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  • Levy Buck posted an update 1 week ago

    Fmoc-FV self-assembly in physiologic conditions resulted in a thermo-sensitive and shear-thinning hydrogel. Notably, the Fmoc-FV hydrogel exhibited cell type-dependent biological activity, so higher cell proliferation was attained in HUVEC or MDA-MB231 cells than WJ-MSCs, indicating a possible need for incorporating cell-adhesion ligands in the Fmoc-FV hydrogel matrix. Therefore, the structural and biological properties of the Fmoc-dipeptide hydrogels are inter-related and can affect their applications in 3D cell culture and regenerative medicine.An efficient asymmetric vinylogous aldol/lactonization cascade reaction between β,γ-unsaturated amides and trifluoromethyl ketones has been developed. Using a chiral cyclohexanediamine-based tertiary amine-thiourea catalyst, optically active trifluoromethyl dihydropyranones have been constructed in moderate-to-excellent yields (up to 99%) with excellent stereoselectivities (96-> 99.5% ee).Recent examples of organic synthesis of fine chemicals and pharmaceuticals in confined spaces of MOFs are highlighted and compared with silica-based ordered porous solids, such as zeolites or mesoporous (organo)silica. These heterogeneous catalysts offer the possibility of stabilizing the desired transition states and/or intermediates during organic transformations of functional groups and (C-C/C-N) bond forming steps towards the desired functional high added value molecular scaffolds. A short introduction on zeolites, mesoporous silica and metal-organic frameworks is followed by relevant applications in which confined active sites in the pores promote single or multi-step organic synthesis of industrially relevant molecules. A critical discussion on the catalytic performances of the different types of hybrid inorganic-organic catalysts in the synthesis of O- and N-containing acyclic and heterocyclic molecules has been presented.The intriguing properties of magnetic nanoparticles have sparked a growing number of theoretical studies as well as practical applications. Here, we provide the first comprehensive study of the influence of interactions on the two main relaxation mechanisms internal (Néel) and Brownian relaxation. While non-interacting magnetic nanoparticles show Debye behavior with an effective relaxation time, many authors use this model also for the interacting case. Since Néel relaxation is typically a thermally activated process on times scales that are many orders of magnitude larger than the underlying micromagnetic times, we use extensive computer simulations employing a Brownian dynamics/Monte-Carlo algorithm to show that dipolar interactions lead to significant deviations from the Debye behavior. We find that Néel and Brownian relaxation can be considered as independent processes for short enough times until dipolar interactions lead to a coupling of these mechanisms, making the interpretation more difficult. We provide mean-field arguments that describe these short and long-time, effective relaxation times well for weak up to moderate interaction strengths. Our findings about the coupling of Brownian and Néel process and the effective relaxation time provide an important theoretical insight that will have also important consequences for the interpretation of magnetic susceptibility measurements and magnetorelaxometry analysis.A Pd(ii)-catalysed direct desulfitative arylation was realized at the C6-position of the 2-pyridone scaffold. Aryl sulfonyl chloride was used as an alternative arylating agent. The required site-selectivity occurred without the strategic installation of a heteroatom containing directing group. Preliminary mechanistic studies revealed that radical species were involved during this process.A new series of molecules bearing a 2,11-dihydro-1H-cyclopenta[de]indeno[1,2-b]quinoline (CPIQ) chromophore with the N-HN type of intramolecular hydrogen bond are strategically designed and synthesized, among which CPIQ-OH, CPIQ-NHAc and CPIQ-NHTs in solution exhibit a single emission band with an anomalously large Stokes shift, whereas CPIQ-NH2 and CPIQ-NHMe show apparent dual-emission property. This, in combination with time-resolved spectroscopy and the computational approach, leads us to conclude that CPIQ-OH, CPIQ-NHAc and CPIQ-NHTs undergo ultrafast, highly exergonic excited-state intramolecular proton transfer (ESIPT), while a finite rate of ESIPT is observed for CPIQ-NH2 and CPIQ-NHMe with a time constant of 117 ps and 39 ps, respectively, in acetonitrile at room-temperature. Further temperature-dependent studies deduce an appreciable ESIPT barrier for CPIQ-NH2 and CPIQ-NHMe. Different from most of the barrier associated ESIPT molecules that are commonly in the thermodynamic-control regime, i.e. found in the thermal pre-equilibrium between excited normal and proton-transfer tautomer states, CPIQ-NH2 and CPIQ-NHMe cases are in the kinetic-control regime where ESIPT is irreversible with a significant barrier. The barrier is able to be tuned by the electronic properties of the -R group in the NR-H proton donor site, resulting in ratiometric fluorescence for normal versus tautomer emission.A novel method for the Rh(iii)-catalyzed oxime-directed C-H amidation of indoles with dioxazolones has been developed. This strategy provides an exclusive site selectivity and the directing group can be easily removed. This transformation features a wide substrate scope, good functional group tolerance and excellent yields, and may serve as a significant tool to construct structurally diverse indole derivatives for the screening of potential pharmaceuticals in the future.We report an effective fluorescence in situ hybridization strategy, named l-DNA tagged FISH (LT-FISH), for highly sensitive RNA detection in fixed cultured cells. see more LT-FISH includes two-step hybridization processes with a l-d chimera oligonucleotide probe and a fluorescence-labeled PCR product tethering a l-DNA tag. The degree of fluorescence enhancement, depending on the length of PCR products, was up to 14-fold when the 606 bp product was used. Endogenous mRNA and miRNA in cancer cells were visualized by utilizing this l-DNA-mediated signal amplification technique.

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