), a rather new thymidine analog incorporated into DNA, has recently been suggested to be a novel highly valid alternative to other dyes for labeling of stem cells and subsequent tracing of their proliferation and differentiation ability. However, our results herein do not at any stage support this recommendation, since EdU severely reduces the viability of stem cells. Accordingly, we found that transplanted EdU-labeled stem cells hardly survive upon in vivo transplantation into regenerating muscle, whereas stem cells labeled in parallel with another dye survived very well and also participated in myofiber formation. Similar data were obtained upon in vitro myogenic culture, and further analysis showed that EdU reduced cell numbers by up to 88 % and increased the cell volume of remaining cells by as much as 91 %. Even at low EdU concentrations, cell survival and phenotype were substantially compromised, and the myogenic differentiation potential was inhibited. Since we examined both primary derived cells and cell lines from several species with the same result, this appears to be a common trait of EdU. We therefore suggest that EdU labeling should be avoided (or used with precaution) for stem cell tracing purposes. Figure
Myoblasts were marked with DiI (red) and EdU (purple), and injected into lesioned skeletal muscle. At day 9 following transplantation, only DiI positive cells were observed and had participated in myofibre formation as (indicated by arrowheads) visualized by red fluorescence signals inside laminin (green) positive multinucleated myofibres. EdU was toxic to the engrafted cells, suggesting that this reagent is non-applicaple for tracing of stem cells. 相似文献
82.
An intramolecular, organocatalyzed Michael addition has been developed to obtain biologically important 2,3‐disubstituted cis‐2,3‐dihydrobenzofurans. By using mandelic acid salts of primary aminocatalysts, derived from cinchona alkaloids, the intramolecular cyclization reaction has been developed to proceed in high yield, with moderate to good diastereoselectivity, and up to 99 % ee. Based on the absolute configuration of the formed 2,3‐disubstituted‐cis‐2,3‐dihydrobenzofurans and by considering the observed substrate scope restrictions, a mechanistic rationalization has been presented. 相似文献
83.
V. Aranda J. M. Christensen M. U. Alzueta P. Glarborg S. Gersen Y. Gao P. Marshall 《国际化学动力学杂志》2013,45(5):283-294
A detailed chemical kinetic model for oxidation of CH3OH at high pressure and intermediate temperatures has been developed and validated experimentally. Ab initio calculations and Rice–Ramsperger–Kassel–Marcus/transition state theory (RRKM/TST) analysis were used to obtain rate coefficients for , , , and . The experiments, involving CH3OH/O2 mixtures diluted in N2, were carried out in a high‐pressure flow reactor at 600–900 K and 20–100 bar, varying the reaction stoichiometry from very lean to fuel‐rich conditions. Under the conditions studied, the onset temperature for methanol oxidation was not dependent on the stoichiometry, whereas increasing pressure shifted the ignition temperature toward lower values. Model predictions of the present experimental results, as well as rapid compression machine data from the literature, were generally satisfactory. The governing reaction pathways have been outlined based on calculations with the kinetic model. Unlike what has been observed for unsaturated hydrocarbons, the oxidation pathways for CH3OH under the investigated conditions were very similar to those prevailing at higher temperatures and lower pressures. At the high pressures, the modeling predictions for onset of reaction were particularly sensitive to the reaction. 相似文献
84.
Prof. Dr. I. Kira Astakhova Prof. Dr. Jesper Wengel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(3):1112-1122
Double‐labeled oligonucleotide probes containing fluorophores interacting by energy‐transfer mechanisms are essential for modern bioanalysis, molecular diagnostics, and in vivo imaging techniques. Although bright xanthene and cyanine dyes are gaining increased prominence within these fields, little attention has thus far been paid to probes containing these dyes internally attached, a fact which is mainly due to the quite challenging synthesis of such oligonucleotide probes. Herein, by using 2′‐O‐propargyl uridine phosphoramidite and a series of xanthenes and cyanine azide derivatives, we have for the first time performed solid‐phase copper(I)‐catalyzed azide–alkyne cycloaddition (CuAAC) click labeling during the automated phosphoramidite oligonucleotide synthesis followed by postsynthetic click reactions in solution. We demonstrate that our novel strategy is rapid and efficient for the preparation of novel oligonucleotide probes containing internally positioned xanthene and cyanine dye pairs and thus represents a significant step forward for the preparation of advanced fluorescent oligonucleotide probes. Furthermore, we demonstrate that the novel xanthene and cyanine labeled probes display unusual and very promising photophysical properties resulting from energy‐transfer interactions between the fluorophores controlled by nucleic acid assembly. Potential benefits of using these novel fluorescent probes within, for example, molecular diagnostics and fluorescence microscopy include: Considerable Stokes shifts (40–110 nm), quenched fluorescence of single‐stranded probes accompanied by up to 7.7‐fold light‐up effect of emission upon target DNA/RNA binding, remarkable sensitivity to single‐nucleotide mismatches, generally high fluorescence brightness values (FB up to 26), and hence low limit of target detection values (LOD down to <5 nM ). 相似文献
85.
Jingbo Chang Guihua Zhou Erik R. Christensen Robert Heideman Junhong Chen 《Analytical and bioanalytical chemistry》2014,406(16):3957-3975
Graphene (G) is attracting significant attention because of its unique physical and electronic properties. The production of graphene through the reduction of graphene oxide (GO) is a low-cost method. The reduction of GO can further lead to electrically conductive reduced GO. These graphene-based nanomaterials are attractive for high-performance water sensors due to their unique properties, such as high specific surface areas, high electron mobilities, and exceptionally low electronic noise. Because of potential risks to the environment and human health arising from heavy-metal pollution in water, G-/GO-based water sensors are being developed for rapid and sensitive detection of heavy-metal ions. In this review, a general introduction to graphene and GO properties, as well as their syntheses, is provided. Recent advances in optical, electrochemical, and electrical detection of heavy-metal ions using graphene or GO are then highlighted. Finally, challenges facing G/GO-based water sensor development and outlook for future research are discussed. 相似文献
86.
We consider the Q-state Potts model in the random-cluster formulation, defined on finite two-dimensional lattices of size L×N with toroidal boundary conditions. Due to the non-locality of the clusters, the partition function Z(L,N) cannot be written simply as a trace of the transfer matrix TL. Using a combinatorial method, we establish the decomposition Z(L,N)=∑l,Dkb(l,Dk)Kl,Dk, where the characters Kl,Dk=i∑N(λi) are simple traces. In this decomposition, the amplitudes b(l,Dk) of the eigenvalues λi of TL are labelled by the number l=0,1,…,L of clusters which are non-contractible with respect to the transfer (N ) direction, and a representation Dk of the cyclic group Cl. We obtain rigorously a general expression for b(l,Dk) in terms of the characters of Cl, and, using number theoretic results, show that it coincides with an expression previously obtained in the continuum limit by Read and Saleur. 相似文献
87.
Rouven F. Pfleger Sören Schlittenhardt Dr. Marcel P. Merkel Prof. Dr. Mario Ruben Prof. Dr. Karin Fink Dr. Christopher E. Anson Prof. Jesper Bendix Prof. Dr. Annie K. Powell 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(61):15086-15095
We report three structurally related single ion Dy compounds using the pentadentate ligand 2,6-bis((E)-1-(2-(pyridin-2-yl)-hydrazineylidene)ethyl)pyridine (H2dapp) [Dy(H2dapp)(NO3)2]NO3 ( 1 ), [Dy(H2dapp)(OAc)2]Cl ( 2 ) and [Dy(H2dapp)(NO3)2]Cl0.92(NO3)0.08 ( 3 ). The (H2dapp) occupies a helical twisted pentagonal equatorial arrangement with two anionic ligands in the axial positions. Further influence on the electronic and magnetic structure is provided by a closely associated counterion interacting with the central N−H group of the (H2dapp). The slow relaxation of the magnetisation shows that the anionic acetates give the greatest slowing down of the magnetisation reversal. Further influence on the relaxation properties of compounds 1 and 2 is the presence of short nitrate-nitrate intermolecular ligand contact opening further lattice relaxation pathways. 相似文献
88.
Platinum‐Promoted Ga/Al2O3 as Highly Active,Selective, and Stable Catalyst for the Dehydrogenation of Propane
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Jesper J. H. B. Sattler Dr. Ines D. Gonzalez‐Jimenez Dr. Lin Luo Brien A. Stears Dr. Andrzej Malek Dr. David G. Barton Dr. Beata A. Kilos Dr. Mark P. Kaminsky Tiny W. G. M. Verhoeven Eline J. Koers Prof. Dr. Marc Baldus Prof. Dr. Bert M. Weckhuysen 《Angewandte Chemie (International ed. in English)》2014,53(35):9251-9256
A novel catalyst material for the selective dehydrogenation of propane is presented. The catalyst consists of 1000 ppm Pt, 3 wt % Ga, and 0.25 wt % K supported on alumina. We observed a synergy between Ga and Pt, resulting in a highly active and stable catalyst. Additionally, we propose a bifunctional active phase, in which coordinately unsaturated Ga3+ species are the active species and where Pt functions as a promoter. 相似文献
89.
Inside Cover: Fluoride‐Bridged {GdIII3MIII2} (M=Cr,Fe, Ga) Molecular Magnetic Refrigerants (Angew. Chem. Int. Ed. 9/2014)
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
90.
Hideyuki Tatsuno Kasper S. Kjr Kristjan Kunnus Tobias C. B. Harlang Cornelia Timm Meiyuan Guo Pavel Chbera Lisa A. Fredin Robert W. Hartsock Marco E. Reinhard Sergey Koroidov Lin Li Amy A. Cordones Olga Gordivska Om Prakash Yizhu Liu Mads G. Laursen Elisa Biasin Frederik B. Hansen Peter Vester Morten Christensen Kristoffer Haldrup Zoltn Nmeth Dorottya Srosin Szemes va Bajnczi Gyrgy Vank Tim B. Van Driel Roberto Alonso‐Mori James M. Glownia Silke Nelson Marcin Sikorski Henrik T. Lemke Dimosthenis Sokaras Sophie E. Canton Asmus O. Dohn Klaus B. Mller Martin M. Nielsen Kelly J. Gaffney Kenneth Wrnmark Villy Sundstrm Petter Persson Jens Uhlig 《Angewandte Chemie (International ed. in English)》2020,59(1):364-372
Iron N‐heterocyclic carbene (NHC) complexes have received a great deal of attention recently because of their growing potential as light sensitizers or photocatalysts. We present a sub‐ps X‐ray spectroscopy study of an FeIINHC complex that identifies and quantifies the states involved in the deactivation cascade after light absorption. Excited molecules relax back to the ground state along two pathways: After population of a hot 3MLCT state, from the initially excited 1MLCT state, 30 % of the molecules undergo ultrafast (150 fs) relaxation to the 3MC state, in competition with vibrational relaxation and cooling to the relaxed 3MLCT state. The relaxed 3MLCT state then decays much more slowly (7.6 ps) to the 3MC state. The 3MC state is rapidly (2.2 ps) deactivated to the ground state. The 5MC state is not involved in the deactivation pathway. The ultrafast partial deactivation of the 3MLCT state constitutes a loss channel from the point of view of photochemical efficiency and highlights the necessity to screen transition‐metal complexes for similar ultrafast decays to optimize photochemical performance. 相似文献