Flindtlauesen3226

A simple protocol for the protection of amines was realized through a base-catalyzed one-pot reaction of dimedone, β-nitroalkene, and amine. Employing this strategy, a variety of amines/amino acids were protected in excellent yields. These acid/base stable protected amines can be deprotected by either ethylene diamine or hydrazine hydrate under mild conditions. The practical application of this orthogonal protecting group was demonstrated by the synthesis of cyclic peptide melanotan II via SPPS.Single crystals represent a benchmark for understanding the bulk properties of halide perovskites. We have indeed studied the dielectric function of lead bromide perovskite single crystals (MAPbBr3, CsPbBr3 and for the first time FAPbBr3) by spectroscopic ellipsometry in the range of 1-5 eV while varying the temperature from 183 to 440 K. An extremely low absorption coefficient in the sub-band gap region was found, indicating the high optical quality of all three crystals. We extracted the band gap values through critical point analysis showing that Tauc-based values are systematically underestimated. Kartogenin The two structural phase transitions, i.e., orthorhombic-tetragonal and tetragonal-cubic, show distinct optical behaviors, with the former having a discontinuous character. The cross-correlation of optical data with DFT calculations evidences the role of octahedral tilting in tailoring the value of the band gap at a given temperature, whereas differences in the thermal expansion affect the slope of the band gap trend as a function of temperature.A photoredox Ni-catalyzed cross-coupling of N-acyl-imides with unactivated alkyl bromides has been developed that enables efficient access to a variety of functionalized alkyl ketones, including unsymmetrical dialkyl ketones, under very mild and operationally practical conditions. The reaction that operates without the need for any preformed carbon nucleophile proceeds via the combination of two different bond activation processes, i.e. Ni-catalyzed imide activation via C(acyl)-N bond cleavage and (TMS)3Si radical-mediated alkyl halide activation via halogen-atom abstraction.Organic fluorescent nanoparticles (FNPs) have become increasingly prevalent in a variety of applications but the creation of organic FNPs using a simple procedure and that possess diverse morphology, multicolor luminescence, and high brightness has been challenging. Herein, a facile strategy to prepare this class of organic FNPs is established by way of preformed organic nanoparticles themselves. It was found that as long as the nanoparticles contained aromatic/heterocyclic rings in their base unit and regardless of morphologies (e.g., small-molecule micelles, polymeric micelles, reverse micelles, solid microspheres, and vesicles), simple UV irradiation can result in the particles exhibiting excitation-wavelength-dependent photoluminescence with considerable quantum yields (∼8.3-16.7% for tested particles). Upon initial investigation of the mechanism, the photoluminescence behavior was attributed to a polycyclic aromatic hydrocarbon (PAH) process. Furthermore, the application of the synthesized organic FNPs in cancer cell imaging is demonstrated as just one of the many potential applications. The straightforward method to supply preformed organic nanoparticles with photoluminescence would be attractive for scientists in both academia and industry.The addition of Mg2+ is found to turn on the fluorescence response of a molecular probe, 3,3'-diformyl-1,1'-bi-2-naphthol, toward chiral amino acids with high enantioselectivity. It is further found that the enantioselective fluorescence responses of the molecular probe in the presence of Mg2+ toward certain amino acids are the opposite of those in the presence of Zn2+, that is, using Mg2+ with an l-amino acid generates much greater fluorescence enhancement than with the corresponding d-amino acid, but using Zn2+ with the d-amino acid gives much greater fluorescence than with the l-enantiomer. Thus, simply changing the metal cation additive allows the chirality sense of the fluorescence-based molecular recognition to be easily regulated.This article addresses the non-Debye-Waller temperature behavior in the intermediate range order for molten MgCl2 and its mixtures with KCl from a theory, Molecular Dynamics, and experimental X-ray scattering perspective and puts these findings in the context of discussions and controversies extending at least four decades. We find that these liquids are defined by two structural motifs. The first motif is associated with chains of positive-negative charge alternation; the second motif, which results in a prepeak in the structure function S(q), is associated with the interaction of Mg2+ and Cl- ions that do not belong to the same charge alternation chain or aggregate. Our complementary X-ray scattering and computational results provide a quantitative explanation for the increase in intensity of the prepeak with temperature as opposed to the behavior of other peaks following normal Debye-Waller behavior. Temperature has opposite effects on the prevalence of each of the two structural motifs, and the enhancement of one pattern appears to be at the detriment of the other. Whereas the intensity in S(q) associated with the charge alternation motif is diminished at higher temperature, the opposite is true for the prepeak associated with intermediate range order due to the second structural motif.This critical appraisal is intended for users of the dimolybdenum method, well-established in electronic circular dichroism (ECD) to determine the absolute configuration of vic-diols and, in particular, for experimental researchers not being experts in chiroptical methods. The main goal is to demonstrate how to avoid misleading and ambiguous conclusions resulting from the rigorous application of the helicity rule by limiting the analysis to the vic-diol unit alone. We particularly focused on multichromophoric systems, especially those that may interfere with the absorption of an in situ formed dimolybdenum tetraacetate-diol complex. In this context, examples are presented of vic-diols for which stereochemical assignment based solely on the helicity rule is ambiguous and does not necessarily lead to correct results. The motivation for choosing these examples was to demonstrate the impact of the structure of the substrate on the complexation process with the metal core and its selectivity. For each selected case, results obtained are analyzed in detail together with a discussion of existing restrictions and choice of a support method to increase the credibility of the conclusion.