全文获取类型
收费全文 | 140篇 |
免费 | 3篇 |
专业分类
化学 | 121篇 |
力学 | 1篇 |
数学 | 8篇 |
物理学 | 13篇 |
出版年
2023年 | 3篇 |
2022年 | 2篇 |
2021年 | 4篇 |
2020年 | 5篇 |
2019年 | 8篇 |
2017年 | 2篇 |
2016年 | 3篇 |
2014年 | 6篇 |
2013年 | 7篇 |
2012年 | 9篇 |
2011年 | 15篇 |
2010年 | 5篇 |
2009年 | 6篇 |
2008年 | 11篇 |
2007年 | 5篇 |
2006年 | 11篇 |
2005年 | 8篇 |
2004年 | 8篇 |
2003年 | 10篇 |
2002年 | 6篇 |
2000年 | 1篇 |
1999年 | 1篇 |
1998年 | 1篇 |
1997年 | 1篇 |
1995年 | 1篇 |
1994年 | 1篇 |
1985年 | 1篇 |
1982年 | 2篇 |
排序方式: 共有143条查询结果,搜索用时 15 毫秒
41.
Clark JL Peinado J Stezowski JJ Vold RL Huang Y Hoatson GL 《The journal of physical chemistry. B》2006,110(51):26375-26387
The crystal structure of a triclinic 2:2 inclusion complex of beta-cyclodextrin with N-acetyl-L-phenylalanine methyl ester has been determined at several temperatures between 298 and 20 K to further study molecular recognition using solid-state supramolecular beta-cyclodextrin complexes. The study reveals kinetic energy dependent changes in guest molecule conformations, orientations, and positions in the binding pocket presented by the crystal lattice. Accompanying these changes are observable differences in guest-guest interactions and hydrogen-bonding interactions in the binding pocket that involve guest molecules, water of hydration molecules, and beta-cyclodextrin molecules. On the basis of the differences observed in the crystal structures, we present a solid-state example of a system that displays the properties of both classical and quantum chemical models. At higher temperatures, the structure conforms to a classical mechanical model with dynamic disorder. At lower temperatures, the observations conform to examples in which there is static disorder representative of models in which quantum states differing in conformation, position, and orientation of components in the crystal structure are occupied. Ab initio theoretical calculations on the different guest molecule conformations have been carried out. Superpositions of theoretical electrostatic surface potential diagrams on the observed molecular positions in the complexes provide confidence that the deconvolution of the guest molecule disorder is acceptable. Temperature-dependent solid-state magic angle spinning deuteron NMR measurements provide evidence for large-amplitude, diffusive motion on a microsecond time scale in the complex. 相似文献
42.
Leland Rosenberger Ronald Baird Erik McCullen Gregory Auner Gina Shreve 《Surface and interface analysis : SIA》2008,40(9):1254-1261
Ten samples of crystalline aluminum nitride (AlN) film were deposited on sapphire and silicon substrates by a plasma source molecular beam method. The samples were analyzed using X‐ray photoelectron spectroscopy (XPS) depth profiling and high‐resolution X‐ray diffraction. Oxygen levels were observed to decrease exponentially from the surface into the bulk film. Aluminum, nitrogen and oxygen peaks were fitted with subpeaks in a consistent manner and the subpeaks were assigned to chemical states. AlN subpeaks were observed at 73.5 eV for Al2p and 396.4 eV for N1s. An N1s subpeak at 395.0 eV was assigned to N? N defects. No direct N? O bonds are assigned; rather it is proposed that an N? Al? O bond sequence is the source of higher binding energy N1s subpeaks. The observations in this study support a model in which oxygen is bound only to aluminum in the form of Al? O octahedral complexes dispersed or clustered throughout the main AlN matrix or as Al? O bonds on the crystal grain boundaries. The data also suggest that the AlN lattice parameters are related to oxygen content, since the c‐axis is observed to increase with increasing oxygen content. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
43.
[reaction: see text] Haloacetal radical cyclizations of alpha- and beta-hydroxyhydrazones provide a direct access to aminosugarlike compounds. Stereocontrol of this process is influenced by stereogenic centers of both the hydroxyhydrazone and the acetal. The outcomes are consistent with chair and twist transition states with the anomeric alkoxy group in pseudoaxial orientations. 相似文献
44.
Florio GM Christie RA Jordan KD Zwier TS 《Journal of the American Chemical Society》2002,124(34):10236-10247
The hormone melatonin (N-acetyl-5-methoxytryptamine) is an indole derivative with a flexible peptide-like side chain attached at the C3 position. Using a combination of two-color resonant two-photon ionization (2C-R2PI), laser-induced fluorescence excitation (LIF), resonant ion-dip infrared spectroscopy (RIDIRS), fluorescence-dip infrared spectroscopy (FDIRS), and UV-UV hole-burning spectroscopy, the conformational preferences of melatonin in a molecular beam have been determined. Three major trans-amide conformers and two minor cis-amide conformers have been identified in the R2PI spectrum and characterized with RIDIRS and FDIRS. Structural assignments are made using the infrared spectra in concert with density functional theory and localized MP2 calculations. Observation of cis-amide melatonin conformers in the molecular beam, despite the large energy gap (approximately 3 kcal/mol) between trans- and cis-amides, is striking because there are at least nine lower-energy trans-amide minima that are not detected. The implications of this observation for cooling and trapping conformational population in a supersonic expansion are discussed. 相似文献
45.
Gina Pecchi Patricio Reyes M. Graciela Jiliberto T. López J. L. G. Fierro 《Journal of Sol-Gel Science and Technology》2006,37(3):169-174
Platinum-supported catalysts prepared by impregnation of mixed CeO2/Al2O3 and CeO2/ZrO2 oxides using the sol-gel method were characterized and used in the combustion of ethyl acetate. In each series, the effect
of CeO2 loading (3 and 5 wt%) was studied. Characterization data from the studied catalysts (specific area measurements, hydrogen
chemisorption, programmed temperature reduction (TPR), X-ray diffraction (XRD), photoelectron spectra (XPS) and transmission
electron microscopy (TEM)) revealed significant changes in porosity and metal dispersion in each series. The catalytic activity
of the solids, evaluated in the total combustion of ethyl acetate, exhibited a positive effect with the addition of Ce in
the zirconia series whereas no significant changes was observed in the alumina series. 相似文献
46.
Gina Vasile Rodica Olar Dana Marinescu Angela Kriza Luminita Marutescu Mariana Carmen Chifiriuc Veronica Lazar Mihaela Badea 《Journal of Thermal Analysis and Calorimetry》2013,111(3):1783-1790
Five new coordinative compounds that contain mixed ligands (4,4′-bipyridine and methacrylate anion) were synthesized and characterized (elemental analysis, IR and UV–Vis spectroscopy, and thermal studies). The complexes are of the type [M(4,4′-bipy)(C4H5O2)2]·nH2O ((1) M:Mn, n = 0; (2) Co, n = 0.5; (3) M:Ni, n = 1.5; (4) M:Cu, n = 0.5; (5) M:Zn, n = 0.5; 4,4′-bipy: 4,4′-bipyridine; C4H5O2: methacrylate anion). All the tested complexes exhibited very low MIC values against Escherichia coli strains and one compound against Staphylococcus aureus. Besides the specific antimicrobial spectrum, these compounds also inhibited the microbial ability to colonize the inert surfaces, acting as potential anti-adherence and biofilm-controlling agents. The thermal behavior provided confirmation of the complexes' compositions as well as the number and the nature of water molecules and the intervals of thermal stability. 相似文献
47.
Max S. Coles Gina Quach Jonathon E. Beves Evan G. Moore 《Angewandte Chemie (International ed. in English)》2020,59(24):9522-9526
The development of photocatalytic reactions has provided many novel opportunities to expand the scope of synthetic organic chemistry. In parallel with progress towards uncovering new reactivity, there is consensus that efforts focused on providing detailed mechanistic insight in order to uncover underlying excited‐state reactions are essential to maximise formation of desired products. With this in mind, we have investigated the recently reported sensitization‐initiated electron transfer (SenI‐ET) reaction for the C?H arylation of activated aryl halides. Using a variety of techniques, and in particular nanosecond transient absorption spectroscopy, we are able to distinguish several characteristic signals from the excited‐state species involved in the reaction, and subsequent kinetic analysis under various conditions has facilitated a detailed insight into the likely reaction mechanism. 相似文献
48.
Emma Werz Rebecca Viere Gina Gassmann Sergei Korneev Edith Malecki Helmut Rosemeyer 《Helvetica chimica acta》2013,96(5):872-888
Three pyrimidine nucleosides, uridine ( 1 ), 5‐methyluridine ( 6 ), and 2′‐deoxythymidine ( 11 ), were converted to amphiphilic nucleolipids. Compounds 1 and 6 were lipophilized by introduction of symmetric ketal moieties with various carbon chain lengths (i.e., 5–17). Two ketal derivatives, 2b and 7a , were additionally further hydrophobized by N(3)‐farnesylation. 2′‐Deoxythymidine was alkylated at N(3) with a cetyl (=hexadecyl) residue, either directly or, after complete orthogonal protection of the sugar OH groups, by Mitsunobu reaction with hexadecan‐1‐ol. Some of the nucleolipids were subsequently converted to their 2‐cyanoethyl phosphoramidites (5′ or 3′), one of which was used for an exemplary synthesis of a lipo‐oligonucleotide. The sequence of this lipo‐oligonucleotide is an encoded manifestation of Pythagoras' law, created with a key table in which the letters of the alphabet, the numbers from 0 to 9 as well as the mostly used mathematical symbols are allocated to a ribonucleic acid triplet of the genetic code. 相似文献
49.
Norman Marin-Astorga Gina Pecchi Patricio Reyes 《Reaction Kinetics and Catalysis Letters》2005,87(1):121-128
Summary Platinum catalysts (1 wt.%) supported on MCM-41 type and SiO2have been prepared, characterized and evaluated in the enantioselective hydrogenation of 1-phenyl-1,2-propanedione at 298
K and 20 bar of hydrogen pressure, using cinchonidine (CD) as chiral modifier. Chemisorption and TEM results revealed that
both catalysts posses similar metal dispersion, however, significant differences in the catalytic behavior were observed.
With dichloromethane as solvent, high hydrogenation rates and ee values around 47% were obtained for the Pt/MCM-41 catalyst.
This fact is attributed to a confinement effect. The initial reaction rate is strongly dependent on the CD concentration,
and the reaction rate (or ee) vsCD concentration plot exhibits bell-type curves. The main products were (R) -1-hydroxy-1-phenylpropanone and (S) -1-hydroxy-1-phenylpropanone.</o:p> 相似文献
50.
Mihaela Badea Rodica Olar Dana Marinescu Gina Vasile 《Journal of Thermal Analysis and Calorimetry》2008,92(1):205-208
This paper reports the investigation of the thermal stability of a series of new complexes with mixed ligands of the type
[M(en)(C3H3O2)2]·nH2O ((1) M=Ni, n=2; (2) M=Cu, n=0; (3) M=Zn, n=2; en=ethylenediamine and (C3H3O2)=acrylate anion). The thermal behaviour steps were investigated in a nitrogen flow. The thermal transformations are complex
processes according to TG and DTA curves including dehydration, ethylenediamine elimination as well as acrylate thermolysis.
The final products of decomposition are the most stable metal oxides except for complex (2) that generates metallic copper. 相似文献