Modification of chiral dimethyl tartrate through transesterification : immobilisation on POSS and enantioselectivity reversion in Sharpless asymmetric epoxidation

Modification of dimethyl tartrate has been investigated through transesterification with aminoalcohols to provide reactive functionalities for the covalent bonding of chiral tartrate to polyhedral oligomeric silsesquioxanes. The transesterification of dimethyl tartrate has been widely studied by means of using different catalytic systems and reaction conditions. Through the proper selection of both, the catalytic system and the reaction conditions, it is possible to achieve the mono- or the bis-substituted tartrate derivative as sole products. All the intermediate chiral tartrate-derived ligands were successfully used in the homogeneous enantioselective epoxidation of allylic alcohols providing moderate enantiomeric excess over the products. Attached amine groups have been used to support the modified tartrate ligands onto a haloaryl-functionalized silsesquioxane moiety. This final chiral tartrate ligand displays enantioselectivity reversion in the asymmetric epoxidation of allylic alcohols with regards to the starting dimethyl tartrate ligand, having both molecules them the same chiral sign. However, the POSS-containing ligand can be easily recovered in almost quantitative yield and reused in asymmetric epoxidation reactions. In addition, recovered silsesquioxane-pendant ligand, though displaying decreasing catalytic activity in recycling epoxidation tests, showed very stable enantioselective behavior

Correlated hopping of bosonic atoms induced by optical lattices

In this work we analyze a particular setup with ultracold atoms trapped in state-dependent lattices. We show that any asymmetry in the contact interaction translates into one of two classes of correlated hopping. After deriving the effective lattice Hamiltonian for the atoms, we obtain analytically and numerically the different phases and quantum phase transitions. We find for weak correlated hopping both Mott insulators and charge density waves, while for stronger correlated hopping the system transitions into a pair superfluid. We demonstrate that this phase exists for a wide range of interaction asymmetries and has interesting correlation properties that differentiate it from an ordinary atomic Bose-Einstein condensate.Comment: 24 pages with 9 figures, to appear in New Journal of Physic

Quantum simulation of Anderson and Kondo lattices with superconducting qubits

We introduce a mapping between a variety of superconducting circuits and a family of Hamiltonians describing localized magnetic impurities interacting with conduction bands. This includes the Anderson model, the single impurity one- and two-channel Kondo problem, as well as the 1D Kondo lattice. We compare the requirements for performing quantum simulations using the proposed circuits to those of universal quantum computation with superconducting qubits, singling out the specific challenges that will have to be addressed.Comment: Longer versio

Activated carbons as catalytic support for Cu nanoparticles

There are a wide range of catalytic applications for Cu-based nanoparticles materials, since Cu is an abundant and inexpensive metal and Cu nanoparticles possess unusual electrical, thermal and optical properties. The possible modification of the chemical and physical properties of these nanoparticles using different synthetic strategies and conditions and/or via postsynthetic chemical treatments has been largely responsible for the rapid growth of interest in these nanomaterials and their applications in catalysis. A previous work have explored the possibilities of SBA-15 (1,2) as support for Cu nanoparticles. In the present contribution, those results will be compared with the use of a carbon material as support, since activated carbon present many advantages with respect SBA, as the high surface area.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Vitamin C activates young LINE-1 elements in mouse embryonic stem cells via H3K9me3 demethylation

This work was supported by grants from the Wellcome Trust/Royal Soci‑ ety (101225/Z/13/Z) and MRC (MR/X008487/1) to M.R.B.; and BBSRC (BB/ T000031/1) to M.R.B. and J.M.F.Background Vitamin C (vitC) enhances the activity of 2-oxoglutarate-dependent dioxygenases, including TET enzymes, which catalyse DNA demethylation, and Jumonji-domain histone demethylases. The epigenetic remodelling promoted by vitC improves the efficiency of induced pluripotent stem cell derivation, and is required to attain a ground-state of pluripotency in embryonic stem cells (ESCs) that closely mimics the inner cell mass of the early blastocyst. However, genome-wide DNA and histone demethylation can lead to upregulation of transposable elements (TEs), and it is not known how vitC addition in culture media affects TE expression in pluripotent stem cells. Results Here we show that vitC increases the expression of several TE families, including evolutionarily young LINE-1 (L1) elements, in mouse ESCs. We find that TET activity is dispensable for L1 upregulation, and that instead it occurs largely as a result of H3K9me3 loss mediated by KDM4A/C histone demethylases. Despite increased L1 levels, we did not detect increased somatic insertion rates in vitC-treated cells. Notably, treatment of human ESCs with vitC also increases L1 protein levels, albeit through a distinct, post-transcriptional mechanism. Conclusion VitC directly modulates the expression of mouse L1s and other TEs through epigenetic mechanisms, with potential for downstream effects related to the multiple emerging roles of L1s in cellular function.Wellcome Trust/Royal Society (101225/Z/13/Z)MRC (MR/X008487/1)BBSRC (BB/T000031/1

NEW LOCALITY AND HOST PLANT RECORDS FOR TWO SPECIES OF NASUTITERMES (ISOPTERA: TERMITIDAE)

NEW LOCALITY AND HOST PLANT RECORDS FOR TWO SPECIES OF NASUTITERMES (ISOPTERA: TERMITIDAE

Corporate board and default risk of financial firms

This paper analyses the impact of corporate board structure on default risk of European banking firms. We focus on four core aspects of boards that have been addressed in Directive 2013/36/ EU to strengthen the corporate governance of banks: the size of boards, their independence, the participation of female directors and CEO duality. We employ panel data analysis to study the 109 European listed banks between 2002 and 2019. Default risk is estimated by Merton’s (1974) distance to default. We take into account the presence of unobservable heterogeneity, simultaneity and dynamic endogeneity and estimate the model using the dynamic difference and dynamic system GMM methodologies. The results show that the size of the board influences banks’ default risk. Furthermore, bank size, firm profitability and GDP also exert a considerable influence

El componente de selección adversa de la horquilla de precios cotizada : una revisión de los modelos de estimación

[email protected] [email protected] de las principales preocupaciones en el área de la microestructura del mercado ha sido la estimación de los componentes no observables de la horquilla de precios a partir de las series de datos que proporcionan los mercados financieros, despertando quizá un mayor interés el de selección adversa por la implicaciones que supone la existencia del mismo. Esto ha provocado el desarrollo de numerosos modelos empíricos que, basándose en las propiedades estadísticas de las series de precios, proporcionan dichas estimaciones. La mayor disponibilidad de datos existentes en los mercados ha permitido el desarrollo en los últimos años de modelos basados en técnicas estadísticas más complejas como son el método generalizado de momentos o la metodología VAR y cuya base de partida es la dinámica de la formación del precio, y, en concreto, cómo la información privada de las transacciones se recoge en los nuevos precios cotizados. El objetivo de este trabajo es analizar este último grupo de trabajos, es decir, aquellos modelos de estimación de los componentes de la horquilla basados en la dinámica de la formación de precios que, además de permitir la estimación del componente de selección adversa en series temporales, suponen una herramienta fundamental para analizar el proceso de incorporación de la información a los precios cotizados en los distintos mercados.One of the main interests of market microstructure is the estimation of the bid–ask spread components from financial data, specially the adverse selection component given the implications of its own existence. As a result, several empirical models based on price time–series statistical properties have been developed in order to estimate them. Recent greater financial data availability has allowed the development of models that focus on price discovery and use more statistical complex methodologies like GMM or VAR. This paper analyses this set of models that allows the estimation of the bid–ask spread components from price dynamics, specifically, the estimation of the adverse selection component in time series. Actually, this sort of models are a powerful tool to investigate how information is incorporated into quotes