全文获取类型
收费全文 | 155篇 |
免费 | 8篇 |
国内免费 | 3篇 |
专业分类
化学 | 131篇 |
晶体学 | 1篇 |
力学 | 4篇 |
数学 | 13篇 |
物理学 | 17篇 |
出版年
2022年 | 1篇 |
2021年 | 1篇 |
2020年 | 3篇 |
2019年 | 4篇 |
2018年 | 4篇 |
2017年 | 2篇 |
2016年 | 5篇 |
2015年 | 3篇 |
2014年 | 3篇 |
2013年 | 7篇 |
2012年 | 9篇 |
2011年 | 8篇 |
2010年 | 5篇 |
2009年 | 2篇 |
2008年 | 14篇 |
2007年 | 16篇 |
2006年 | 17篇 |
2005年 | 12篇 |
2004年 | 12篇 |
2003年 | 7篇 |
2002年 | 5篇 |
2001年 | 3篇 |
1999年 | 3篇 |
1996年 | 2篇 |
1995年 | 1篇 |
1992年 | 1篇 |
1991年 | 2篇 |
1990年 | 3篇 |
1989年 | 1篇 |
1987年 | 1篇 |
1985年 | 1篇 |
1982年 | 1篇 |
1977年 | 2篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1971年 | 1篇 |
1941年 | 2篇 |
排序方式: 共有166条查询结果,搜索用时 421 毫秒
111.
Elin Abraham Callum W. Bailey Timothy D.W. Claridge Stephen G. Davies Kenneth B. Ling Barbara Odell Thomas L. Rees Paul M. Roberts Angela J. Russell Andrew D. Smith Lorna J. Smith Helen R. Storr Miles J. Sweet Amber L. Thompson James E. Thomson George E. Tranter David J. Watkin 《Tetrahedron: Asymmetry》2010,21(13-14):1797-1815
The solid state and solution phase conformational preferences of a homologous series of β-peptides derived from (S,S)-2-aminocyclopentanecarboxylic acid (transpentacin) have been investigated using a variety of spectroscopic and crystallographic techniques. These studies indicate that the hexamer and pentamer persist as a 12-helix in both the solid state and solution phase. Although the conformational traits of a 12-helix are exhibited by oligomers with as few as three residues in the solid state, in solution the trimer exists as an equilibrium of many alternative conformers whilst the tetramer has been shown to predominantly exist in either a 12-helix or a turn-type conformation. 相似文献
112.
Strømgaard K Piazzi L Olsen CA Franzyk H Jaroszewski JW 《Magnetic resonance in chemistry : MRC》2006,44(11):1013-1022
Acid-base properties of the natural polyamine wasp toxin PhTX-433 (1) and seven synthetic analogues [PhTX-343 (2), PhTX-334 (3), PhTX-443 (4), PhTX-434 (5), PhTX-344 (6), PhTX-444 (7), and PhTX-333 (8)], each having four protolytic sites, were characterized by 13C NMR spectroscopy. Nonlinear, multiparameter, simultaneous fit of all chemical shift data obtained from the NMR titration curves yielded macroscopic pKa values as well as intrinsic chemical shift data of all differently protonated macrospecies. Analyses of the chemical shift data demonstrated strong interactions between all four sites and provided information about complex relationships between chemical shift values and protonation state. Deprotonation of fully protonated forms starts at the central amino group of the polyamine moiety, and the extent of this trend depends on the distance to the flanking, protonated amino groups. The pKa1 values of 1-8 are in the range 8.2-9.4. Hence, some of the toxins are incompletely protonated at the pH and ionic strength conditions used for assessment of their interactions with ionotropic glutamate and nicotinic acetylcholine receptors, and the degree of protonation is expected to have pharmacological importance in the ion-channel binding event. 相似文献
113.
The reactions of nitrile oxides with monosubstituted dipolarophiles, such as propiolamide, typically afford proportionally 80 % or more of the 3,5-disubstituted cycloadducts. By contrast, the reactions of 6(A)-deoxy-6(A)-propynamido-beta-cyclodextrin with 4-tert-butylbenzonitrile oxide and 4-phenylbenzonitrile oxide afford >90 % and approximately 85 % of the corresponding 3,4-disubstituted isoxazoles, respectively. As well as reversing the regioselectivity, the cyclodextrin increases the rates of these cycloadditions. The extent of the acceleration is up to more than three orders of magnitude for the production of the cycloadduct preferred by the cyclodextrin, but even the rate of reaction to give the less favored regioisomer is increased. With 6(A)-deoxy-6(A)-propynamido-beta-cyclodextrin, the cycloadducts are not easily separated from the cyclodextrin, as the amide bond is not readily cleaved. In comparison, the regioselectivity of the cycloadditions of 4-tert-butylbenzonitrile oxide with acrylic acid, methacrylic acid, and crotonic acid is also altered by formation of the corresponding cyclodextrin esters, by factors of 500, >10, and >100, respectively. The rates of cycloaddition are also increased by up to 475 times, and in these cases the products of cycloaddition are readily released from the cyclodextrin through ester hydrolysis. Incorporating these processes into a reaction cycle, acylation of beta-cyclodextrin with p-nitrophenyl acrylate and subsequent treatment first with 4-tert-butylbenzonitrile oxide and then with base, the latter to catalyze ester hydrolysis and regenerate the beta-cyclodextrin, affords proportionally fivefold more of the 3,4-disubstituted isoxazoline than is produced directly from acrylic acid. 相似文献
114.
115.
We show that the anomalous negative excess entropy of mixing characteristic of aqueous lower alcohols containing hydrophobic groups is quantitatively consistent with a model exploiting only the experimentally observed molecular-scale segregation of the components across the entire concentration range. The simple model presented here, which uses plausible interatomic distances as its only free parameters, obviates the need to invoke "iceberg" or other water restructuring concepts which, though frequently postulated in explaining the hydrophobic interaction, are unsupported by recent experiments. 相似文献
116.
Satterfield MB Sniegoski LT Sharpless KE Welch MJ Hornikova A Zhang NF Pfeiffer CM Fazili Z Zhang M Nelson BC 《Analytical and bioanalytical chemistry》2006,385(3):612-622
Total homocysteine (tHCY) and folate are interrelated biomarkers for arteriosclerosis and coronary heart disease. Although many different methods for both tHCY and folate are clinically available, the intermethod and interlaboratory results are often poor, resulting in the need for a matrix reference material and reference methods. The National Institute of Standards and Technology (NIST) has developed isotope dilution liquid chromatography/mass spectrometry (LC/MS) and liquid chromatography/ tandem mass spectrometry (LC/MS/MS) methods for determination of tHCY and several folate forms including 5-methyltetrahydrofolic acid (5MT) and folic acid (FA). Additionally, a method for simultaneous measurement of tHCY, 5MT, and FA has been developed and validated. In collaboration with the Centers for Disease Control and Prevention (CDC), mass spectrometric methods and methods used in clinical laboratories have been applied to characterize a new Standard Reference Material (SRM), SRM 1955, "Homocysteine and Folate in Human Serum," containing low, medium, and high levels of tHCY and 5MT. Additionally, FA, 5-formyltetrahydrofolic acid (5FT), vitamin B12, and total folate values are provided. Use of the new SRM should improve clinical measurements and will permit traceability to internationally recognized certified reference materials, as described by European Directive 98/79/EC on in vitro diagnostic medical devices. 相似文献
117.
Michael J. Welch Polly Ellerbe Susan S.-C. Tai Richard G. Christensen Lorna T. Sniegoski Lane C. Sander Curtis S. Phinney 《Fresenius' Journal of Analytical Chemistry》1995,352(1-2):61-65
Substance abuse is a major problem worldwide. There is considerable emphasis placed upon testing individuals for evidence of use of controlled substances. Because the consequences of a positive test can be quite severe, laboratories conducting such tests must rigorously follow a carefully designed quality assurance program. Such a QA program should include use of reference materials to assure that the methods used to detect and quantify drugs are providing accurate results. The National Institute of Standards and Technology (NIST) supports accuracy in drugs of abuse testing by providing Standard Reference Materials (SRMs) with certified concentrations of drugs of abuse in urine- and hair-based reference materials. NIST, working in collaboration with the College of American Pathologists (CAP), has developed urine-based SRMs for marijuana metabolite, cocaine metabolite, morphine and codeine, and morphine glucuronide and CAP Reference Materials for amphetamines and phencyclidine. Certification measurements performed at NIST involve two independent methods for each analyte, one of which always uses GC/MS with the other usually being an LC method with either MS or UV detection. Work has recently been completed on a seven component drug in urine SRM. In addition NIST conducts research in the analysis of hair for drugs of abuse. To assist laboratories testing hair for that purpose, NIST has developed two drugs in hair reference materials.College of American Pathologists Research Associate at NIST 相似文献
118.
119.
Overcoming the Crystallization Bottleneck: A Family of Gigantic Inorganic {Pdx}L (x=84, 72) Palladium Macrocycles Discovered using Solution Techniques
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)
Lorna G. Christie Dr. Andrew J. Surman Dr. Rachel A. Scullion Dr. Feng Xu Dr. De‐Liang Long Prof. Leroy Cronin 《Angewandte Chemie (International ed. in English)》2016,55(41):12741-12745
The {Pd84}Ac wheel, initially discovered serendipitously, is the only reported giant palladium macrocycle—a unique structure that spontaneously assembles from small building blocks. Analogues of this structure are elusive. A new modular route to {Pd84}Ac is described, allowing incorporation of other ligands, and a new screening approach to cluster discovery. Structural assignments were made of new species from solution experiments, overcoming the need for crystallographic analysis. As a result, two new palladium macrocycles were discovered: a structural analogue of the existing {Pd84}Ac wheel with glycolate ligands, {Pd84}Gly , and the next in a magic number series for this cluster family—a new {Pd72}Prop wheel decorated with propionate ligands. These findings confirm predictions of a magic number rule for the family of {Pdx} macrocycles. Furthermore, structures with variable fractions of functional ligands were obtained. Together these discoveries establish palladium clusters as a new class of tunable nanostructures. In facilitating the discovery of species that would not have been discovered by orthodox crystallization approaches, this work also demonstrates the value of solution‐based screening and characterization in cluster chemistry, as a means to decouple cluster formation, discovery, and isolation. 相似文献
120.
Refka Guermazi Lorna Royer Laurent Galmiche Gilles Clavier Pierre Audebert Ahmed Hedhli 《Journal of fluorescence》2016,26(4):1349-1356
Following the case of tetrazines substituted with perfluorinated alkyl chains, separated by two methylene groups from the tetrazine core, a new series of analogous tetrazines, but featuring only one methylene group between the fluorescent core and the perfluorinated chain, have been synthesized, and their photo-physical properties investigated. Their fluorescence quantum yields in acetonitrile are in same range than chloroalkoxytetrazines, which make them interesting candidates for light emission. Surprisingly, the quantum yields are lower with one methylene group, rather than two methylene groups separating the fluorinated chain from the emitting core, in the case of unsymmetrical compounds, while they are superior in the case of symmetrical ones. This unusual observation is discussed in the article. 相似文献