Synthesis, structure and reactivity of Pd and Ir complexes based on new lutidine-derived NHC/phosphine mixed pincer ligands

Coordination studies of new lutidine-derived hybrid NHC/phosphine ligands (CNP) to Pd and Ir have been performed. Treatment of the square-planar [Pd(CNP)Cl](AgCl2) complex 2a with KHMDS produces the selective deprotonation at the CH2P arm of the pincer to yield the pyridine-dearomatised complex 3a. A series of cationic [Ir(CNP)(cod)]+ complexes 4 has been prepared by reaction of the imidazolium salts 1 with Ir(acac)(cod). These derivatives exhibit in the solid state, and in solution, a distorted trigonal bipyramidal structure in which the CNP ligands adopt an unusual C(axial)–N(equatorial)–P(equatorial) coordination mode. Reactions of complexes 4 with CO and H2 yield the carbonyl species 5a(Cl) and 6a(Cl), and the dihydrido derivatives 7, respectively. Furthermore, upon reaction of complex 4b(Br) with base, selective deprotonation at the methylene CH2P arms is observed. The, thus formed, deprotonated Ir complex 8b reacts with H2 in a ligand-assisted process leading to the trihydrido complex 9b, which can also be obtained by reaction of 7b(Cl) with H2 in the presence of KOtBu. Finally, the catalytic activity of Ir–CNP complexes in the hydrogenation of ketones has been briefly assessed.CTQ2013-45011-P, CTQ2016-80814-R and CTQ2014 -51912-RE

Controlled manipulation of enzyme specificity through immobilization-induced flexibility constraints

It is thought that during immobilization enzymes, as dynamic biomolecules, may become distorted and this may alter their catalytic properties. However, the effects of different immobilization strategies on enzyme rigidity or flexibility and their consequences in specificity and stereochemistry at large scale has not been yet clearly evaluated and understood. This was here investigated by using as model an ester hydrolase, isolated from a bacterium inhabiting a karstic lake, with broad substrate spectrum (72 esters being converted; 61.5 U mg$^{-1}$ for glyceryl tripropionate) but initially non-enantiospecific. We found that the enzyme (7 nm × 4.4 nm × 4.2 nm) could be efficiently ionic exchanged inside the pores (9.3 nm under dry conditions) of amino-functionalized ordered mesoporous material (NH$_{2}$-SBA-15), achieving a protein load of 48 mg g−1, and a specific activity of 4.5 ± 0.1 U mg$^{-1}$. When the enzyme was site-directed immobilized through His interaction with an immobilized cationon the surface of two types of magnetic micro-particles through hexahistidine-tags, protein loads up to 10.2 μg g$^{-1}$ and specific activities of up to 29.9 ± 0.3 U mg$^{-1}$, were obtained. We found that ionically exchanged enzyme inside pores of NH2-SBA-15 drastically narrowed the substrate range (17 esters), to an extent much higher than ionically exchanged enzyme on the surface of magnetic micro-particles (up to 61 esters). This is attributed to differences in surface chemistry, particle size, and substrate accessibility to the active site tunnel. Our results also suggested, for the first time, that immobilization of enzymes in pores of similar size may alter the enzyme structures and produce enzyme active centers with different configuration which promote stereochemical conversions in a manner different to those arising from surface immobilization, where the strength of the ionic exchange also has an influence. This was shown by demonstrating that when the enzyme was introduced inside pores with a diameter (under dry conditions) slightly higher than that of the enzyme crystal structure a biocatalyst enantiospecific for ethyl (R)-4-chloro-3-hydroxybutyrate was produced, a feature not found when using wider pores. By contrast, immobilization on the surface of ferromagnetic microparticles produced selective biocatalysts for methyl (S)-(+)-mandelate or methyl (S)-lactate depending on the functionalization. This study illustrates the benefits of extensive analysis of the substrate spectra to better understand the effects of different immobilization strategies on enzyme flexibility/rigidity, as well as substrate specificity and stereochemistry. Our results will help to design tunable materials and interfaces for a controlled manipulation of specificity and to transform non-enantiospecific enzymes into stereo-chemically substrate promiscuous biocatalysts capable of converting multiple chiral molecules

Instructional Changes Adopted for an Engineering Course: Cluster Analysis on Academic Failure

As first-year students come from diverse backgrounds, basic skills should be accessible to everyone as soon as possible. Transferring such skills to these students is challenging, especially in highly technical courses. Ensuring that essential knowledge is acquired quickly promotes the student’s self-esteem and may positively influence failure rates. Metaphors can help do this. Metaphors are used to understand the unknown. This paper shows how we made a turn in student learning at the University of Almeria. Our hypothesis assumed that metaphors accelerate the acquisition of basic knowledge so that other skills built on that foundation are easily learned. With these goals in mind, we changed the way we teach by using metaphors and abstract concepts in a computer organisation course, a technical course in the first year of an information technology engineering degree. Cluster analysis of the data on collective student performance after this methodological change clearly identified two distinct groups. These two groups perfectly matched the before and after scenarios of the use of metaphors. The study was conducted during 11 academic years (2002/2003 to 2012/2013). The 475 observations made during this period illustrate the usefulness of this change in teaching and learning, shifting from a propositional teaching/learning model to a more dynamic model based on metaphors and abstractions. Data covering the whole period showed favourable evolution of student achievement and reduced failure rates, not only in this course, but also in many of the following more advanced courses.The paper is structured in five sections. The first gives an introduction, the second describes the methodology. The third section describes the sample and the study carried out. The fourth section presents the results and, finally, the fifth section discusses the main conclusions

Controlled manipulation of enzyme specificity through immobilization-induced flexibility constraints

It is thought that during immobilization enzymes, as dynamic biomolecules, may become distorted and this may alter their catalytic properties. However, the effects of different immobilization strategies on enzyme rigidity or flexibility and their consequences in specificity and stereochemistry at large scale has not been yet clearly evaluated and understood. This was here investigated by using as model an ester hydrolase, isolated from a bacterium inhabiting a karstic lake, with broad substrate spectrum (72 esters being converted; 61.5 U mg−1 for glyceryl tripropionate) but initially non-enantiospecific. We found that the enzyme (7 nm × 4.4 nm × 4.2 nm) could be efficiently ionic exchanged inside the pores (9.3 nm under dry conditions) of amino-functionalized ordered mesoporous material (NH2-SBA-15), achieving a protein load of 48 mg g−1, and a specific activity of 4.5 ± 0.1 U mg−1. When the enzyme was site-directed immobilized through His interaction with an immobilized cationon the surface of two types of magnetic micro-particles through hexahistidine-tags, protein loads up to 10.2 μg g−1 and specific activities of up to 29.9 ± 0.3 U mg−1, were obtained. We found that ionically exchanged enzyme inside pores of NH2-SBA-15 drastically narrowed the substrate range (17 esters), to an extent much higher than ionically exchanged enzyme on the surface of magnetic micro-particles (up to 61 esters). This is attributed to differences in surface chemistry, particle size, and substrate accessibility to the active site tunnel. Our results also suggested, for the first time, that immobilization of enzymes in pores of similar size may alter the enzyme structures and produce enzyme active centers with different configuration which promote stereochemical conversions in a manner different to those arising from surface immobilization, where the strength of the ionic exchange also has an influence. This was shown by demonstrating that when the enzyme was introduced inside pores with a diameter (under dry conditions) slightly higher than that of the enzyme crystal structure a biocatalyst enantiospecific for ethyl (R)-4-chloro-3-hydroxybutyrate was produced, a feature not found when using wider pores. By contrast, immobilization on the surface of ferromagnetic microparticles produced selective biocatalysts for methyl (S)-(+)-mandelate or methyl (S)-lactate depending on the functionalization. This study illustrates the benefits of extensive analysis of the substrate spectra to better understand the effects of different immobilization strategies on enzyme flexibility/rigidity, as well as substrate specificity and stereochemistry. Our results will help to design tunable materials and interfaces for a controlled manipulation of specificity and to transform non-enantiospecific enzymes into stereo-chemically substrate promiscuous biocatalysts capable of converting multiple chiral molecules.This project received funding from the European Union’s Horizon 2020 research and innovation program Blue Growth: Unlockingthe potential of Seas and Oceans under grant agreement no. 634486 (project acronym INMARE). This research was also supported by the grants PCIN-2014-107 (within ERA NET IB2 grant nr. ERA-IB-14-030 - MetaCat), PCIN-2017-078 (within the ERA-MarineBiotech grant ProBone), BIO2014-54494-R, MAT2016-77496-R, BIO2017-85522-R, and CTQ2016-79138-R from the Spanish Ministry of Economy, Industry and Competitiveness. A.B. acknowledges the support from the Spanish Ministry of Economy, Industry and Competitiveness (MAT2017-88808-R grant), María de Maeztu Units of Excellence Programme (MDM-2016-0618), and the Diputación de Guipúzcoa for current funding in the frame of Gipuzkoa Fellows program. G.D. thanks the German Federal Ministry of Education and Research (BMBF, Grant No. 031A095C) for funding in the frame of the Molecular Interaction Engineering program (Biotechnologie 2020+). The authors gratefully acknowledge financial support provided by the European Regional Development Fund (ERDF). C.C. thanks the Spanish Ministry of Economy, Industry and Competitiveness for a PhD fellowship (Grant BES-2015-073829).Peer ReviewedPostprint (published version

Dust properties of Lyman break galaxies at z∼3z\sim3

We explore from a statistical point of view the far-infrared (far-IR) and sub-millimeter (sub-mm) properties of a large sample of LBGs (22,000) at z~3 in the COSMOS field. The large number of galaxies allows us to split it in several bins as a function of UV luminosity, UV slope, and stellar mass to better sample their variety. We perform stacking analysis in PACS (100 and 160 um), SPIRE (250, 350 and 500 um) and AzTEC (1.1 mm) images. Our stacking procedure corrects the biases induced by galaxy clustering and incompleteness of our input catalogue in dense regions. We obtain the full IR spectral energy distributions (SED) of subsamples of LBGs and derive the mean IR luminosity as a function of UV luminosity, UV slope, and stellar mass. The average IRX is roughly constant over the UV luminosity range, with a mean of 7.9 (1.8 mag). However, it is correlated with UV slope, and stellar mass. We investigate using a statistically-controlled stacking analysis as a function of (stellar mass, UV slope) the dispersion of the IRX-UVslope and IRX-M* plane. Our results enable us to study the average relation between star-formation rate (SFR) and stellar mass, and we show that our LBG sample lies on the main sequence of star formation at z~3.Comment: Accepted to A&A, 17 Pages, 14 Figures, 2 Table

Multiwavelength characterisation of an ACT-selected, lensed dusty star-forming galaxy at z=2.64

We present \ci\,(2--1) and multi-transition $^{12}$CO observations of a dusty star-forming galaxy, ACT\,J2029+0120, which we spectroscopically confirm to lie at $z$\,=\,2.64. We detect CO(3--2), CO(5--4), CO(7--6), CO(8--7), and \ci\,(2--1) at high significance, tentatively detect HCO$^{+}$(4--3), and place strong upper limits on the integrated strength of dense gas tracers (HCN(4--3) and CS(7--6)). Multi-transition CO observations and dense gas tracers can provide valuable constraints on the molecular gas content and excitation conditions in high-redshift galaxies. We therefore use this unique data set to construct a CO spectral line energy distribution (SLED) of the source, which is most consistent with that of a ULIRG/Seyfert or QSO host object in the taxonomy of the \textit{Herschel} Comprehensive ULIRG Emission Survey. We employ RADEX models to fit the peak of the CO SLED, inferring a temperature of T$\sim$117 K and $n_{\text{H}_2}\sim10^5$ cm$^{-3}$, most consistent with a ULIRG/QSO object and the presence of high density tracers. We also find that the velocity width of the \ci\ line is potentially larger than seen in all CO transitions for this object, and that the $L'_{\rm C\,I(2-1)}/L'_{\rm CO(3-2)}$ ratio is also larger than seen in other lensed and unlensed submillimeter galaxies and QSO hosts; if confirmed, this anomaly could be an effect of differential lensing of a shocked molecular outflow.Comment: Accepted for publication in Ap

Reactivity of TpMe2-containing hydride-iridafurans with alkenes, alkynes, and H2

The TpMe2-containing hydride-iridafurans 2a,b (TpMe2 = hydrotris(3,5-dimethylpyrazolyl)borate) cleanly reacted with ethylene to give the bicyclic derivatives 6a,b. Formation of the latter complexes is a reversible process, and it is proposed to occur by an electrocyclic ring closure that takes place between C2H4 and the 16e unsaturated intermediates A, resulting from hydride migration to the α carbon of the metallacycle. Similar reactions were observed with a variety of alkynes RC≡CR (R = H, Ph, CO2Me) and R′C≡CH (R′= CO2Me, Ph, CMe3), with the regioselectivity observed for the latter substrates depending on the nature of R′. In the case of Me3SiC≡CH the structure of an unexpected byproduct indicates that an alkyne–vinylidene rearrangement has taken place on the metal coordination sphere during the reaction, and this observation suggests that in the mechanism of all these coupling processes the corresponding π adducts are active intermediates. Finally, complexes 2a,b reacted with H2 to give products derived from the hydrogenation of their alkenyl arms.Ministerio de Ciencia e Innovación CTQ2010-17476. Consolider Ingenio 2010 CSD 2007-0006Junta de Andalucía FQM-119, P09-FQM-483

Influence of Thickness on the Holographic Parameters of H-PDLC Materials

For photopolymers the compound concentrations and final thickness of the sample should be known in order to model hologram formation and introduce the reaction-diffusion kinetics of the monomer-polymer system. In principle the cell thickness can be controlled by bead spacers between the two pieces of ITO glass. In this paper we report a study of the influence of thickness on the holographic properties of this type of materials. To fit the physical and optical thickness of the samples we used the rigorous coupled wave analysis assuming an exponential decay in the refractive index modulation

Influence of Thickness on the Holographic Parameters of H-PDLC Materials

For photopolymers the compound concentrations and final thickness of the sample should be known in order to model hologram formation and introduce the reaction-diffusion kinetics of the monomer-polymer system. In principle the cell thickness can be controlled by bead spacers between the two pieces of ITO glass. In this paper we report a study of the influence of thickness on the holographic properties of this type of materials. To fit the physical and optical thickness of the samples we used the rigorous coupled wave analysis assuming an exponential decay in the refractive index modulation