全文获取类型
收费全文 | 526篇 |
免费 | 27篇 |
专业分类
化学 | 368篇 |
晶体学 | 10篇 |
力学 | 9篇 |
数学 | 60篇 |
物理学 | 106篇 |
出版年
2023年 | 12篇 |
2022年 | 15篇 |
2021年 | 28篇 |
2020年 | 18篇 |
2019年 | 13篇 |
2018年 | 9篇 |
2017年 | 10篇 |
2016年 | 23篇 |
2015年 | 15篇 |
2014年 | 13篇 |
2013年 | 32篇 |
2012年 | 51篇 |
2011年 | 45篇 |
2010年 | 18篇 |
2009年 | 22篇 |
2008年 | 25篇 |
2007年 | 33篇 |
2006年 | 30篇 |
2005年 | 29篇 |
2004年 | 20篇 |
2003年 | 15篇 |
2002年 | 14篇 |
2001年 | 10篇 |
2000年 | 3篇 |
1999年 | 3篇 |
1998年 | 3篇 |
1997年 | 7篇 |
1996年 | 9篇 |
1995年 | 1篇 |
1994年 | 1篇 |
1993年 | 2篇 |
1992年 | 2篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1986年 | 2篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1979年 | 3篇 |
1978年 | 2篇 |
1977年 | 3篇 |
1976年 | 2篇 |
1975年 | 1篇 |
排序方式: 共有553条查询结果,搜索用时 15 毫秒
111.
112.
Dr. Lara Villarino Prof. Kathryn E. Splan Dr. Eswar Reddem M. Sc. Lur Alonso‐Cotchico M. Sc. Cora Gutiérrez de Souza Prof. Agustí Lledós Prof. Jean‐Didier Maréchal Dr. Andy‐Mark W. H. Thunnissen Prof. Gerard Roelfes 《Angewandte Chemie (International ed. in English)》2018,57(26):7785-7789
An artificial heme enzyme was created through self‐assembly from hemin and the lactococcal multidrug resistance regulator (LmrR). The crystal structure shows the heme bound inside the hydrophobic pore of the protein, where it appears inaccessible for substrates. However, good catalytic activity and moderate enantioselectivity was observed in an abiological cyclopropanation reaction. We propose that the dynamic nature of the structure of the LmrR protein is key to the observed activity. This was supported by molecular dynamics simulations, which showed transient formation of opened conformations that allow the binding of substrates and the formation of pre‐catalytic structures. 相似文献
113.
Ferrighi L Marchesan D Ruud K Frediani L Coriani S 《The Journal of chemical physics》2005,123(20):204104
We present an implementation of the polarizable continuum model in its integral equation formulation for the calculation of the magnetizabilities of solvated molecules. The gauge-origin independence of the calculated magnetizabilities and the fast basis set convergence are ensured through the use of London atomic orbitals. Our implementation can use Hartree-Fock and multiconfigurational self-consistent-field (MCSCF) wave functions as well as density-functional theory including hybrid functionals such as B3LYP. We present the results of dielectric continuum effects on water and pyridine using MCSCF wave functions, as well as dielectric medium effects on the magnetizability of the aromatic amino acids as a model for how a surrounding protein environment affects the magnetizability of these molecules. It is demonstrated that the dielectric medium effects on the magnetizability anisotropies of the aromatic amino acids may be substantial, being as large as 25% in the case of tyrosine. 相似文献
114.
Gelson Manzoni de Oliveira Prof. Dr. Lara Regina Soccol Gris Lenice de Lourenço Marques Ernesto Schulz Lang 《无机化学与普通化学杂志》2007,633(4):610-614
Sulfathiazole reacts with [Ph3PAu(CH3COO)] in benzene and with Ag(CH3COO) in methanol giving [(sulfathiazolato)AuPPh3] ( 1 ) and {[Ag(sulfathiazolato)]2}n ( 2 ). While the lattice of 1 contains single molecules with linear N–Au–P bonds, compound 2 performs a polymeric, one‐dimensional assembling of [Ag(sulfathiazolato)]2 dimers linked through intermolecular Ag···O=S=O interactions along the crystallographic axis b. The silver atoms achieve a tetrahedral configuration through Ag–Ag contacts which measure 2.8427(4) Å, considerably shorter than the normal bonding distance of metallic silver. 相似文献
115.
G. Wytze Meindersma Lara M. Galán Sánchez Antje R. Hansmeier André B. de Haan 《Monatshefte für Chemie / Chemical Monthly》2007,1(2):1125-1136
Ionic liquids offer tremendous opportunities to intensify reactions and separations in process technologies by tuning their
physical and chemical properties. Several ionic liquids are suitable for the separation of aromatic and aliphatic hydrocarbons.
CO2 absorption behavior was influenced by the functionalized chains appended to the room temperature ionic liquid (RTIL) cation.
Ionic liquids seem able to combine the chemical features of amine solutions with the characteristic advantages of the physical
solvents used for CO2 absorption. 相似文献
116.
Bioremediation of toluene and naphthalene in liquid cultures of bacteria grown in the presence of these aromatic compounds as unique sources of carbon was investigated by gas chromatography (GC). For this purpose, a method based on the use of GC with flame ionization detection was developed and validated. Validation was carried out in terms of limit of detection (LOD), limit of quantitation (LOQ), linearity, precision and trueness. In the case of naphthalene, LOD and LOQ values of 0.43 and 0.72 mg kg(-1) were achieved. Linearity was established over one order of magnitude in the range of interest, i.e. 10-100 mg kg(-1). Excellent precision was obtained both in terms of intra-day repeatability and between-day precision on two concentration levels (RSD% lower than 0.5%). A recovery of 97.9 +/- 0.2% (n=3) was calculated by addition of 640 mg kg(-1) of naphthalene to the Bushnell & Haas mineral salts basal solution containing the micro-organisms. Findings clearly showed a reduction of the naphthalene content equal to 50% and 75% after two and four weeks of contact with the micro-organisms, whereas a lower degradation was shown in the case of toluene. Finally bioremediation activity was ascribed to two different microbial populations, Bordetella Petrii and Bacillus Sphericus, which survived in the polluted medium. 相似文献
117.
Lim H Eng J Yates JR Tollaksen SL Giometti CS Holden JF Adams MW Reich CI Olsen GJ Hays LG 《Journal of the American Society for Mass Spectrometry》2003,14(9):957-970
A comparative analysis of protein identification for a total of 162 protein spots separated by two-dimensional gel electrophoresis from two fully sequenced archaea, Methanococcus jannaschii and Pyrococcus furiosus, using MALDI-TOF peptide mass mapping (PMM) and mu LC-MS/MS is presented. 100% of the gel spots analyzed were successfully matched to the predicted proteins in the two corresponding open reading frame databases by mu LC-MS/MS while 97% of them were identified by MALDI-TOF PMM. The high success rate from the PMM resulted from sample desalting/concentrating with ZipTip(C18) and optimization of several PMM search parameters including a 25 ppm average mass tolerance and the application of two different protein molecular weight search windows. By using this strategy, low-molecular weight (<23 kDa) proteins could be identified unambiguously with less than 5 peptide matches. Nine percent of spots were identified as containing multiple proteins. By using mu LC-MS/MS, 50% of the spots analyzed were identified as containing multiple proteins. mu LC-MS/MS demonstrated better protein sequence coverage than MALDI-TOF PMM over the entire mass range of proteins identified. MALDI-TOF and PMM produced unique peptide molecular weight matches that were not identified by mu LC-MS/MS. By incorporating amino acid sequence modifications into database searches, combined sequence coverage obtained from these two complimentary ionization methods exceeded 50% for approximately 70% of the 162 spots analyzed. This improved sequence coverage in combination with enzymatic digestions of different specificity is proposed as a method for analysis of post-translational modification from 2D-gel separated proteins. 相似文献
118.
P. L. López-de-Alba S. García González J. Gómez Lara 《Journal of Radioanalytical and Nuclear Chemistry》1989,136(3):203-210
The precipitation of uranyl ion with 2-hydroxy-1-naphthaldehyde /2H–1N=HL/ was studied. The solid complex /orange crystals/ was characterized by IR, UV-Vis spectra. Uranium was determined as U3O8 after calcination of the complex at 850°C /37.78% U experimental, 36.64% U calculated for C22H14O6U, UO2L2/. Using a statistical experimental design, the best conditions for quantitative precipitation were obtained. A gravimetric method for the determination of UO
2
2+
is proposed by weighing the complex after drying at 110°C.On leave from Instituto de Química, U.N.A.M. 相似文献
119.
Bianchi L Dell'Erba C Maccagno M Petrillo G Rizzato E Sancassan F Severi E Tavani C 《The Journal of organic chemistry》2005,70(22):8734-8738
[reaction: see text] In prosecution of previous work on the thermal cyclization of 1-aryl-4-methanesulfonyl-2-nitro-3-phenylsulfonyl-1,3-butadienes (7), the 3-unsubstituted derivatives 8, deriving from the initial ring opening of 3-nitrothiophene (2), have been likewise found herein to undergo cyclization, followed by aromatization, in analogous mild experimental conditions, leading to the ring-fused homo- or heteroaromatic nitro derivatives 10. The concerted electrocyclic nature of the process is strongly supported by the outcome of tests based on the variation of the polarity of the solvent or of the electron density on the aryl of 8. Thus, the successful application of the process to the non-phenylsulfonyl-activated 8 significantly widens the scope of a synthetically valuable overall ring-opening/ring-closing procedure from nitrothiophenes. Support to the recently renewed interest in thermal 6pi electrocyclizations as a tool for the construction of the benzene ring is furthermore provided. 相似文献
120.
Araujo E Rodríguez-Malave AJ González AM Rojas OJ Peñaloza N Bullón J Lara MA Dmitrieva N 《Applied biochemistry and biotechnology》2002,97(2):91-103
In this work, the effect of Fento’s reagent on the degradation of residual Kraft black liquor was investigated. The effect
of Fenton’s reagent on the black liquor degradation was dependent on the concentration of H2O2. At low concentrations (5 and 15 mM) of H2O2, Fenton’s reagent caused the degradation of phenolic groups (6.8 and 44.8%, respectively), the reduction of reaction medium
pH (18.2%), and the polymerization of black liquor lignin. At a high concentration (60 mM) of H2O2, Fenton’s reagent induced an extensive degradation of lignin (95–100%) and discoloration of the black liquor. In the presence
of traces of iron, the addition of H2O2 alone induced mainly lignin fragmentation. In conclusion, Fenton’s reagent and H2O2 alone can degrade residual Kraft black liquor under acidic conditions at room temperature. 相似文献