Evolution in the field of the total synthesis of natural products has led to exciting developments over the last decade. Numerous chemoselective and enantioselective methodologies have emerged from ...total syntheses, resulting in efficient access to many important natural product targets. This Review highlights recent developments concerning dearomatization, a powerful strategy for the total synthesis of architecturally complex natural products wherein planar, aromatic scaffolds are converted to three‐dimensional molecular architectures.
1, 2, …︁ 3 dearomaticity: The conversion of planar, aromatic scaffolds (arenes, phenols, and heteroarenes) into three‐dimensional molecular architectures is a powerful strategy for the total synthesis of complex natural products. This Review highlights recent developments and outlines future perspectives and opportunities for catalytic, enantioselective dearomatization processes.
A biomimetic semisynthesis of the diterpenoid (+)-providencin (2) and the unexpected novel C14 regioisomer 3 was achieved by photoirradiation of the proposed biosynthetic cembranoid precursor ...(−)-bipinnatin E (1). The absolute configuration assignments of 1 and 2 by correlation were established by X-ray analysis. A combination of NOESY data and photochemical reaction results revealed that both C2 and C14 positions of the macrocycle (−)-1 are suitable for hydrogen abstraction, thus affording an explanation to the mixture of cyclobutane photoproduct isomers obtained by a Norrish–Yang cyclization. These results also support the proposed biosynthetic hypothesis describing the genuine photochemical transformation of (−)-1 into (+)-2, without refuting that both regioisomer products 2/3 might be artifacts of isolation.
The on-demand generation of pure quantum excitations is important for the operation of quantum systems, but it is particularly difficult for a system of fermions. This is because any perturbation ...affects all states below the Fermi energy, resulting in a complex superposition of particle and hole excitations. However, it was predicted nearly 20 years ago that a Lorentzian time-dependent potential with quantized flux generates a minimal excitation with only one particle and no hole. Here we report that such quasiparticles (hereafter termed levitons) can be generated on demand in a conductor by applying voltage pulses to a contact. Partitioning the excitations with an electronic beam splitter generates a current noise that we use to measure their number. Minimal-excitation states are observed for Lorentzian pulses, whereas for other pulse shapes there are significant contributions from holes. Further identification of levitons is provided in the energy domain with shot-noise spectroscopy, and in the time domain with electronic Hong-Ou-Mandel noise correlations. The latter, obtained by colliding synchronized levitons on a beam splitter, exemplifies the potential use of levitons for quantum information: using linear electron quantum optics in ballistic conductors, it is possible to imagine flying-qubit operation in which the Fermi statistics are exploited to entangle synchronized electrons emitted by distinct sources. Compared with electron sources based on quantum dots, the generation of levitons does not require delicate nanolithography, considerably simplifying the circuitry for scalability. Levitons are not limited to carrying a single charge, and so in a broader context n-particle levitons could find application in the study of full electron counting statistics. But they can also carry a fraction of charge if they are implemented in Luttinger liquids or in fractional quantum Hall edge channels; this allows the study of Abelian and non-Abelian quasiparticles in the time domain. Finally, the generation technique could be applied to cold atomic gases, leading to the possibility of atomic levitons.
Celotno besedilo
Dostopno za:
DOBA, IJS, IZUM, KILJ, KISLJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
The ribosome is centrally situated to sense metabolic states, but whether its activity, in turn, coherently rewires transcriptional responses is unknown. Here, through integrated chemical-genetic ...analyses, we found that a dominant transcriptional effect of blocking protein translation in cancer cells was inactivation of heat shock factor 1 (HSF1), a multifaceted transcriptional regulator of the heat-shock response and many other cellular processes essential for anabolic metabolism, cellular proliferation, and tumorigenesis. These analyses linked translational flux to the regulation of HSF1 transcriptional activity and to the modulation of energy metabolism. Targeting this link with translation initiation inhibitors such as rocaglates deprived cancer cells of their energy and chaperone armamentarium and selectively impaired the proliferation of both malignant and premalignant cells with early-stage oncogenic lesions.
ALMA observations have revealed nuclear dusty molecular disks or tori with characteristic sizes 15−40 pc in the few Seyferts and low -luminosity AGN that have been studied so far. These structures ...are generally decoupled both morphologically and kinematically from the host galaxy disk. We present ALMA observations of the CO(2–1) and CO(3–2) molecular gas transitions and associated (sub-) millimeter continua of the nearby Seyfert 1.5 galaxy NGC 3227 with angular resolutions 0.085 − 0.21″ (7–15 pc). On large scales, the cold molecular gas shows circular motions as well as streaming motions on scales of a few hundred parsecs that are associated with a large-scale bar. We fit the nuclear ALMA 1.3 mm emission with an unresolved component and an extended component. The 850 μm emission shows at least two extended components, one along the major axis of the nuclear disk, and the other along the axis of the ionization cone. The molecular gas in the central region (1″ ∼ 73 pc) shows several CO clumps with complex kinematics that appears to be dominated by noncircular motions. While we cannot conclusively demonstrate the presence of a warped nuclear disk, we also detected noncircular motions along the kinematic minor axis. They reach line-of-sight velocities of v − vsys = 150 − 200 km s−1. Assuming that the radial motions are in the plane of the galaxy, we interpret them as a nuclear molecular outflow due to molecular gas in the host galaxy that is entrained by the AGN wind. We derive molecular outflow rates of 5 M⊙ yr−1 and 0.6 M⊙ yr−1 at projected distances of up to 30 pc to the northeast and southwest of the AGN, respectively. At the AGN location we estimate a mass in molecular gas of 5 × 105 M⊙ and an equivalent average column density N(H2) = 2 − 3 × 1023 cm−2 in the inner 15 pc. The nuclear CO(2–1) and CO(3–2) molecular gas and submillimeter continuum emission of NGC 3227 do not resemble the classical compact torus. Rather, these emissions extend for several tens of parsecs and appear connected with the circumnuclear ring in the host galaxy disk, as found in other local AGN.
We report a chiral-squaramide-catalyzed enantio- and diastereoselective synthesis of α-allyl amino esters. The optimized protocol provides access to N-carbamoyl-protected amino esters via ...nucleophilic allylation of readily accessible α-chloro glycinates. A variety of useful α-allyl amino esters were prepared, including crotylated products bearing vicinal stereocenters that are inaccessible through enolate alkylation, with high enantioselectivity (up to 97% ee) and diastereoselectivity (>10:1). The reactions display first-order kinetic dependence on both the α-chloro glycinate and the nucleophile, consistent with rate-limiting C–C bond formation. Computational analysis of the uncatalyzed reaction predicts an energetically inaccessible iminium intermediate, and a lower energy concerted SN2 mechanism.
ABSTRACT
Polycyclic Aromatic Hydrocarbons (PAHs) are carbon-based molecules resulting from the union of aromatic rings and related species, which are likely responsible for strong infrared emission ...features. In this work, using a sample of 50 Seyfert galaxies (DL < 100 Mpc) we compare the circumnuclear (inner kpc) PAH emission of AGN to that of a control sample of star-forming galaxies (22 luminous infrared galaxies and 30 H ii galaxies), and investigate the differences between central and extended PAH emission. Using Spitzer/InfraRed Spectrograph spectral data of Seyfert and star-forming galaxies and newly developed PAH diagnostic model grids, derived from theoretical spectra, we compare the predicted and observed PAH ratios. We find that star-forming galaxies and AGN-dominated systems are located in different regions of the PAH diagnostic diagrams. This suggests that not only are the size and charge of the PAH molecules different, but also the nature and hardness of the radiation field that excite them. We find tentative evidence that PAH ratios in AGN-dominated systems are consistent with emission from larger PAH molecules (Nc > 300–400) as well as neutral species. By subtracting the spectrum of the central source from the total, we compare the PAH emission in the central versus extended region of a small sample of AGN. In contrast to the findings for the central regions of AGN-dominated systems, the PAH ratios measured in the extended regions of both type 1 and type 2 Seyfert galaxies can be explained assuming similar PAH molecular size distribution and ionized fractions of molecules to those seen in central regions of star-forming galaxies (100 < Nc < 300).
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