全文获取类型
收费全文 | 289篇 |
免费 | 28篇 |
专业分类
化学 | 277篇 |
晶体学 | 2篇 |
力学 | 6篇 |
数学 | 19篇 |
物理学 | 13篇 |
出版年
2023年 | 10篇 |
2022年 | 2篇 |
2021年 | 12篇 |
2020年 | 16篇 |
2019年 | 14篇 |
2018年 | 8篇 |
2017年 | 3篇 |
2016年 | 13篇 |
2015年 | 6篇 |
2014年 | 15篇 |
2013年 | 14篇 |
2012年 | 25篇 |
2011年 | 31篇 |
2010年 | 14篇 |
2009年 | 14篇 |
2008年 | 23篇 |
2007年 | 19篇 |
2006年 | 15篇 |
2005年 | 26篇 |
2004年 | 15篇 |
2003年 | 9篇 |
2002年 | 7篇 |
2001年 | 1篇 |
1998年 | 1篇 |
1995年 | 1篇 |
1994年 | 1篇 |
1993年 | 1篇 |
1985年 | 1篇 |
排序方式: 共有317条查询结果,搜索用时 15 毫秒
1.
Cyrille Chenavier 《Journal of Pure and Applied Algebra》2019,223(2):721-737
We introduce the notion of syzygy for a set of reduction operators and relate it to the notion of syzygy for presentations of algebras. We give a method for constructing a linear basis of the space of syzygies for a set of reduction operators. We interpret these syzygies in terms of the confluence property from rewriting theory. This enables us to optimise the completion procedure for reduction operators based on a criterion for detecting useless reductions. We illustrate this criterion with an example of construction of commutative Gröbner basis. 相似文献
2.
Cyrille Charpentier Jérémy Salaam Dr. Aline Nonat Fabio Carniato Dr. Olivier Jeannin Dr. Isabel Brandariz Dr. David Esteban-Gomez Dr. Carlos Platas-Iglesias Dr. Loïc J. Charbonnière Prof. Mauro Botta 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(24):5407-5418
The heptadentate ligand L was shown to form an extremely stable Gd complex at neutral pH with a pGd value of 18.4 at pH 7.4. The X-ray crystal structures of the complexes formed with Gd and Tb displayed two very different coordination behaviors being, respectively, octa- and nonacoordinated. The relaxometric properties of the Gd complex were studied by field-dependent relaxivity measurements at various temperatures and by 17O NMR spectroscopy. The pH-dependence of the longitudinal relaxivity profile indicated large changes around neutral pH leading to a very large value of 10.1 mm −1⋅s−1 (60 MHz, 298 K) at pH 4.7. The changes were attributed to an increase of the hydration number from one water molecule in basic conditions to two at acidic pH. A similar trend was observed for the luminescence of the Eu complex, confirming the change in hydration state. DOSY experiments were performed on the Lu analogue, pointing to the absence of dimers in solution in the considered pH range. A breathing mode of the complex was postulated, which was further supported by 1H and 31P NMR spectroscopy of the Yb complex at varying pH and was finally modeled by DFT calculations. 相似文献
3.
Zhewen Lu Junqiu Jiang Yi Yang Joshua Lacey Michael J. Brear 《Proceedings of the Combustion Institute》2021,38(1):243-250
This work investigates the oxidation of hydrogen near its second explosion limit in a turbulent flow reactor at pressures of 1 to 8 bar, temperatures of 950 K and an equivalence ratio of 0.035. The concentrations of H2, O2 and H2O are measured along the reactor and simulated using several kinetic models from the literature. These experiments demonstrate evident negative pressure dependence from roughly 1 to 4 bar, with further increases in pressure resuming its positive impact on reaction rates. The simulated and measured species concentrations along the reactor generally agree within a factor of 2.Further investigation is then conducted to measure the rate coefficient of reaction H + O2 (+ M) = HO2 (+M) (R2), which is one of the most sensitive reactions in hydrogen's oxidation chemistry at these conditions. This investigation is conducted by using nitric oxide (NO) as a dopant and measuring the resulting, quasi-steady-state concentrations of NO2. The rate coefficients are obtained at 950 – 1010 K. Combined with literature results, an Arrhenius expression is proposed, = 4.50 × 1020 (T/K)?1.73 [cm6 mole?2 s?1], for the reaction rate at the low-pressure limit over 500 K – 2000 K with N2 as the bath gas. Simulations using the models from the literature with the proposed Arrhenius expression for this reaction then demonstrate improved agreement with the experiments. 相似文献
4.
Eleanor L. Atkinson Jessica Iegre Paul D. Brear Elizabeth A. Zhabina Marko Hyvnen David R. Spring 《Molecules (Basel, Switzerland)》2021,26(7)
Protein kinases are a large class of enzymes with numerous biological roles and many have been implicated in a vast array of diseases, including cancer and the novel coronavirus infection COVID-19. Thus, the development of chemical probes to selectively target each kinase is of great interest. Inhibition of protein kinases with ATP-competitive inhibitors has historically been the most widely used method. However, due to the highly conserved structures of ATP-sites, the identification of truly selective chemical probes is challenging. In this review, we use the Ser/Thr kinase CK2 as an example to highlight the historical challenges in effective and selective chemical probe development, alongside recent advances in the field and alternative strategies aiming to overcome these problems. The methods utilised for CK2 can be applied to an array of protein kinases to aid in the discovery of chemical probes to further understand each kinase’s biology, with wide-reaching implications for drug development. 相似文献
5.
Walid Mabrouk Ridha Lafi Jean Franois Fauvarque Amor Hafiane Cyrille Sollogoub 《先进技术聚合物》2021,32(1):304-314
The purpose of this work is to study the desalination of brackish water using a new ion exchange membrane, made from sulfochlorated polyethersulfone (Cl‐PES), and crosslinked using aminated polyethersulfone (NH2‐PES) as a crosslinking reagent. This membrane, named ClNH2 membrane, has been obtained by reaction between Cl‐PES with 1.3 SO2Cl groups per monomer unit and 0.2 equivalent amount of NH2‐PES. ClNH2 membrane has been characterized in terms of contact angle, transport number, intrinsic conductivity, and water uptake (as a function of temperature). Electrodialysis performances of the newly synthetized membranes have been measured using an electrodialysis cell at a laboratory scale and compared to commercial membranes. All the experiments have been performed using synthetic brackish water solutions prepared from sodium chloride salts with different concentrations (varying from 0.5 to 5.0 g/L). The concentration of different water samples obtained has been found to be below the amount recommended by the World Health Organization (WHO) for drinking water. 相似文献
6.
7.
8.
Mattia Mazza Cyrille Alliot Corinne Sinquin Sylvia Colliec-Jouault Pascal E. Reiller Sandrine Huclier-Markai 《Molecules (Basel, Switzerland)》2021,26(4)
(1) Background: Exopolysaccharide (EPS) derivatives, produced by Alteromonas infernus bacterium, showed anti-metastatic properties. They may represent a new class of ligands to be combined with theranostic radionuclides, such as 47Sc/44Sc. The goal of this work was to investigate the feasibility of such coupling. (2) Methods: EPSs, as well as heparin used as a drug reference, were characterized in terms of molar mass and dispersity using Asymmetrical Flow Field-Flow Fractionation coupled to Multi-Angle Light Scattering (AF4-MALS). The intrinsic viscosity of EPSs at different ionic strengths were measured in order to establish the conformation. To determine the stability constants of Sc with EPS and heparin, a Free-ion selective radiotracer extraction (FISRE) method has been used. (3) Results: AF4-MALS showed that radical depolymerization produces monodisperse EPSs, suitable for therapeutic use. EPS conformation exhibited a lower hydrodynamic volume for the highest ionic strengths. The resulting random-coiled conformation could affect the complexation with metal for high concentration. The LogK of Sc-EPS complexes have been determined and showing that they are comparable to the Sc-Hep. (4) Conclusions: EPSs are very promising to be coupled with the theranostic pair of scandium for Nuclear Medicine. 相似文献
9.
10.
Advances on the Determination of the Astatine Pourbaix Diagram: Predomination of AtO(OH)2− over At− in Basic Conditions 下载免费PDF全文
Dumitru‐Claudiu Sergentu Dr. David Teze Dr. Andréa Sabatié‐Gogova Dr. Cyrille Alliot Ning Guo Dr. Fadel Bassal Dr. Isidro Da Silva Prof. Dr. David Deniaud Dr. Rémi Maurice Dr. Julie Champion Dr. Nicolas Galland Dr. Gilles Montavon 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(9):2964-2971
It is generally assumed that astatide (At?) is the predominant astatine species in basic aqueous media. This assumption is questioned in non‐complexing and non‐reductive aqueous solutions by means of high‐pressure anion‐exchange chromatography. Contrary to what is usually believed, astatide is found to be a minor species at pH=11. A different species, which also bears a single negative charge, becomes predominant when the pH is increased beyond 7. Using competition experiments, an equilibrium constant value of 10?6.9 has been determined for the formation of this species from AtO(OH) with the exchange of one proton. The identification of this species, AtO(OH)2?, is achieved through relativistic quantum mechanical calculations, which rule out the significant formation of the AtO2? species, while leading to a hydrolysis constant of AtO(OH) in excellent agreement with experiment when the AtO(OH)2? species is considered. Beyond the completion of the Pourbaix diagram of astatine, this new information is of interest for the development of 211At radiolabeling protocols. 相似文献