A new chiral dirhodium tetracarboxylate catalyst, Rh2(S-2-Cl-5-BrTPCP)4, has been developed for C–H functionalization reactions by means of donor/acceptor carbene intermediates. The dirhodium ...catalyst contains four (S)-1-(2-chloro-5-bromophenyl)-2,2-diphenylcyclopropane-1-carboxylate ligands, in which all four 2-chloro-5-bromophenyl groups are on the same face of the catalyst, leading to a structure, which is close to C 4 symmetric. The catalyst induces highly site selective functionalization of remote, unactivated methylene C–H bonds even in the presence of electronically activated benzylic C–H bonds, which are typically favored using earlier established dirhodium catalysts, and the reactions proceed with high levels of diastereo- and enantioselectivity. This C–H functionalization method is applicable to a variety of aryl and heteroaryl derivatives. Furthermore, the potential of this methodology was illustrated by sequential C–H functionalization reactions to access the macrocyclic core of the cylindrocyclophane class of natural products.
A highly effective synthesis of 2,3-fused pyrroles from cyclic ketones has been achieved. The transformation includes a rhodium-catalyzed reaction of 4-alkenyl-1-sulfonyl-1,2,3-triazoles featuring an ...unusual 4π electrocyclization. The methodology was further extended to the synthesis of indoles using a one-pot reaction starting from 1-ethynylcyclohexenes.
C–H functionalization is a very active research field that has attracted the interest of scientists from many disciplines. This Outlook describes the collaborative efforts within the NSF CCI Center ...for Selective C–H Functionalization (CCHF) to develop catalyst-controlled selective methods to enhance the synthetic potential of C–H functionalization.
The synthesis of complex organic compounds usually relies on controlling the reactions of the functional groups. In recent years, it has become possible to carry out reactions directly on the C-H ...bonds, previously considered to be unreactive. One of the major challenges is to control the site-selectivity because most organic compounds have many similar C-H bonds. The most well developed procedures so far rely on the use of substrate control, in which the substrate has one inherently more reactive C-H bond or contains a directing group or the reaction is conducted intramolecularly so that a specific C-H bond is favoured. A more versatile but more challenging approach is to use catalysts to control which site in the substrate is functionalized. p450 enzymes exhibit C-H oxidation site-selectivity, in which the enzyme scaffold causes a specific C-H bond to be functionalized by placing it close to the iron-oxo haem complex. Several studies have aimed to emulate this enzymatic site-selectivity with designed transition-metal catalysts but it is difficult to achieve exceptionally high levels of site-selectivity. Recently, we reported a dirhodium catalyst for the site-selective functionalization of the most accessible non-activated (that is, not next to a functional group) secondary C-H bonds by means of rhodium-carbene-induced C-H insertion. Here we describe another dirhodium catalyst that has a very different reactivity profile. Instead of the secondary C-H bond, the new catalyst is capable of precise site-selectivity at the most accessible tertiary C-H bonds. Using this catalyst, we modify several natural products, including steroids and a vitamin E derivative, indicating the applicability of this method of synthesis to the late-stage functionalization of complex molecules. These studies show it is possible to achieve site-selectivity at different positions within a substrate simply by selecting the appropriate catalyst. We hope that this work will inspire the design of even more sophisticated catalysts, such that catalyst-controlled C-H functionalization becomes a broadly applied strategy for the synthesis of complex molecules.
In craniates, opsin‐based photopigments expressed in the eye encode molecular ‘light sensors’ that constitute the initial protein in photoreception and the activation of the phototransduction ...cascade. Since the cloning and sequencing of the first vertebrate opsin gene (bovine rod opsin) nearly 30 years ago (Ovchinnikov Yu 1982, FEBS Letters, 148, 179–191; Hargrave et al. 1983, Biophysics of Structure & Mechanism, 9, 235–244; Nathans & Hogness 1983, Cell, 34, 807–814), it is now well established that variation in the subtypes and spectral properties of the visual pigments that mediate colour and dim‐light vision is a prevalent mechanism for the molecular adaptation to diverse light environments. In this review, we discuss the origins and spectral tuning of photopigments that first arose in the agnathans to sample light within the ancient aquatic landscape of the Early Cambrian, detailing the molecular changes that subsequently occurred in each of the opsin classes independently within the main branches of extant jawed gnathostomes. Specifically, we discuss the adaptive changes that have occurred in the photoreceptors of craniates as they met the ecological challenges to survive in quite differing photic niches, including brightly lit aquatic surroundings; the deep sea; the transition to and from land; diurnal, crepuscular and nocturnal environments; and light‐restricted fossorial settings. The review ends with a discussion of the limitations inherent to the ‘nocturnal‐bottleneck’ hypothesis relevant to the evolution of the mammalian visual system and a proposition that transition through a ‘mesopic‐bottleneck’ may be a more appropriate model.
Optoelectronic properties are unraveled for formamidinium tin triiodide (FASnI3) thin films, whose background hole doping density is varied through SnF2 addition during film fabrication. ...Monomolecular charge‐carrier recombination exhibits both a dopant‐mediated part that grows linearly with hole doping density and remnant contributions that remain under tin‐enriched processing conditions. At hole densities near 1020 cm−3, a strong Burstein–Moss effect increases absorption onset energies by ≈300 meV beyond the bandgap energy of undoped FASnI3 (shown to be 1.2 eV at 5 K and 1.35 eV at room temperature). At very high doping densities (1020 cm−3), temperature‐dependent measurements indicate that the effective charge‐carrier mobility is suppressed through scattering with ionized dopants. Once the background hole concentration is nearer 1019 cm−3 and below, the charge‐carrier mobility increases with decreasing temperature according to ≈T−1.2, suggesting that it is limited mostly by intrinsic interactions with lattice vibrations. For the lowest doping concentration of 7.2 × 1018 cm−3, charge‐carrier mobilities reach a value of 67 cm2 V−1 s−1 at room temperature and 470 cm2 V−1 s−1 at 50 K. Intraexcitonic transitions observed in the THz‐frequency photoconductivity spectra at 5 K reveal an exciton binding energy of only 3.1 meV for FASnI3, in agreement with the low bandgap energy exhibited by this perovskite.
The absorption, photoluminescence, charge‐carrier dynamics, and mobility are investigated in FASnI3 thin films with hole doping densities ranging from 1018 to 1020 cm−3. Doping is found to limit charge recombination and transport only at the highest doping densities. At lower hole densities, FASnI3 displays many characteristics equal to or superior than those of lead‐based analogs and typical low‐bandgap inorganic semiconductors.
Abstract
We explore constraints on the joint photometric and morphological evolution of typical low redshift galaxies as they move from the blue cloud through the green valley and on to the red ...sequence. We select Galaxy And Mass Assembly (GAMA) survey galaxies with 10.25 < log(M*/M⊙) < 10.75 and z < 0.2 classified according to their intrinsic u* − r* colour. From single component Sérsic fits, we find that the stellar mass-sensitive K-band profiles of red and green galaxy populations are very similar while g-band profiles indicate more disc-like morphologies for the green galaxies: apparent (optical) morphological differences arise primarily from radial mass-to-light ratio variations. Two-component fits show that most green galaxies have significant bulge and disc components and that the blue to red evolution is driven by colour change in the disc. Together, these strongly suggest that galaxies evolve from blue to red through secular disc fading and that a strong bulge is present prior to any decline in star formation. The relative abundance of the green population implies a typical time-scale for traversing the green valley ∼1–2 Gyr and is independent of environment, unlike that of the red and blue populations. While environment likely plays a rôle in triggering the passage across the green valley, it appears to have little effect on time taken. These results are consistent with a green valley population dominated by (early type) disc galaxies that are insufficiently supplied with gas to maintain previous levels of disc star formation, eventually attaining passive colours. No single event is needed to quench their star formation.
We discuss the construction of the Galaxy And Mass Assembly (GAMA) 10h region (G10) using publicly available data in the Cosmic Evolution Survey region (COSMOS) in order to extend the GAMA survey to ...z ∼ 1 in a single deg2 field. In order to obtain the maximum number of high precision spectroscopic redshifts we re-reduce all archival zCOSMOS-bright data and use the GAMA automatic cross-correlation redshift fitting code autoz. We use all available redshift information (autoz, zCOSMOS-bright 10k, PRIMUS, VVDS, SDSS and photometric redshifts) to calculate robust best-fitting redshifts for all galaxies and visually inspect all 1D and 2D spectra to obtain 16 583 robust redshifts in the full COSMOS region. We then define the G10 region to be the central ∼1 deg2 of COSMOS, which has relatively high spectroscopic completeness, and encompasses the CHILES VLA region. We define a combined r < 23.0 mag and i < 22.0 mag G10 sample (selected to have the highest bijective overlap) with which to perform future analysis, containing 9861 sources with reliable high-precision VLT-VIMOS spectra. All tables, spectra and imaging are available at http://ict.icrar.org/cutout/G10.
ABSTRACT
We report on our combined analysis of HST, VLT/MUSE, VLT/SINFONI, and ALMA observations of the local Seyfert 2 galaxy, NGC 5728 to investigate in detail the feeding and feedback of the ...active galactic nucleus (AGN). The data sets simultaneously probe the morphology, excitation, and kinematics of the stars, ionized gas, and molecular gas over a large range of spatial scales (10 pc to 10 kpc). NGC 5728 contains a large stellar bar that is driving gas along prominent dust lanes to the inner 1 kpc where the gas settles into a circumnuclear ring. The ring is strongly star forming and contains a substantial population of young stars as indicated by the lowered stellar velocity dispersion and gas excitation consistent with H ii regions. We model the kinematics of the ring using the velocity field of the CO (2–1) emission and stars and find it is consistent with a rotating disc. The outer regions of the disc, where the dust lanes meet the ring, show signatures of inflow at a rate of 1 M$\odot$ yr−1. Inside the ring, we observe three molecular gas components corresponding to the circular rotation of the outer ring, a warped disc, and the nuclear stellar bar. The AGN is driving an ionized gas outflow that reaches a radius of 250 pc with a mass outflow rate of 0.08 M$\odot$ yr−1 consistent with its luminosity and scaling relations from previous studies. While we observe distinct holes in CO emission which could be signs of molecular gas removal, we find that largely the AGN is not disrupting the structure of the circumnuclear region.
Abstract
We investigate the relationship between star formation activity and outflow properties on kiloparsec scales in a sample of 28 star-forming galaxies at
z
∼ 2–2.6, using adaptive optics ...assisted integral field observations from SINFONI on the Very Large Telescope. The narrow and broad components of the H
α
emission are used to simultaneously determine the local star formation rate surface density (
), and the outflow velocity
and mass outflow rate
, respectively. We find clear evidence for faster outflows with larger mass loading factors at higher
. The outflow velocities scale as
∝
0.34±0.10
, which suggests that the outflows may be driven by a combination of mechanical energy released by supernova explosions and stellar winds, as well as radiation pressure acting on dust grains. The majority of the outflowing material does not have sufficient velocity to escape from the galaxy halos, but will likely be re-accreted and contribute to the chemical enrichment of the galaxies. In the highest
regions the outflow component contains an average of ∼45% of the H
α
flux, while in the lower
regions only ∼10% of the H
α
flux is associated with outflows. The mass loading factor,
η
=
/SFR, is positively correlated with
but is relatively low even at the highest
:
η
≲ 0.5 × (380 cm
−3
/
n
e
). This may be in tension with the
η
≳ 1 required by cosmological simulations, unless a significant fraction of the outflowing mass is in other gas phases and has sufficient velocity to escape the galaxy halos.
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