Efficient C(sp³)−H Carbonylation of Light and Heavy Hydrocarbons with Carbon Monoxide via Hydrogen Atom Transfer Photocatalysis in Flow

Despite their abundance in organic molecules, considerable limitations still exist in synthetic methods that target the direct C−H functionalization at sp3-hybridized carbon atoms. This is even more the case for light alkanes, which bear some of the strongest C−H bonds known in Nature, requiring extreme activation conditions that are not tolerant to most organic molecules. To bypass these issues, synthetic chemists rely on prefunctionalized alkyl halides or organometallic coupling partners. However, new synthetic methods that target regioselectively C−H bonds in a variety of different organic scaffolds would be of great added value, not only for the late-stage functionalization of biologically active molecules but also for the catalytic upgrading of cheap and abundant hydrocarbon feedstocks. Here, we describe a general, mild and scalable protocol which enables the direct C(sp3)−H carbonylation of saturated hydrocarbons, including natural products and light alkanes, using photocatalytic hydrogen atom transfer (HAT) and gaseous carbon monoxide (CO). Flow technology was deemed crucial to enable high gas-liquid mass transfer rates and fast reaction kinetics, needed to outpace deleterious reaction pathways, but also to leverage a scalable and safe process.</p

Theoretical understanding of the increment of upon protonation of pyridine peripheral octupolar molecules: Toward nonlinear optical sensors

6 pages, 6 tables, 4 figures.In this article, we present a computational study of the nonlinear optical properties of pyridine-based octupolar molecules in their neutral and fully triprotonated states. The effect of the core substitution and the degree of conjugation with the periphery has been also established and confirms the possibility of fine-tuning the nonlinear optical response. Computations involving the time-dependent density-functional theory approach serve to further explore the existence of excited states with nonzero dipole moment. From these results, the origin of the high second-order nonlinear optical activity upon protonation is addressed.The present work was supported in part by the Dirección General de Enseñanza Superior DGES, MEC, Spain through research Project Nos. CTQ2006-14987-C02-01 and CTQ2005-01368. The authors are also indebted to Junta de Andalucía and Gobierno de Aragón Spain for funding their research groups FQM-0159 and E39. M.C.R.D. is grateful to the MEC/Fulbright for her Postdoctoral Fellowship at the Georgia Institute of Techology. J.C. is grateful to the MEC of Spain for an I3 professorship position of Chemistry at the University of Málaga and M.M.O. acknowledges the MEC for a personal grant.Peer reviewe

Dual role of benzophenone enables a fast and scalable C-4 selective alkylation of pyridines in flow

The efficient C-4 selective modification of pyridines is a major challenge for the synthetic community. Current strategies are plagued with at least one drawback regarding functional group-tolerant electronic activation of the heteroarene, mild generation of the required alkyl radicals, regioselectivity, safety and/or scalability. Herein, we describe a fast, safe and scalable flow process which allows preparation of said C-4 alkylated pyridines. The process involves a photochemical hydrogen atom transfer (HAT) event to generate the carbon-centered radicals needed to alkylate the C-2 blocked pyridine. In a two-step streamlined flow process, this light-mediated alkylation step is combined with a nearly instantaneous inline removal of the blocking group. Notably, cheap benzophenone plays a dual role in the pyridine alkylation mechanism by activating the hydrocarbon feedstock reagents via a HAT mechanism, and by acting as a benign, terminal oxidant. The key role of benzophenone in the operative reaction mechanism has also been revealed through a combination of experimental and computational studies

Optical performance of the JWST MIRI flight model: characterization of the point spread function at high-resolution

The Mid Infra Red Instrument (MIRI) is one of the four instruments onboard the James Webb Space Telescope (JWST), providing imaging, coronagraphy and spectroscopy over the 5-28 microns band. To verify the optical performance of the instrument, extensive tests were performed at CEA on the flight model (FM) of the Mid-InfraRed IMager (MIRIM) at cryogenic temperatures and in the infrared. This paper reports on the point spread function (PSF) measurements at 5.6 microns, the shortest operating wavelength for imaging. At 5.6 microns the PSF is not Nyquist-sampled, so we use am original technique that combines a microscanning measurement strategy with a deconvolution algorithm to obtain an over-resolved MIRIM PSF. The microscanning consists in a sub-pixel scan of a point source on the focal plane. A data inversion method is used to reconstruct PSF images that are over-resolved by a factor of 7 compared to the native resolution of MIRI. We show that the FWHM of the high-resolution PSFs were 5-10% wider than that obtained with Zemax simulations. The main cause was identified as an out-of-specification tilt of the M4 mirror. After correction, two additional test campaigns were carried out, and we show that the shape of the PSF is conform to expectations. The FWHM of the PSFs are 0.18-0.20 arcsec, in agreement with simulations. 56.1-59.2% of the total encircled energy (normalized to a 5 arcsec radius) is contained within the first dark Airy ring, over the whole field of view. At longer wavelengths (7.7-25.5 microns), this percentage is 57-68%. MIRIM is thus compliant with the optical quality requirements. This characterization of the MIRIM PSF, as well as the deconvolution method presented here, are of particular importance, not only for the verification of the optical quality and the MIRI calibration, but also for scientific applications.Comment: 13 pages, submitted to SPIE Proceedings vol. 7731, Space Telescopes and Instrumentation 2010: Optical, Infrared, and Millimeter Wav

Interfacing single-atom catalysis with continuous-flow organic electrosynthesis

The global warming crisis has sparked a series of environmentally cautious trends in chemistry, allowing us to rethink the way we conduct our synthesis, and to incorporate more earth-abundant materials in our catalyst design. “Single-atom catalysis” has recently appeared on the catalytic spectrum, and has truly merged the benefits that homogeneous and heterogeneous analogues have to offer. Further still, the possibility to activate these catalysts by means of a suitable electric potential could pave the way for a true integration of diverse synthetic methodologies and renewable electricity. Despite their esteemed benefits, single-atom electrocatalysts are still limited to the energy sector (hydrogen evolution reaction, oxygen reduction, etc.) and numerous examples in the literature still invoke the use of precious metals (Pd, Pt, Ir, etc.). Additionally, batch electroreactors are employed, which limit the intensification of such processes. It is of paramount importance that the field continues to grow in a more sustainable direction, seeking new ventures into the space of organic electrosynthesis and flow electroreactor technologies. In this piece, we discuss some of the progress being made with earth abundant homogeneous and heterogeneous electrocatalysts and flow electrochemistry, within the context of organic electrosynthesis, and highlight the prospects of alternatively utilizing single-atom catalysts for such applications

D-π-A compounds with tunable intramolecular charge transfer achieved by incorporation of butenolide nitriles as acceptor moieties

Chromophores where a polyenic spacer separates a 4H-pyranylidene or benzothiazolylidene donor and three different butenolide nitriles have been synthesized and characterized. The role of 2(5H)-furanones as acceptor units on the polarization and the second-order nonlinear (NLO) properties has been studied. Thus, their incorporation gives rise to moderately polarized structures with NLO responses that compare favorably to those of related compounds featuring more efficient electron-withdrawing moieties. Derivatives of the proaromatic butenolide PhFu show the best nonlinearities. Benzothiazolylidene-containing chromophores present less alternated structures than their pyranylidene analogues, and, unlike most merocyanines, the degree of charge transfer does not decrease on lengthening the π-bridge.Financial support from MICINN-FEDER (CTQ2011-22727 and MAT2011-27978- C02-02), MINECO (CTQ2014-52331R), and Gobierno de Aragon-Fondo Social Europeo (E39 and E04) is gratefully acknowledged. Research at the Universidad de Malaga was supported by MINECO (CTQ2012-33733) and Junta de Andalucıa (P09-4708).Peer Reviewe

The success of Quercus ilex plantations in agricultural fields in eastern Spain

Twenty-five years after planting, we measured the survival, growth and reproduction of 153 Quercus ilex plantations promoted by the afforestation programme of the European Union’s Common Agricultural Policy in agricultural fields in the east of the Iberian Peninsula, as a function of climatic aridity and stand characteristics related to water supply and competition among trees for water. Using field sampling, we found that, on average, 80% of the trees in plantations survived, more than 55% had already produced acorns and the tallest tree in each field exceeded 4 m, which are all higher values than those reported for forest plantations of this species in the same area and which represent the overcoming of the limitations imposed by climatic aridity on the natural regeneration of the species. A small proportion of the variation in all success variables was explained by water-related plantation characteristics, such as planting density, drought intensity in the year after planting, and soil permeability. However, climatic aridity only influenced the proportion of reproductive trees, but not the other variables of plantation success. However, most of the variation in planting success variables was linked to who owned the field, which nursery produced the seedlings, and the year of planting. Our results support the idea that the deep soils of agricultural fields counteract the negative effect of climatic aridity on plant performance, but that it is necessary to standardise nursery and planting practices, adapt planting density to the environmental characteristics of the site and provide irrigation supply in the early years to ensure the success of future plantations

Diquat Derivatives: Highly Active, Two-Dimensional Nonlinear Optical Chromophores with Potential Redox Switchability

In this article, we present a detailed study of structure−activity relationships in diquaternized 2,2′-bipyridyl (diquat) derivatives. Sixteen new chromophores have been synthesized, with variations in the amino electron donor substituents, π-conjugated bridge, and alkyl diquaternizing unit. Our aim is to combine very large, two-dimensional (2D) quadratic nonlinear optical (NLO) responses with reversible redox chemistry. The chromophores have been characterized as their PF_6^− salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. Their visible absorption spectra are dominated by intense π → π^* intramolecular charge-transfer (ICT) bands, and all show two reversible diquat-based reductions. First hyperpolarizabilities β have been measured by using hyper-Rayleigh scattering with an 800 nm laser, and Stark spectroscopy of the ICT bands affords estimated static first hyperpolarizabilities β_0. The directly and indirectly derived β values are large and increase with the extent of π-conjugation and electron donor strength. Extending the quaternizing alkyl linkage always increases the ICT energy and decreases the E_(1/2) values for diquat reduction, but a compensating increase in the ICT intensity prevents significant decreases in Stark-based β_0 responses. Nine single-crystal X-ray structures have also been obtained. Time-dependent density functional theory clarifies the molecular electronic/optical properties, and finite field calculations agree with polarized HRS data in that the NLO responses of the disubstituted species are dominated by ‘off-diagonal’ β_(zyy) components. The most significant findings of these studies are: (i) β_0 values as much as 6 times that of the chromophore in the technologically important material (E)-4′-(dimethylamino)-N-methyl-4-stilbazolium tosylate; (ii) reversible electrochemistry that offers potential for redox-switching of optical properties over multiple states; (iii) strongly 2D NLO responses that may be exploited for novel practical applications; (iv) a new polar material, suitable for bulk NLO behavior

Precise measurement of the top quark mass in the dilepton channel at D0

We measure the top quark mass (mt) in ppbar collisions at a center of mass energy of 1.96 TeV using dilepton ttbar->W+bW-bbar->l+nubl-nubarbbar events, where l denotes an electron, a muon, or a tau that decays leptonically. The data correspond to an integrated luminosity of 5.4 fb-1 collected with the D0 detector at the Fermilab Tevatron Collider. We obtain mt = 174.0 +- 1.8(stat) +- 2.4(syst) GeV, which is in agreement with the current world average mt = 173.3 +- 1.1 GeV. This is currently the most precise measurement of mt in the dilepton channel.Comment: 7 pages, 4 figure