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31.
S=1/2 One‐Dimensional Random‐Exchange Ferromagnetic Zigzag Ladder,Which Exhibits Competing Interactions in a Critical Regime 下载免费PDF全文
Susan N. Herringer Dr. Mercè Deumal Dr. Jordi Ribas‐Arino Prof. Juan J. Novoa Prof. Christopher P. Landee Prof. Jan L. Wikaira Prof. Mark M. Turnbull 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(27):8355-8362
The synthesis, crystal structure, and magnetic properties (from a combined experimental and First‐Principles Bottom‐Up theoretical study) of the new compound catena‐dichloro(2‐Cl‐3Mpy)copper(II), 1 , [2‐Cl‐3Mpy=2‐chloro‐3‐methylpyridine] are described and rationalized. Crystals of 1 present well isolated magnetic 1D chains (no 3D order was experimentally observed down to 1.8 K) and magnetic frustration stemming from competing ferromagnetic nearest‐neighbor (JNN) interactions and antiferromagnetic next‐nearest neighbor (JNNN) interactions, in which α=JNNN/JNN <?0.25. These magnetic interactions give rise to a unique magnetic topology: a two‐leg zigzag ladder composed of edge‐sharing up‐down triangles with antiferromagnetic interactions along the rails and ferromagnetic interactions along the zigzag chain that connects the rails. Crystals of 1 also present a random distribution of the 2‐Cl‐3Mpy groups, which are arranged in two different orientations, each with a 50 % occupancy. This translates into a random static structural disorder within each chain by virtue of which the value of the JNN magnetic interactions can randomly take one of the following three values: 53, 36, and 16 cm?1. The structural disorder does not affect the JNNN value, which in all cases is approximately ?9 cm?1. A proper statistical treatment of this disorder provides a computed magnetic susceptibility curve that reproduces the main features of the experimental data. 相似文献
32.
Multiple Stable Conformations Account for Reversible Concentration‐Dependent Oligomerization and Autoinhibition of a Metamorphic Metallopeptidase 下载免费PDF全文
Mar López‐Pelegrín Dr. Núria Cerdà‐Costa Dr. Anna Cintas‐Pedrola Fátima Herranz‐Trillo Dr. Pau Bernadó Dr. Juan R. Peinado Dr. Joan L. Arolas Prof. Dr. F. Xavier Gomis‐Rüth 《Angewandte Chemie (International ed. in English)》2014,53(40):10624-10630
Molecular plasticity controls enzymatic activity: the native fold of a protein in a given environment is normally unique and at a global free‐energy minimum. Some proteins, however, spontaneously undergo substantial fold switching to reversibly transit between defined conformers, the “metamorphic” proteins. Here, we present a minimal metamorphic, selective, and specific caseinolytic metallopeptidase, selecase, which reversibly transits between several different states of defined three‐dimensional structure, which are associated with loss of enzymatic activity due to autoinhibition. The latter is triggered by sequestering the competent conformation in incompetent but structured dimers, tetramers, and octamers. This system, which is compatible with a discrete multifunnel energy landscape, affords a switch that provides a reversible mechanism of control of catalytic activity unique in nature. 相似文献
33.
Joan Miguel‐vila María Toms‐Gamasa Jos L. Mascareas 《Angewandte Chemie (International ed. in English)》2020,59(40):17628-17633
Metal‐mediated intracellular reactions are becoming invaluable tools in chemical and cell biology, and hold promise for strongly impacting the field of biomedicine. Most of the reactions reported so far involve either uncaging or redox processes. Demonstrated here for the first time is the viability of performing multicomponent alkyne cycloaromatizations inside live mammalian cells using ruthenium catalysts. Both fully intramolecular and intermolecular cycloadditions of diynes with alkynes are feasible, the latter providing an intracellular synthesis of appealing anthraquinones. The power of the approach is further demonstrated by generating anthraquinone AIEgens (AIE=aggregation induced emission) that otherwise do not go inside cells, and by modifying the intracellular distribution of the products by simply varying the type of ruthenium complex. 相似文献
34.
Dr. Carles Acosta-Silva Prof. Joan Bertran Prof. Vicenç Branchadell Prof. Antoni Oliva 《Chemphyschem》2020,21(22):2594-2604
The effect of solvent reaction fields and oriented electric fields on the Kemp elimination reaction between methylamine or imidazole and 5-nitrobenzisoxazole has been theoretically studied. The Kemp reaction is the most widely used for the design of new enzymes. Our results, using the SMD continuous model for solvents, are in quite good agreement with the experimental fact that the rate of the analogous reaction with butylamine is one order of magnitude smaller in water than in acetonitrile. In the case of external electric fields, our results show that they can increase or decrease the energy barrier depending on the magnitude and orientation of the field. A duly oriented electric field may have a notable catalytic effect on the reaction. So, external electric fields and reaction fields due to the medium can contribute to the design of new enzymes. Several factors that must be taken into account to increase the catalytic effect are discussed. 相似文献
35.
Nativitat Valls Josep Bonjoch Carlos Del Alamo Joan Bosch 《Helvetica chimica acta》1992,75(1):137-144
A stereodivergent synthesis of enantiomerically pure E-nor-15-azayohimbines via condensation of tryptamine with derivatives of pyroglutamate 4 is reported. When the Pictet-Spengler reaction was induced in refluxing aqueous AcOH a nearly equimolar ratio of lactams 7 and 8 was obtained, whereas under kinetic control (TFA, room temperature) the trans-derivative 8 was the major product. In contrast, cyclization of amido acetal 12 with TsOH gave the cis-derivative 7 as preponderant component. 相似文献
36.
Jaume Llibre Marco Antonio Teixeira Joan Torregrosa 《Mathematical Physics, Analysis and Geometry》2007,10(3):237-249
The goal of this paper is double. First, we illustrate a method for studying the bifurcation of limit cycles from the continuum
periodic orbits of a k-dimensional isochronous center contained in ℝ
n
with n ⩾ k, when we perturb it in a class of differential systems. The method is based in the averaging theory. Second, we consider a particular polynomial differential
system in the plane having a center and a non-rational first integral. Then we study the bifurcation of limit cycles from
the periodic orbits of this center when we perturb it in the class of all polynomial differential systems of a given degree.
As far as we know this is one of the first examples that this study can be made for a polynomial differential system having
a center and a non-rational first integral.
The first and third authors are partially supported by a MCYT/FEDER grant MTM2005-06098-C01, and by a CIRIT grant number 2005SGR-00550.
The second author is partially supported by a FAPESP–BRAZIL grant 10246-2. The first two authors are also supported by the
joint project CAPES–MECD grant HBP2003-0017. 相似文献
37.
38.
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
39.
Di Turo Francesca Parra Rafael Piquero-Cilla Joan Favero Gabriele Doménech-Carbó Antonio 《Journal of Solid State Electrochemistry》2019,23(3):771-781
Journal of Solid State Electrochemistry - Electrochemical impedance spectroscopy (EIS) and voltammetry of immobilized particles (VIMP) measurements using air-saturated mineral water and... 相似文献
40.