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1.
The existence of a homoclinic orbit in dynamical systems implies chaotic behaviour with positive entropy. In this work, we determine explicitly the Markov shifts associated to certain Smale horseshoe homoclinic orbits which allow us to compute a lower bound for the topological entropy that such a system can have. It is done associating a heteroclinic orbit which belongs to the same isotopy class and then determining the Markov partition of the dynamical core of an end periodic mapping. 相似文献
2.
Highly Axial Magnetic Anisotropy in a N3O5 Dysprosium(III) Coordination Environment Generated by a Merocyanine Ligand 下载免费PDF全文
Pramila Selvanathan Gang Huang Thierry Guizouarn Dr. Thierry Roisnel Dr. Guglielmo Fernandez‐Garcia Dr. Federico Totti Dr. Boris Le Guennic Dr. Guillaume Calvez Dr. Kévin Bernot Dr. Lucie Norel Prof. Stéphane Rigaut 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(43):15222-15226
A spiropyran‐based switchable ligand isomerizes upon reaction with lanthanide(III) precursors to generate complexes with an unusual N3O5 coordination sphere. The air‐stable dysprosium(III) complex shows a hysteresis loop at 2 K and a very strong axial magnetic anisotropy generated by the merocyanine phenolate donor. 相似文献
3.
This work presents the implementation of a high‐order, finite‐volume scheme suitable for rotor flows. The formulation is based on the variable extrapolation MUSCL‐scheme, where high‐order spatial accuracy (up to fourth‐order) is achieved using correction terms obtained through successive differentiation. A variety of results are presented, including 2‐ and 3‐dimensional test cases. Results with the proposed scheme, showed better wake and higher resolution of vortical structures compared with the standard MUSCL, even when coarse meshes were employed. The method was also demonstrated for 3‐dimensional unsteady flows using overset and moving grids for the UH‐60A rotor in forward flight and the Enhanced Rotorcraft Innovative Concept Achievement tiltrotor in aeroplane mode. For medium grids, the present method adds reasonable CPU and memory overheads and offers good accuracy on relatively coarse grids. 相似文献
4.
Dr. Arianna Melillo Dr. Antonio Franconetti Prof. Dr. Mercedes Alvaro Prof. Dr. Belen Ferrer Prof. Hermenegildo Garcia 《Chemistry (Weinheim an der Bergstrasse, Germany)》2023,29(1):e202202625
Hydrogenation of multiple bonds are among the most general and important organic reactions. Typical heterogeneous catalysts are based on transition metal nanoparticles, including noble metals. Data are presented here showing that metal nodes of MIL-101(Cr) and UiO-66 in the absence of occluded metal nanoparticles can promote hydrogenation of polarized X=Y double bonds of nitro and carbonyl groups. The catalytic activity is a function of the composition of the metal node and the organic linker. It is proposed that the reaction mechanism is based on the operation of frustrated Lewis acid/base pairs. 相似文献
5.
Karen A. Gonzalez Sarah Kazemeini Dustyn C. Weber Paula A. Cordero Elizabeth M. Garcia Cory A. Rusinek 《Electroanalysis》2023,35(9):e202300098
Trace metals are required in the body as they play a significant role in several biochemical processes. Moreover, certain heavy metals are beneficial at appropriate levels. Copper (Cu), for example, is essential for red blood cell formation, bone strength, and infant growth. Despite these fundamental roles, Cu can become toxic at high levels. Other heavy metals such as lead (Pb), cadmium (Cd), manganese (Mn), and mercury (Hg), have been identified to cause acute and chronic health complications. For these reasons, rapid, real-time quantification of such metals in biological media is of interest to improving human health outcomes. Electrochemical methods offer numerous advantages, such as portability, capability to be miniaturized, low cost, and ease-of-use. In this review, we examine recent developments in electrochemical sensing for the detection of heavy metals in biological media. To meet the requirements for inclusion in this review, the electrochemical sensor must have been evaluated in biological media (blood, serum, sweat, saliva, urine, brain tissue/cells). Several applications are explored to examine recent advancements in electrochemical sensing within these matrices. Addressing the challenges through materials, device, and system innovations, it is expected that electrochemical sensing of heavy metals in biological media will facilitate future diagnoses and treatments in healthcare. 相似文献
6.
Antônio Gomes dos Santos Neto Franciele de Matos Morawski Ana Caroline Ferreira Santos Cláudia Quintino da Rocha Roberto Batista de Lima Marília Oliveira Fonseca Goulart Clenilton Costa dos Santos Flávio Colmati Antônio Euzébio Goulart Santana Marco Aurélio Suller Garcia Auro Atsushi Tanaka 《Electroanalysis》2023,35(5):e202200390
Here, we report multiwalled carbon nanotubes (MWCNTs) functionalized with γ-cyclodextrins (γCD) as a novel electrochemical strategy for Rutin determination, showing superior performance than β-cyclodextrins (βCD) modified MWCNTs, suggesting an adequate environment for host-guest interactions. Under optimized conditions, the sensor showed a linear range of 39–975 nmol L−1 and a limit of detection of 7 nmol L−1. When tested with quercetin, catechin, and caffeine, the platform presented high selectivity with an interference response <10 %. The method was employed to quantify Rutin in spiked pharmaceutical and herbal extracts, providing recovery of 93–98.4 %. Also, HPLC-PDA confirmed the method‘s accuracy. 相似文献
7.
Optimization of Experimental Parameters to Explore Small‐Ligand/Aptamer Interactions through Use of 1H NMR Spectroscopy and Molecular Modeling 下载免费PDF全文
Dr. Florence Souard Dr. Sandrine Perrier Dr. Vincent Noël Dr. Claire Fave Emmanuelle Fiore Prof. Eric Peyrin Prof. Julian Garcia Dr. Cécile Vanhaverbeke 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(44):15740-15748
Aptamers constitute an emerging class of molecules designed and selected to recognize any given target that ranges from small compounds to large biomolecules, and even cells. However, the underlying physicochemical principles that govern the ligand‐binding process still have to be clarified. A major issue when dealing with short oligonucleotides is their intrinsic flexibility that renders their active conformation highly sensitive to experimental conditions. To overcome this problem and determine the best experimental parameters, an approach based on the design‐of‐experiments methodology has been developed. Here, the focus is on DNA aptamers that possess high specificity and affinity for small molecules, L ‐tyrosinamide, and adenosine monophosphate. Factors such as buffer, pH value, ionic strength, Mg2+‐ion concentration, and ligand/aptamer ratio have been considered to find the optimal experimental conditions. It was then possible to gain new insight into the conformational features of the two ligands by using ligand‐observed NMR spectroscopic techniques and molecular mechanics. 相似文献
8.
9.
Acceleration of Acetal Hydrolysis by Remote Alkoxy Groups: Evidence for Electrostatic Effects on the Formation of Oxocarbenium Ions 下载免费PDF全文
Dr. Angie Garcia Douglas A. L. Otte Dr. Walter A. Salamant Jillian R. Sanzone Prof. K. A. Woerpel 《Angewandte Chemie (International ed. in English)》2015,54(10):3061-3064
In contrast to observations with carbohydrates, experiments with 4‐alkoxy‐substituted acetals indicate that an alkoxy group can accelerate acetal hydrolysis by up to 20‐fold compared to substrates without an alkoxy group. The acceleration of ionization in more flexible acetals can be up to 200‐fold when compensated for inductive effects. 相似文献
10.
Ammonia Activation by a Nickel NCN‐Pincer Complex featuring a Non‐Innocent N‐Heterocyclic Carbene: Ammine and Amido Complexes in Equilibrium 下载免费PDF全文
Rudy M. Brown Dr. Javier Borau Garcia Juuso Valjus Christopher J. Roberts Dr. Heikki M. Tuononen Dr. Masood Parvez Prof. Roland Roesler 《Angewandte Chemie (International ed. in English)》2015,54(21):6274-6277
A Ni0‐NCN pincer complex featuring a six‐membered N‐heterocyclic carbene (NHC) central platform and amidine pendant arms was synthesized by deprotonation of its NiII precursor. It retained chloride in the square‐planar coordination sphere of nickel and was expected to be highly susceptible to oxidative addition reactions. The Ni0 complex rapidly activated ammonia at room temperature, in a ligand‐assisted process where the carbene carbon atom played the unprecedented role of proton acceptor. For the first time, the coordinated (ammine) and activated (amido) species were observed together in solution, in a solvent‐dependent equilibrium. A structural analysis of the Ni complexes provided insight into the highly unusual, non‐innocent behavior of the NHC ligand. 相似文献