全文获取类型
收费全文 | 766篇 |
免费 | 7篇 |
国内免费 | 2篇 |
专业分类
化学 | 402篇 |
晶体学 | 1篇 |
力学 | 5篇 |
数学 | 61篇 |
物理学 | 306篇 |
出版年
2020年 | 4篇 |
2019年 | 6篇 |
2018年 | 3篇 |
2015年 | 7篇 |
2014年 | 9篇 |
2013年 | 20篇 |
2012年 | 22篇 |
2011年 | 37篇 |
2010年 | 15篇 |
2009年 | 17篇 |
2008年 | 38篇 |
2007年 | 19篇 |
2006年 | 26篇 |
2005年 | 29篇 |
2004年 | 23篇 |
2003年 | 17篇 |
2002年 | 10篇 |
2001年 | 22篇 |
2000年 | 20篇 |
1999年 | 10篇 |
1998年 | 10篇 |
1997年 | 9篇 |
1996年 | 18篇 |
1995年 | 17篇 |
1994年 | 16篇 |
1993年 | 31篇 |
1992年 | 27篇 |
1991年 | 12篇 |
1990年 | 16篇 |
1989年 | 11篇 |
1988年 | 12篇 |
1987年 | 13篇 |
1986年 | 14篇 |
1985年 | 21篇 |
1984年 | 9篇 |
1983年 | 11篇 |
1982年 | 15篇 |
1981年 | 8篇 |
1980年 | 13篇 |
1979年 | 19篇 |
1978年 | 6篇 |
1977年 | 19篇 |
1976年 | 16篇 |
1975年 | 12篇 |
1974年 | 7篇 |
1973年 | 13篇 |
1972年 | 4篇 |
1971年 | 4篇 |
1969年 | 7篇 |
1968年 | 4篇 |
排序方式: 共有775条查询结果,搜索用时 0 毫秒
21.
22.
When three-dimensional NMR spectra are presented as two stereoscopic images, they create a convincing three-dimensional impression for the viewer. In an extension of this principle, we record plane projections of a three-dimensional spectrum at different angles, and use this limited information to reconstruct the entire spectrum. Projections onto different skew planes are derived by Fourier transformation of signals acquired while the two evolution parameters are incremented simultaneously at different rates. By limiting the amount of data gathering, this offers an appreciable economy of instrument time. Normally two to six different projections suffice, depending on the complexity of the spectra. There is an order-of-magnitude speed advantage over the conventional methodology, where both evolution dimensions must be explored independently. Results are presented for reconstructed HNCA and HN(CO)CA spectra of ubiquitin and the HNCO spectrum of a 187-residue protein HasA. 相似文献
23.
Gamble BM Gallagher PA Shoemaker JA Parks AN Freeman DM Schwegel CA Creed JT 《The Analyst》2003,128(12):1458-1461
This paper evaluates the chemical stability of four arsenosugars using tetramethylammonium hydroxide (TMAOH) as an extraction solvent. This solvent was chosen because of the near quantitative removal of these arsenicals from difficult to extract seafood (oysters and shellfish). Four arsenosugars (3-[5'-deoxy-5'-(dimethylarsinoyl)-beta-ribofuranosyloxy]-2-hydroxypropylene glycol--As(328), 3-5'-deoxy-5'-(dimethylarsinoyl)-beta-ribofuranosyloxy]-2-hydroxypropanesulfonic acid--As(392), 3-[5'-deoxy-5'-(dimethylarsinoyl)-beta-ribofuranosyloxy]-2-hydroxypropyl hydrogen sulfate--As(408), and 3-[5'-deoxy-5'-(dimethylarsinoyl)-beta-ribofuranosyloxy]-2-hydroxypropyl-2,3-hydroxypropyl phosphate--As(482)) were evaluated. The stability of these four arsenosugars were studied independently in a solution of 2.5% TMAOH at 60 degrees C over a period of up to 8 h. Two arsenosugars, As(328) and As(392), were found to be relatively stable in this solution for up to 8 h. However, As(408) and As(482) formed detectable quantities of dimethylarsinic acid (DMAA) and As(328) within 0.5 and 2 h, respectively. It was found that 97% of As(408) degrades after 8 h of treatment producing 3.4 times as much DMAA as As(328). This is contrary to As(482), which produces 13 times as much As(328) as DMAA and only 37% of the As(482) was converted by the 8 h treatment at 60 degrees C. These degradation products led to the investigation of weaker TMAOH extraction solvents. Three different concentrations (2.5%, 0.83% and 0.25%) were used to determine the effect of TMAOH concentration on the degradation rate of As(408). By reducing the TMAOH concentration to 0.83%, the conversion of the arsenosugar to As(328) and DMAA is nearly eliminated (less than 5% loss). Arsenosugars, As(408) and As(482), were also studied in 253 mM NaOH to verify the degradation products. The NaOH experiments were conducted to investigate a possible hydroxide based reaction mechanism. Similar degradation plots were found for each arsenosugar when compared to the 2.5% TMAOH data. A mechanism has been proposed for the formation of As(328) from As(408) and As(482) in base via an SN2 reaction (hydroxide attack) at the side chain carbon adjacent to the inorganic ester. The formation of DMAA is observed in all arsenosugars after prolonged exposure. This probably occurs via an SN2 attack at the arsenic atom. 相似文献
24.
Dr. Aaron R. Finney Dr. Sébastien Lectez Dr. Colin L. Freeman Prof. John H. Harding Dr. Stephen Stackhouse 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(37):8725-8740
A better understanding of the solution chemistry of the lanthanide (Ln) salts in water would have wide ranging implications in materials processing, waste management, element tracing, medicine and many more fields. This is particularly true for minerals processing, given governmental concerns about lanthanide security of supply and the drive to identify environmentally sustainable processing routes. Despite much effort, even in simple systems, the mechanisms and thermodynamics of LnIII association with small anions remain unclear. In the present study, molecular dynamics (MD), using a newly developed force field, provide new insights into LnCl3(aq) solutions. The force field accurately reproduces the structure and dynamics of Nd3+, Gd3+ and Er3+ in water when compared to calculations using density functional theory (DFT). Adaptive-bias MD simulations show that the mechanisms for ion pairing change from dissociative to associative exchange depending upon cation size. Thermodynamics of association reveal that whereas ion pairing is favourable, the equilibrium distribution of species at low concentration is dominated by weakly bound solvent-shared and solvent-separated ion pairs, rather than contact ion pairs, reconciling a number of contrasting observations of LnIII–Cl association in the literature. In addition, we show that the thermodynamic stabilities of a range of inner sphere and outer sphere coordination complexes are comparable and that the kinetics of anion binding to cations may control solution speciation distributions beyond ion pairs. The techniques adopted in this work provide a framework with which to investigate more complex solution chemistries of cations in water. 相似文献
25.
Wilson PF Freeman CG McEwan MJ Milligan DB Allardyce RA Shaw GM 《Rapid communications in mass spectrometry : RCM》2002,16(5):427-432
We report measurements of residual vapour levels of xylenes and trimethylbenzenes, present following a floor re-surfacing procedure, using the technique of selected ion flow tube mass spectrometry (SIFT-MS). A subject exposed to controlled amounts of xylene and mesitylene was monitored by direct breath exhalation over a 4-hour period after exposure to the volatile organic compounds (VOCs) had stopped. The headspace gases above 5 mL blood samples taken over this period were also monitored. The decays of the solvent levels with time were fitted to a two-compartment model with residence times for xylene and mesitylene of 0.37 h and 0.38 h, respectively (compartment one) and 2.5 h and 2.8 h, respectively (compartment two). 相似文献
26.
27.
Wenzel TJ Freeman BE Sek DC Zopf JJ Nakamura T Yongzhu J Hirose K Tobe Y 《Analytical and bioanalytical chemistry》2004,378(6):1536-1547
Chiral crown ethers 1 and 5 are useful enantiomeric discriminating agents in 1H NMR spectroscopy for neutral and protonated primary amines, amino acids, and amino alcohols. The presence of the carboxylic acid groups in 1 and 5 provide sites at which ytterbium(III) can bind. Adding ytterbium(III) nitrate to crown–substrate mixtures in methanol-d4 causes shifts in the spectra of substrates and often enhances the chiral discrimination in the 1H NMR spectrum. The enhancement in enantiomeric discrimination that occurs in the presence of ytterbium(III) allows lower concentrations of the crown ether to be used in chiral recognition studies. Several amide derivatives of 1 were prepared and evaluated as chiral NMR discriminating agents, although except for 1e, these were less effective than 1. 相似文献
28.
J. Stephen Clark Rebecca P. Freeman Andrew W. Thomas Claire Wilson 《Tetrahedron letters》2004,45(47):8639-8642
A concise enantioselective synthesis of the cyclic ether core of the marine natural product (+)-laurenyne has been accomplished using ring-closing metathesis for medium-ring construction. 相似文献
29.
30.
JO Freeman ME Murphy JC Sherman 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(36):11409-11416
We have reported a template assembled synthetic protein (cavitein?Q4) as an unexpected dimer in the solid state and as a monomer-dimer equilibrium in solution. We have since reported an ability to bias a cavitein's monomer-dimer equilibrium in solution by sequence design involving histidine metal chelation or disulfide incorporation. However, little remains known about the forces contributing to dimeric cavitein crystal nucleation and lattice stabilization. We, therefore, designed glutamine variants to probe factors involved in dimeric cavitein crystallization. It was found that a key glutamate hydrogen-bonding interaction between dimers is integral to crystal formation and stabilization. Additionally, we obtained a crystal structure of a cavitein (Q4-E3H) designed to bias the dimeric structure via histidine metal coordination. The resolved structure indicates a histidine cluster interaction that likely accounts for the biased dimeric form observed in solution. 相似文献