全文获取类型
收费全文 | 3478篇 |
免费 | 78篇 |
国内免费 | 22篇 |
专业分类
化学 | 2175篇 |
晶体学 | 12篇 |
力学 | 145篇 |
数学 | 521篇 |
物理学 | 725篇 |
出版年
2024年 | 4篇 |
2023年 | 35篇 |
2022年 | 81篇 |
2021年 | 118篇 |
2020年 | 101篇 |
2019年 | 84篇 |
2018年 | 61篇 |
2017年 | 47篇 |
2016年 | 135篇 |
2015年 | 94篇 |
2014年 | 137篇 |
2013年 | 173篇 |
2012年 | 230篇 |
2011年 | 258篇 |
2010年 | 150篇 |
2009年 | 129篇 |
2008年 | 206篇 |
2007年 | 200篇 |
2006年 | 213篇 |
2005年 | 197篇 |
2004年 | 152篇 |
2003年 | 135篇 |
2002年 | 134篇 |
2001年 | 50篇 |
2000年 | 28篇 |
1999年 | 31篇 |
1998年 | 33篇 |
1997年 | 39篇 |
1996年 | 37篇 |
1995年 | 28篇 |
1994年 | 26篇 |
1993年 | 19篇 |
1992年 | 11篇 |
1991年 | 15篇 |
1990年 | 14篇 |
1989年 | 11篇 |
1988年 | 15篇 |
1987年 | 9篇 |
1986年 | 11篇 |
1985年 | 11篇 |
1984年 | 10篇 |
1983年 | 11篇 |
1982年 | 13篇 |
1981年 | 14篇 |
1980年 | 8篇 |
1979年 | 13篇 |
1978年 | 7篇 |
1977年 | 5篇 |
1975年 | 10篇 |
1974年 | 5篇 |
排序方式: 共有3578条查询结果,搜索用时 15 毫秒
101.
Luca Mazzei Michele Cianci Stefano Benini Stefano Ciurli 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(52):12145-12158
Urease uses a cluster of two NiII ions to activate a water molecule for urea hydrolysis. The key to this unsurpassed enzyme is a change in the conformation of a flexible structural motif, the mobile flap, which must be able to move from an open to a closed conformation to stabilize the chelating interaction of urea with the NiII cluster. This conformational change brings the imidazole side chain functionality of a critical histidine residue, αHis323, in close proximity to the site that holds the transition state structure of the reaction, facilitating its evolution to the products. Herein, we describe the influence of the solution pH in modulating the conformation of the mobile flap. High-resolution crystal structures of urease inhibited in the presence of N-(n-butyl)phosphoric triamide (NBPTO) at pH 6.5 and pH 7.5 are described and compared to the analogous structure obtained at pH 7.0. The kinetics of urease in the absence and presence of NBPTO are investigated by a calorimetric assay in the pH 6.0–8.0 range. The results indicate that pH modulates the protonation state of αHis323, which was revealed to have pKa=6.6, and consequently the conformation of the mobile flap. Two additional residues (αAsp224 and αArg339) are shown to be key factors for the conformational change. The role of pH in modulating the catalysis of urea hydrolysis is clarified through the molecular and structural details of the interplay between protein conformation and solution acidity in the paradigmatic case of a metalloenzyme. 相似文献
102.
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
103.
Maroni Fabio Bruni Pantaleone Suzuki Naoki Aihara Yuichi Croce Fausto 《Journal of Solid State Electrochemistry》2019,23(6):1697-1703
Journal of Solid State Electrochemistry - All-solid-state batteries represent the next generation of electrochemical energy storage systems. A tin-carbon nanocomposite material is prepared by the... 相似文献
104.
Amorati R Catarzi F Menichetti S Pedulli GF Viglianisi C 《Journal of the American Chemical Society》2008,130(1):237-244
Rotation about the Ar-S bond in ortho-(alkylthio)phenols strongly affects the bond dissociation enthalpy (BDE) and the reactivity of the OH group. Newly synthesized sulfur containing heterocycles 3 and 4, where the -SR group is almost coplanar with the phenolic ring, are characterized by unusually low BDE(O-H) values (79.6 and 79.2 kcal/mol, respectively) and by much higher reactivities toward peroxyl radicals than the ortho-methylthio derivative 1 (82.0 kcal/mol). The importance of the intramolecular hydrogen bond (IHB) in determining the BDE(O-H) was demonstrated by FT-IR experiments, which showed that in heterocycles 3 and 4 the IHB between the phenolic OH group and the S atom is much weaker than that present in 1. Since the IHB can be formed only if the -SR group adopts an out-of-plane geometry, this interaction is possible only in the methylthio derivative 1 and not in 3 and 4. The additive contribution to the phenolic BDE(O-H) of the -SR substituent therefore varies from -3.1 to +2.8 kcal/mol for the in-plane and out-of-plane conformations, respectively. These results may be relevant to understanding the role of the tyrosine-cysteine link in the active site of galactose oxidase, an important enzyme that catalyzes the two-electron aerobic oxidation of primary alcohols to aldehydes. The switching of the ortho -SR substituent between perpendicular and planar conformations may account for the catalytic efficiency of this enzyme. 相似文献
105.
Giorgio Olivo Giorgio Capocasa Barbara Ticconi Osvaldo Lanzalunga Stefano Di Stefano Miquel Costas 《Angewandte Chemie (International ed. in English)》2020,59(31):12703-12708
Predictability is a key requirement to encompass late‐stage C?H functionalization in synthetic routes. However, prediction (and control) of reaction selectivity is usually challenging, especially for complex substrate structures and elusive transformations such as remote C(sp3)?H oxidation, as it requires distinguishing a specific C?H bond from many others with similar reactivity. Developed here is a strategy for predictable, remote C?H oxidation that entails substrate binding to a supramolecular Mn or Fe catalyst followed by elucidation of the conformation of the host‐guest adduct by NMR analysis. These analyses indicate which remote C?H bonds are suitably oriented for the oxidation before carrying out the reaction, enabling prediction of site selectivity. This strategy was applied to late‐stage C(sp3)?H oxidation of amino‐steroids at C15 (or C16) positions, with a selectivity tunable by modification of catalyst chirality and metal. 相似文献
106.
Raffaella Suriano Jasmin Hume Marco Cereda Marco De Fazio Marco Bianchessi Marinella Levi Stefano Turri 《Surface and interface analysis : SIA》2011,43(12):1498-1508
There is a great need to improve the biocompatibility of silicon‐based lab‐on‐chip substrate materials for reliable quantitative analysis of biological solutions. These advanced microdevice surfaces need not only be biocompatible but also have surfaces of defined wettability characteristics. The inhibition of biomolecular activity due to microdevice surface interaction is common and can result in inaccurate results or decreased reaction yields. In this work we investigate different techniques for the chemical functionalization of oxidized silicon (SiOx) surfaces in order to: (i) obtain defined hydrophobic/hydrophilic surfaces; and (ii) increase the efficiency of performing Real‐Time Polymerase Chain Reaction (PCR) on a silicon‐based lab‐on‐chip. Silicon oxide surfaces are functionalized by grafting alkylic chain silanes and poly(ethylene glycol) (PEG) chains to the surfaces, rendering them hydrophobic or hydrophilic. Functionalized surfaces are characterized through contact angle and atomic force microscopy (AFM) measurements, showing stable hydrophobic surfaces with contact angles of 69–78° and layer thicknesses of 11–15 Å and hydrophilic surfaces displaying contact angles of 5–6° and thicknesses of 22–52 Å. PCR experiments carried out directly on bare silicon oxide lab‐on‐chip surfaces show low yields of DNA amplification. Hydrophobic surfaces decrease the inhibition of PCR. Hydrophilic surfaces are a major improvement on the bare silicon oxide exhibiting the same maximum reaction yield as obtained with a standard thermocycler. We have found that the best results are associated with PEG modified surfaces, which prove very suitable for the fabrication of reliable PCR silicon lab‐on‐chips. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
107.
N-(β-Hydroxy)amides can be cyclised by reaction with diisopropylcarbodiimide (DIC) to give the corresponding 2-oxazolines in high yields. The reaction requires only very mild Lewis-acid catalysis (5 mol % Cu(OTf)2) and can be accomplished with simple heating, or in very short reaction times under microwave irradiation. 相似文献
108.
Nine samples of N-acetyl-3,4-methylenedioxyamphetamine (N-acetyl-MDA), prepared according to the most common synthetic procedures, are submitted to (2)H NMR spectroscopy. The relative deuterium content at the various sites of the molecule is shown to depend on its synthetic history. The technique provides a chemical fingerprint of N-acetyl-MDAs and it can be used to trace back the precursor materials and the synthetic pathways employed in the preparation of the samples. 相似文献
109.
Agnese Abate Elisabetta Brenna Giovanni Fronza Claudio Fuganti FrancescoG. Gatti Stefano Serra Enrica Zardoni 《Helvetica chimica acta》2004,87(4):765-780
All the enantiomerically enriched stereoisomers of Clarycet ® ( 1 ), Florol ® ( 2 ), and Rhubafuran ® ( 3 ) were prepared by biocatalysis routes. Their absolute configurations were established, and their olfactory properties were fully evaluated. 相似文献
110.
Costuas K Cador O Justaud F Le Stang S Paul F Monari A Evangelisti S Toupet LC Lapinte C Halet JF 《Inorganic chemistry》2011,50(24):12601-12622
The role of the nitrogen atom on the electronic and magnetic couplings of the mono-oxidized and bi-oxidized pyridine-containing complex models [2,6-{Cp(dpe)Fe-C≡C-}(2)(NC(5)H(3))](n+) and [3,5-{Cp(dpe)Fe-C≡C-}(2)(NC(5)H(3))](n+) is theoretically tackled with the aid of density-functional theory (DFT) and multireference configuration interaction (MR-CI) calculations. Results are analyzed and compared to those obtained for the reference complex [1,3-{Cp*(dppe)Fe-C≡C-)}(2)(C(6)H(4))](n+). The mono-oxidized species show an interesting behavior at the borderline between spin localization and delocalization and one through-bond communication path among the two involving the central ring, is favored. Investigation of the spin state of the dicationic complexes indicates ferromagnetic coupling, which can differ in magnitude from one complex to the other. Very importantly, electronic and magnetic properties of these species strongly depend not only upon the location of the nitrogen atom in the ring versus that of the organometallic end-groups but also upon the architectural arrangement of one terminus, with respect to the other and/or vis-à-vis the central ring. To help validate the theoretical results, the related families of compounds [1,3-{Cp*(dppe)Fe-C≡C-)}(2)(C(6)H(4))](n+), [2,6-{Cp*(dppe)Fe-C≡C-}(2)(NC(5)H(3))](n+), [3,5-{Cp*(dppe)Fe-C≡C-}(2)(NC(5)H(3))](n+) (n = 0-2) were experimentally synthesized and characterized. Electrochemical, spectroscopic (infrared (IR), M?ssbauer), electronic (near-infrared (NIR)), and magnetic properties (electron paramagnetic resonance (EPR), superconducting quantum interference device (SQUID)) are discussed and interpreted in the light of the theoretical data. The set of data obtained allows for many strong conclusions to be drawn. A N atom in the long branch increases the ferromagnetic interaction between the two Fe(III) spin carriers (J > 500 cm(-1)), whereas, when placed in the short branch, it dramatically reduces the magnetic exchange in the di-oxidized species (J = 2.14(5) cm(-1)). In the mixed-valence compounds, when the N atom is positioned on the long branch, the intermediate excited state is higher in energy than the different ground-state conformers and the relaxation process provides exclusively the Fe(II)/Fe(III) localized system (H(ab) ≠ 0). Positioning the N atom on the short branch modifies the energy profile and the diabatic mediating state lies just above the reactant and product diabatic states. Consequently, the LMCT transition becomes less energetic than the MMCT transition. Here, the direct coupling does not occur (H(ab) = 0) and only the coupling through the bridge (c) and the reactant (a) and product (b) diabatic states is operating (H(ac) = H(bc) ≠ 0). 相似文献