全文获取类型
收费全文 | 272篇 |
免费 | 19篇 |
专业分类
化学 | 169篇 |
晶体学 | 1篇 |
力学 | 13篇 |
数学 | 35篇 |
物理学 | 38篇 |
无线电 | 35篇 |
出版年
2024年 | 2篇 |
2023年 | 7篇 |
2022年 | 10篇 |
2021年 | 17篇 |
2020年 | 20篇 |
2019年 | 16篇 |
2018年 | 12篇 |
2017年 | 6篇 |
2016年 | 18篇 |
2015年 | 8篇 |
2014年 | 13篇 |
2013年 | 18篇 |
2012年 | 18篇 |
2011年 | 15篇 |
2010年 | 5篇 |
2009年 | 5篇 |
2008年 | 9篇 |
2007年 | 9篇 |
2006年 | 15篇 |
2005年 | 7篇 |
2004年 | 6篇 |
2003年 | 5篇 |
2002年 | 6篇 |
2001年 | 4篇 |
2000年 | 4篇 |
1999年 | 2篇 |
1998年 | 1篇 |
1997年 | 2篇 |
1996年 | 2篇 |
1995年 | 4篇 |
1994年 | 1篇 |
1993年 | 2篇 |
1992年 | 3篇 |
1991年 | 2篇 |
1990年 | 2篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1984年 | 1篇 |
1983年 | 2篇 |
1978年 | 1篇 |
1965年 | 2篇 |
1928年 | 1篇 |
1925年 | 1篇 |
1903年 | 1篇 |
1900年 | 2篇 |
1869年 | 1篇 |
排序方式: 共有291条查询结果,搜索用时 0 毫秒
281.
Christine M. Davidson Alison Nordon Graham J. Urquhart Franco Ajmone-Marsan Mattia Biasioli Armando C. Duarte 《International journal of environmental analytical chemistry》2013,93(8):589-601
A study has been conducted to assess the quality and comparability of measurement of aqua-regia-soluble cadmium, chromium, copper, iron, manganese, nickel, lead, and zinc in urban soils within a small cohort of European research laboratories specializing in soil science or environmental analytical chemistry. An initial survey indicated that highly variable levels of analytical quality control (e.g. use of certified reference materials) were routinely implemented in participant laboratories. When a set of soil samples—differing in metal contents and in characteristics such as pH and organic-matter content—were exchanged and analysed, approximately 20% of results differed from target values by more than 25%. A principal-component analysis was applied to data for chromium, copper, nickel, lead, and zinc, and proved successful in assessing overall laboratory performance. The study indicates that greater prominence needs to be given to quality assurance and control if comparable data are to be generated in international, collaborative research projects. 相似文献
282.
283.
Mattia Riccardo Monaco Belén Poladura Dr. Miriam Diaz de Los Bernardos Markus Leutzsch Dr. Richard Goddard Prof. Dr. Benjamin List 《Angewandte Chemie (International ed. in English)》2014,53(27):7063-7067
Organocatalysis, catalysis using small organic molecules, has recently evolved into a general approach for asymmetric synthesis, complementing both metal catalysis and biocatalysis. 1 Its success relies to a large extent upon the introduction of novel and generic activation modes. 2 Remarkably though, while carboxylic acids have been used as catalyst directing groups in supramolecular transition‐metal catalysis, 3 a general and well‐defined activation mode for this useful and abundant substance class is still lacking. Herein we propose the heterodimeric association of carboxylic acids with chiral phosphoric acid catalysts as a new activation principle for organocatalysis. This self‐assembly increases both the acidity of the phosphoric acid catalyst and the reactivity of the carboxylic acid. To illustrate this principle, we apply our concept in a general and highly enantioselective catalytic aziridine‐opening reaction with carboxylic acids as nucleophiles. 相似文献
284.
G. Barone C. Giancola T. H. Lilley C. A. Mattia R. Puliti 《Journal of Thermal Analysis and Calorimetry》1992,38(12):2771-2778
Enthalpies and temperatures of fusion or transition for four substituted dipeptides (Nacetylamides of glycyl-L-alanine (NAGAA),L-alanyl-L-alanine (NAA2A),L-prolyl-glycine (NAPGA) andL-leucyl-L-proline monohydrate (NALPA·H2O)) were determined by differential scanning calorimetry and the entropies of fusion derived. The results obtained have been compared with those of the corresponding substituted aminoacids and some of their racemic crystalline mixtures. The enthalpies and entropies of fusion of some substituted aminoacids have been redetermined. The results are discussed in comparison with crystal structural data, which has been reported in the literature or determined recently by some of the authors. Rationalization of the fusion parameters was attempted mainly on the basis of the number of intramolecular hydrogen bonds and the packing densities in the crystals.This work was carried out with the financial support from the Italian C.N.R. (Rome) and from the Ministry of University and Scientific and Technological Research. 相似文献
285.
Single‐Molecule Magnetism,Enhanced Magnetocaloric Effect,and Toroidal Magnetic Moments in a Family of Ln4 Squares 下载免费PDF全文
Chinmoy Das Shefali Vaidya Tulika Gupta Jamie M. Frost Mattia Righi Prof. Dr. Euan K. Brechin Prof. Dr. Marco Affronte Prof. Dr. Gopalan Rajaraman Prof. Dr. Maheswaran Shanmugam 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(44):15639-15650
Three cationic [Ln4] squares (Ln=lanthanide) were isolated as single crystals and their structures solved as [Dy4(μ4‐OH)(HL)(H2L)3(H2O)4]Cl2?(CH3OH)4?(H2O)8 ( 1 ), [Tb4(μ4‐OH)(HL)(H2L)3(MeOH)4]Cl2?(CH3OH)4?(H2O)4 ( 2 ) and [Gd4(μ4‐OH)(HL)(H2L)3(H2O)2(MeOH)2]Br2?(CH3OH)4?(H2O)3 ( 3 ). The structures are described as hydroxo‐centered squares of lanthanide ions, with each edge of the square bridged by a doubly deprotonated H2L2? ligand. Alternating current magnetic susceptibility measurements show frequency‐dependent out‐of‐phase signals with two different thermally assisted relaxation processes for 1 , whereas no maxima in χM“ appears above 2.0 K for complex 2 . For 1 , the estimated effective energy barrier for these two relaxation processes is 29 and 100 K. Detailed ab initio studies reveal that complex 1 possesses a toroidal magnetic moment. The ab initio calculated anisotropies of the metal ions in complex 1 were employed to simulate the magnetic susceptibility by using the Lines model (POLY_ANISO) and this procedure yields J1=+0.01 and J2=?0.01 cm?1 for 1 as the two distinct exchange interactions between the DyIII ions. Similar parameters are also obtained for complex 1 (and 2 ) from specific heat measurements. A very weak antiferromagnetic super‐exchange interaction (J1=?0.043 cm?1 and g=1.99) is observed between the metal centers in 3 . The magnetocaloric effect (MCE) was estimated by using field‐dependent magnetization and temperature‐dependent heat‐capacity measurements. An excellent agreement is found for the ?ΔSm values extracted from these two measurements for all three complexes. As expected, 3 shows the largest ?ΔSm variation (23 J Kg?1 K?1) among the three complexes. The negligible magnetic anisotropy of Gd indeed ensures near degeneracy in the (2S+1) ground state microstates, and the weak super‐exchange interaction facilitates dense population of low‐lying excited states, all of which are likely to contribute to the MCE, making complex 3 an attractive candidate for cryogenic refrigeration. 相似文献
286.
Marchini M Mingozzi M Colombo R Guzzetti I Belvisi L Vasile F Potenza D Piarulli U Arosio D Gennari C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(20):6195-6207
The synthesis of eight bifunctional diketopiperazine (DKP) scaffolds is described; these were formally derived from 2,3-diaminopropionic acid and aspartic acid (DKP-1-DKP-7) or glutamic acid (DKP-8) and feature an amine and a carboxylic acid functional group. The scaffolds differ in the configuration at the two stereocenters and the substitution at the diketopiperazinic nitrogen atoms. The bifunctional diketopiperazines were introduced into eight cyclic peptidomimetics containing the Arg-Gly-Asp (RGD) sequence. The resulting RGD peptidomimetics were screened for their ability to inhibit biotinylated vitronectin binding to the purified integrins α(v)β(3) and α(v)β(5), which are involved in tumor angiogenesis. Nanomolar IC(50) values were obtained for the RGD peptidomimetics derived from trans DKP scaffolds (DKP-2-DKP-8). Conformational studies of the cyclic RGD peptidomimetics by (1)H?NMR spectroscopy experiments (VT-NMR and NOESY spectroscopy) in aqueous solution and Monte Carlo/Stochastic Dynamics (MC/SD) simulations revealed that the highest affinity ligands display well-defined preferred conformations featuring intramolecular hydrogen-bonded turn motifs and an extended arrangement of the RGD sequence [Cβ(Arg)-Cβ(Asp) average distance ≥8.8??]. Docking studies were performed, starting from the representative conformations obtained from the MC/SD simulations and taking as a reference model the crystal structure of the extracellular segment of integrin α(v)β(3) complexed with the cyclic pentapeptide, Cilengitide. The highest affinity ligands produced top-ranked poses conserving all the important interactions of the X-ray complex. 相似文献
287.
With a large number of experimental and modelling papers reporting higher than expected liquid flow rates in both hydrophobic and hydrophilic nanochannels published in the last few years, there is a need to develop a coherent theoretical framework to explain these phenomena. In this work we will introduce a complete modelling and present a comparison between experimental data and predicted flows, showing good agreement. 相似文献
288.
Dr. Mattia Moiola Dr. Antonio Bova Dr. Stefano Crespi Dr. Misal G. Memeo Prof. Mariella Mella Prof. Herman S. Overkleeft Dr. Bogdan I. Florea Prof. Paolo Quadrelli 《ChemistryOpen》2019,8(6):770-780
Anthracenenitrile oxide undergoes 1,3-dipolar cycloaddition reaction with propargyl bromide affording the expected isoxazole as single regioisomer, suitably synthetically elaborated and functionalized with a protected triple bond. The introduction of a bromine atom at the position C10 of the anthracene moiety allows for inserting a variety of aromatic and heterocyclic substituents through Suzuki coupling. A two-way synthetic route can lead to simple isoxazole derivatives or, after N−O bond reductive cleavage and BF3 complexation, enamino ketone boron complexes. The photophysical properties of both the substituted isoxazoles and the corresponding boron complexes were investigated to show the potentialities for the employment as fluorescent tags in imaging techniques. The quite good quantum yield values confirm the suitability of these compounds in the cellular environment. Scope and limitations of the methodology are discussed. 相似文献
289.
Kasper Tolborg Dr. Mads R. V. Jørgensen Dr. Mattia Sist Dr. Aref Mamakhel Dr. Jacob Overgaard Prof. Dr. Bo B. Iversen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(27):6814-6822
The covalent nature of the low-barrier N−H−N hydrogen bonds in the negative thermal expansion material H3[Co(CN)6] has been established by using a combination of X-ray and neutron diffraction electron density analysis and theoretical calculations. This finding explains why negative thermal expansion can occur in a material not commonly considered to be built from rigid linkers. The pertinent hydrogen atom is located symmetrically between two nitrogen atoms in a double-well potential with hydrogen above the barrier for proton transfer, thus forming a low-barrier hydrogen bond. Hydrogen is covalently bonded to the two nitrogen atoms, which is the first experimentally confirmed covalent hydrogen bond in a network structure. Source function calculations established that the present N−H−N hydrogen bond follows the trends observed for negatively charge-assisted hydrogen bonds and low-barrier hydrogen bonds previously established for O−H−O hydrogen bonds. The bonding between the cobalt and cyanide ligands was found to be a typical donor–acceptor bond involving a high-field ligand and a transition metal in a low-spin configuration. 相似文献
290.
In this paper, we introduce and study Carleson and sampling measures on Bernstein spaces on a class of quadratic CR manifold called Siegel CR manifolds. These are spaces of entire functions of exponential type whose restrictions to the given Siegel CR manifold are -integrable with respect to a natural measure. For these spaces, we prove necessary and sufficient conditions for a Radon measure to be a Carleson or a sampling measure. We also provide sufficient conditions for sampling sequences. 相似文献