全文获取类型
收费全文 | 152篇 |
免费 | 3篇 |
国内免费 | 1篇 |
专业分类
化学 | 118篇 |
力学 | 2篇 |
数学 | 18篇 |
物理学 | 18篇 |
出版年
2023年 | 1篇 |
2022年 | 8篇 |
2021年 | 5篇 |
2020年 | 1篇 |
2019年 | 2篇 |
2018年 | 2篇 |
2017年 | 2篇 |
2016年 | 1篇 |
2015年 | 2篇 |
2013年 | 6篇 |
2012年 | 4篇 |
2011年 | 14篇 |
2010年 | 4篇 |
2009年 | 4篇 |
2008年 | 6篇 |
2007年 | 10篇 |
2006年 | 11篇 |
2005年 | 5篇 |
2004年 | 11篇 |
2003年 | 3篇 |
2001年 | 7篇 |
2000年 | 4篇 |
1999年 | 1篇 |
1998年 | 4篇 |
1997年 | 2篇 |
1994年 | 3篇 |
1993年 | 2篇 |
1992年 | 2篇 |
1991年 | 3篇 |
1990年 | 3篇 |
1989年 | 2篇 |
1988年 | 1篇 |
1986年 | 4篇 |
1984年 | 2篇 |
1983年 | 2篇 |
1982年 | 3篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1977年 | 2篇 |
1974年 | 1篇 |
1973年 | 2篇 |
1971年 | 1篇 |
1936年 | 1篇 |
排序方式: 共有156条查询结果,搜索用时 31 毫秒
1.
2.
3.
We have determined the optimized structures, relative energies and intramolecular reactions for two anionic forms of malonic acid, anion malonate(-1) (HO(2)CCH(2)CO(2)(-)) and malonate(-2) ((-)O(2)CCH(2)CO(2)(-)). For this purpose we employed accurate quantum chemistry calculations using second-order M?ller-Plesset perturbation theory and Density Functional Theory with an aug'-cc-p-VTZ basis set to determine the structures and energies, and a novel metadynamics method based on Car-Parrinello molecular dynamics for the thermal reactions. For both malonates, we found new isomers (keto and enol structures) characterized by CO(2) rotations and intramolecular proton transfers. These proton transfers characterize the keto-enol tautomerism that takes place both in the monoanion and dianion. In all cases, the keto tautomer is the more stable configuration. The metadynamics method allows the system to explore the potential energy surface in a few picoseconds, crossing activation barriers of 20-50 kcal/mol. 相似文献
4.
D. E. Damiani E. D. Pérez Millán A. J. Rouco 《Reaction Kinetics and Catalysis Letters》1988,36(1):15-20
A H2 chemisorption and TPR study of Ru–Ag/SiO2 catalysts reveals that after oxidation at 373 K this systems behaves like Ru–Cu/SiO2. High temperature oxidation, however, does not result in the separation of the metal like in the Ru–Cu case but in the redispersion of Ag on top of the Ru particles.
H2 Ru–Ag/SiO2 , 373 Ru–Cu/SiO2. , , , Ru–Cu, Ag Ru.相似文献
5.
Solubility measurements of 1-butene in water, from 20 to 50°C and at atmospheric pressure, were carried out using a Ben-Naim/Baer-type apparatus. The experimental results have a precision of about ±0.3%. Using accurate thermodynamic relations, the Ostwald coefficients at the experimental conditions and at infinite dilution, the mole fractions of the dissolved gas at the gas partial pressure of 101.325 kPa and the Henry coefficients at the water vapor pressure were calculated. The mole fraction of dissolved gas were fitted to the Clarke, Glew, and Weiss equation and thermodynamic quantities, standard molar Gibbs energy, entropy, and enthalpy changes, for the process of transferring the 1-butene molecules from the gaseous to the water phase, were computed. Moreover, solubility measurements of 1-butene in an aqueous medium for the cultivation of Xanthobacter Py2 in the same temperature range were also performed at atmospheric pressure. These solubility data are approximately 2.6% lower than those observed in pure water. 相似文献
6.
Dr. Celeste Are Dr. Maria Pérez Dr. Roberto Ballette Dr. Stefano Proto Dr. Federica Caso Nihan Yayik Prof. Joan Bosch Prof. Mercedes Amat 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(69):15929-15933
The synthesis of enantiopure ABCE and ABCD tetracyclic advanced intermediates en route to madangamine alkaloids and studies for the construction of the triunsaturated 15-membered D ring of madangamine B and the saturated 13-membered D ring of madangamine E are reported. 相似文献
7.
A series of cyclophanes composed of two triarylelement caps linked by two-atom bridges has been synthesized. The bridgehead functional groups include phosphines in combination with amines, hydrosilanes, methylsilanes, and ethoxysilanes. Computational studies accurately predicted that when the bridgehead substituents are small (lone pairs or protons), an in,in bridgehead stereochemistry is strongly favored, but larger bridgehead substituents favor the formations of in,out stereoisomers. The X-ray structures, spectra, and reactivity of these compounds are discussed, as well as the resolution of one of the cyclophanes into pure enantiomers. 相似文献
8.
Celeste de Jesus Pereira Franco Oberdan Oliveira Ferreira ngelo Antnio Barbosa de Moraes Everton Luiz Pompeu Varela Lidiane Diniz do Nascimento Sandro Percrio Mozaniel Santana de Oliveira Eloisa Helena de Aguiar Andrade 《Molecules (Basel, Switzerland)》2021,26(11)
Essential oils (EOs) were extracted from Eugenia patrisii, E. punicifolia, and Myrcia tomentosa, specimens A and B, using hydrodistillation. Gas chromatography coupled with mass spectrometry (GC/MS) was used to identify the volatile constituents present, and the antioxidant capacity of EOs was determined using diphenylpicryl-hydrazyl (DPPH) and trolox equivalent antioxidant capacity (TEAC) assays. For E. patrisii, germacrene D (20.03%), bicyclogermacrene (11.82%), and (E)-caryophyllene (11.04%) were identified as the major constituents of the EOs extracted from specimen A, whereas specimen B primarily comprised γ-elemene (25.89%), germacrene B (8.11%), and (E)-caryophyllene (10.76%). The EOs of E. punicifolia specimen A contained β-Elemene (25.12%), (E)-caryophyllene (13.11%), and bicyclogermacrene (9.88%), while specimen B was composed of (E)-caryophyllene (11.47%), bicyclogermacrene (5.86%), β-pinene (5.86%), and γ-muurolene (5.55%). The specimen A of M. tomentosa was characterized by γ-elemene (12.52%), germacrene D (11.45%), and (E)-caryophyllene (10.22%), while specimen B contained spathulenol (40.70%), α-zingiberene (9.58%), and γ-elemene (6.89%). Additionally, the chemical composition of the EOs was qualitatively and quantitatively affected by the collection period. Furthermore, the EOs of the studied specimens, especially specimen A of E. punicifolia, showed a greater antioxidant activity in DPPH rather than TEAC, as represented by a significantly high inhibition percentage (408.0%). 相似文献
9.
Giulia Festa Claudia Scatigno Francesco Armetta Maria Luisa Saladino Veronica Ciaramitaro Viviana Mollica Nardo Rosina Celeste Ponterio 《Molecules (Basel, Switzerland)》2022,27(1)
Spectral preprocessing data and chemometric tools are analytical methods widely applied in several scientific contexts i.e., in archaeometric applications. A systematic classification of natural powdered pigments of organic and inorganic nature through Principal Component Analysis with a multi-instruments spectroscopic study is presented here. The methodology allows the access to elementary and molecular unique benchmarks to guide and speed up the identification of an unknown pigment and its recipe. This study is conducted on a set of 48 powdered pigments and tested on a real-case sample from the wall painting in S. Maria Delle Palate di Tusa (Messina, Italy). Four spectroscopic techniques (X-ray Fluorescence, Raman, Attenuated Total Reflectance and Total Reflectance Infrared Spectroscopies) and six different spectrometers are tested to evaluate the impact of different setups. The novelty of the work is to use a systematic approach on this initial dataset using the entire spectroscopic energy range without any windows selection to solve problems linked with the manipulation of large analytes/materials to find an indistinct property of one or more spectral bands opening new frontiers in the dataset spectroscopic analyses. 相似文献
10.
An overview of analytical methodologies for the determination of antibiotics in environmental waters 总被引:3,自引:0,他引:3
The widespread occurrence of antibiotics as contaminants in the aquatic environment has increased attention in the last years. The concern over the release of antibiotics into the environment is related primarily to the potential for the development of antimicrobial resistance among microorganisms. This article presents an overview of analytical methodologies for the determination of quinolone (Qs) and fluoroquinolone (FQs), macrolide (MLs), tetracycline (TCs), sulfonamide (SAs) antibiotics and trimethoprim (TMP) in different environmental waters. The analysis of these antibiotics has usually been carried out by high-performance liquid chromatography (HPLC) coupled to mass spectrometry (MS) or tandem mass spectrometry (MS/MS) and to a lesser extent by ultraviolet (UV) or fluorescence detection (FD). A very important step before LC analysis is sample preparation and extraction leading to elimination of interferences and prevention of matrix effect and preconcentration of target analytes. 相似文献