全文获取类型
收费全文 | 834篇 |
免费 | 31篇 |
国内免费 | 9篇 |
专业分类
化学 | 501篇 |
晶体学 | 1篇 |
力学 | 17篇 |
数学 | 124篇 |
物理学 | 231篇 |
出版年
2021年 | 7篇 |
2020年 | 6篇 |
2019年 | 10篇 |
2018年 | 10篇 |
2016年 | 15篇 |
2015年 | 11篇 |
2014年 | 19篇 |
2013年 | 37篇 |
2012年 | 42篇 |
2011年 | 40篇 |
2010年 | 27篇 |
2009年 | 18篇 |
2008年 | 54篇 |
2007年 | 47篇 |
2006年 | 31篇 |
2005年 | 40篇 |
2004年 | 44篇 |
2003年 | 25篇 |
2002年 | 45篇 |
2001年 | 19篇 |
2000年 | 20篇 |
1999年 | 13篇 |
1998年 | 17篇 |
1997年 | 15篇 |
1996年 | 10篇 |
1995年 | 9篇 |
1994年 | 8篇 |
1993年 | 12篇 |
1992年 | 6篇 |
1991年 | 8篇 |
1990年 | 4篇 |
1989年 | 8篇 |
1988年 | 5篇 |
1987年 | 6篇 |
1986年 | 12篇 |
1985年 | 18篇 |
1984年 | 5篇 |
1983年 | 9篇 |
1982年 | 13篇 |
1981年 | 14篇 |
1980年 | 12篇 |
1979年 | 10篇 |
1978年 | 14篇 |
1977年 | 10篇 |
1976年 | 15篇 |
1975年 | 11篇 |
1974年 | 8篇 |
1973年 | 9篇 |
1972年 | 5篇 |
1971年 | 4篇 |
排序方式: 共有874条查询结果,搜索用时 46 毫秒
41.
42.
Ronald G. Cavell Chih Y. Wong Robert McDonald 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4)
Abstract Neutral hexacoordinate phosphorus(V) compounds of a number of univalent bidentate ligands are known.l,2 The silylated forms of tridentate, dianionic Schiff base ligands: N-(2-hydroxyphenyl)salicylideneamine H2LI, N-(4-tert-butyl-2-hydroxyphenyl)-salicylideneamine H2LII, N-(2-hydroxy-4-nitrophenyl)salicylidene-amine H2LIII, and 2,2′-azodiphenol H2LIV gave, with halogeno- and (trifluoromethyl)halogenophosphoranes, neutral hexa-coordinate derivatives with bis-chelate structures. The ligands form bicyclic five- and six-membered chelate rings in a meridional conformation, with two P-O bonds and one N→P donor bond. Hexacoordinate structures were evidenced by high-field 31P NMR chemical shifts (-136 to -148 ppm), characteristic J PF coupling patterns and was further substantiated by crystal structures of Cl3LII (A) and F3PLII (B). 相似文献
43.
Dr. Fu Chen Dr. Guibin Ma Dr. Guy M. Bernard Prof. Roderick E. Wasylishen Prof. Ronald G. Cavell Dr. Robert McDonald Dr. Michael J. Ferguson 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(8):2826-2838
Several 1:1 adducts of gallium trihalides with triarylphosphines, X3Ga(PR3) (X=Cl, Br, and I; PR3=triarylphosphine ligand), were investigated by using solid‐state 69/71Ga and 31P NMR spectroscopy at different magnetic‐field strengths. The 69/71Ga nuclear quadrupolar coupling parameters, as well as the gallium and phosphorus magnetic shielding tensors, were determined. The magnitude of the 71Ga quadrupolar coupling constants (CQ(71Ga)) range from approximately 0.9 to 11.0 MHz . The spans of the gallium magnetic shielding tensors for these complexes, δ11?δ33, range from approximately 30 to 380 ppm; those determined for phosphorus range from 10 to 40 ppm. For any given phosphine ligand, the gallium nuclei are most shielded for X=I and least shielded for X=Cl, a trend previously observed for InIII–phosphine complexes. This experimental trend, attributed to spin‐orbit effects of the halogen ligands, is reproduced by DFT calculations. The signs of CQ(69/71Ga) for some of the adducts were determined from the analysis of the 31P NMR spectra acquired with magic angle spinning (MAS). The 1J(69/71Ga,31P) and ΔJ(69/71Ga, 31P) values, as well as their signs, were also determined; values of 1J(71Ga,31P) range from approximately 380 to 1590 Hz. Values of 1J(69/71Ga,31P) and ΔJ(69/71Ga,31P) calculated by using DFT have comparable magnitudes and generally reproduce experimental trends. Both the Fermi‐contact and spin‐dipolar Fermi‐contact mechanisms make important contributions to the 1J(69/71Ga,31P) tensors. The 31P NMR spectra of several adducts in solution, obtained as a function of temperature, are contrasted with those obtained in the solid state. Finally, to complement the analysis of NMR spectra for these adducts, single‐crystal X‐ray diffraction data for Br3Ga[P(p‐Anis)3] and I3Ga[P(p‐Anis)3] were obtained. 相似文献
44.
dm Tlgyesi Tams Farkas Mria Blint Thomas J. McDonald Virender K. Sharma 《Molecules (Basel, Switzerland)》2021,26(4)
Alternaria toxins are emerging mycotoxins whose regulation and standardization are in progress by the European Commission and the European Committee for Standardization. This paper describes a dilute and shoot approach to determine five Alternaria toxins in selected food samples using liquid chromatography–tandem mass spectrometry (LC-MS/MS). The strategy involves sample extraction with acidified aqueous methanol, followed by a solvent change accomplished via sample evaporation and reconstitution. The quantification is based on isotope dilution, applying all corresponding isotopically labeled internal standards to compensate possible matrix effects of the analysis. The main advantages of the present method over other existing methods includes simple and effective sample preparation, as well as detection with high sensitivity. The five-fold sample dilution can decrease matrix effects, which were evaluated with both external and internal standard methods. The results demonstrated a limit of quantification lower than 1.0 µg/kg for all five analytes for the first time. The newly presented method showed acceptable accuracy (52.7–111%) when analyzing naturally contaminated and spiked standard samples at the described levels. The method was validated for tomato-based and flour samples (wheat, rye, and maize). The absolute recovery ranged from 66.7% to 91.6% (RSD < 10%). The developed method could be an alternative approach for those laboratories that exclude sample cleanup and pre-concentration of state-of-the-art instruments with enhanced sensitivity. 相似文献
45.
Copper‐Catalyzed α‐Amination of Phosphonates and Phosphine Oxides: A Direct Approach to α‐Amino Phosphonic Acids and Derivatives
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)
Stacey L. McDonald Prof. Dr. Qiu Wang 《Angewandte Chemie (International ed. in English)》2014,53(7):1867-1871
A direct approach to important α‐amino phosphonic acids and its derivatives has been developed by using copper‐catalyzed electrophilic amination of α‐phosphonate zincates with O‐acyl hydroxylamines. This amination provides the first example of C? N bond formation which directly introduces acyclic and cyclic amines to the α‐position of phosphonates in one step. The reaction is readily promoted at room temperature with as little as 0.5 mol % of catalyst, and demonstrates high efficiency on a broad substrate scope. 相似文献
46.
Paolo Pirovano Adriana M. Magherusan Ciara McGlynn Andrew Ure Amy Lynes Dr. Aidan R. McDonald 《Angewandte Chemie (International ed. in English)》2014,53(23):5946-5950
Metal‐bound superoxide intermediates are often implicated as electrophilic oxidants in dioxygen‐activating metalloenzymes. In the nonheme iron α‐ketoglutarate dependent oxygenases and pterin‐dependent hydroxylases, however, FeIII–superoxide intermediates are postulated to react by nucleophilic attack on electrophilic carbon atoms. By reacting a CuII–superoxide complex ( 1 ) with acyl chloride substrates, we have found that a metal–superoxide complex can be a very reactive nucleophile. Furthermore, 1 was found to be an efficient nucleophilic deformylating reagent, capable of Baeyer–Villiger oxidation of a number of aldehyde substrates. The observed nucleophilic chemistry represents a new domain for metal–superoxide reactivity. Our observations provide support for the postulated role of metal–superoxide intermediates in nonheme iron α‐ketoglutarate dependent and pterin‐dependent enzymes. 相似文献
47.
Stacey L. McDonald Charles E. Hendrick Prof. Dr. Qiu Wang 《Angewandte Chemie (International ed. in English)》2014,53(18):4667-4670
Direct amination of heteroarenes and arenes has been achieved in a one‐pot C? H zincation/copper‐catalyzed electrophilic amination procedure. This amination method provides an efficient and rapid approach to access a diverse range of heteroaromatic and aromatic amines including those previously inaccessible using C? H amination methods. The mild reaction conditions and good functional‐group compatibility demonstrate its great potential for the synthesis of important and complex amines. 相似文献
48.
49.
Investigation of N‐Heterocyclic Carbene‐Supported Group 12 Triflates as Pre‐catalysts for Hydrosilylation/Borylation
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Matthew M. D. Roy Dr. Michael J. Ferguson Dr. Robert McDonald Prof. Dr. Eric Rivard 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(50):18236-18246
N‐Heterocyclic carbene (NHC) complexes of Cd and Hg triflates (OTf) were prepared and their attempted conversion into rare cadmium and mercury hydrides was explored. In contrast to zinc, which forms stable [ZnH]+ complexes with NHCs, the heavier Cd and Hg congeners could not be formed; the increased instability of Cd‐H and Hg‐H units was rationalized with the aid of computations. It was also discovered that the dimeric adduct [IPr?Cd(μ‐OTf)2]2 (IPr=[(HCNDipp)2C:]; Dipp=2,6‐iPr2C6H3) is an active precatalyst for the hydrosilylation and hydroborylation of hindered aldehydes and ketones. The related zinc congener was inactive as a catalyst highlighting a distinct advantage of using heavy Group 12 metals to promote catalytic hydrosilylation/borylation. 相似文献
50.
Alain C Schuler BM McDonald KL 《The Journal of the Acoustical Society of America》2002,111(2):990-995
The neural processes underlying concurrent sound segregation were examined by using event-related brain potentials. Participants were presented with complex sounds comprised of multiple harmonics, one of which could be mistuned so that it was no longer an integer multiple of the fundamental. In separate blocks of trials, short-, middle-, and long-duration sounds were presented and participants indicated whether they heard one sound (i.e., buzz) or two sounds (i.e., buzz plus another sound with a pure-tone quality). The auditory stimuli were also presented while participants watched a silent movie in order to evaluate the extent to which the mistuned harmonic could be automatically detected. The perception of the mistuned harmonic as a separate sound was associated with a biphasic negative-positive potential that peaked at about 150 and 350 ms after sound onset, respectively. Long duration sounds also elicited a sustained potential that was greater in amplitude when the mistuned harmonic was perceptually segregated from the complex sound. The early negative wave, referred to as the object-related negativity (ORN), was present during both active and passive listening, whereas the positive wave and the mistuning-related changes in sustained potentials were present only when participants attended to the stimuli. These results are consistent with a two-stage model of auditory scene analysis in which the acoustic wave is automatically decomposed into perceptual groups that can be identified by higher executive functions. The ORN and the positive waves were little affected by sound duration, indicating that concurrent sound segregation depends on transient neural responses elicited by the discrepancy between the mistuned harmonic and the harmonic frequency expected based on the fundamental frequency of the incoming stimulus. 相似文献