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The fully coordinated complex is predicted to be U+(N2)8, which has a cubic structure. The vibrational frequencies predicted by theory are consistently lower than those in the experiment, independent of the isomeric structure or spin state of the complexes. Despite its failure to reproduce the infrared spectra, theory provides an average U+-N2 dissociation energy of 11.8 ± 0.5 kcal/mol, in good agreement with the value from the experiments.Environmentally sensitive fluorescent amino acids (FlAAs) have been used extensively to probe biological interactions. However, most of these amino acids are large and do not resemble amino acid side chains. Here, we report the enantioselective synthesis of two small and environmentally sensitive fluorescent amino acids bearing 7-dialkylaminocoumarin side chains by alkylation of a Ni(II) glycine Schiff base complex. These amino acids exhibit a large increase in fluorescence as environment polarity decreases. One of these FLAAs was incorporated into a highly active analog of the cyclic lipopeptide antibiotic paenibacterin by Fmoc solid-phase peptide synthesis via a new and very efficient route. This peptide was used to probe the interaction of the antibiotic with model liposomes, lipopolysaccharides, and live bacteria.An improved procedure for the preparation of aerogel granules of polytetrafluoroethylene-graphene oxide (PTFE-GO) with a composition of 5050 (in wt %) and a specific density of 35 ± 2 mg/cm3 is described. The technique practically excludes the granule cracking. The specific density of the pellets after reduction using hydrazine vapor and annealing at 370 °C decreased to 29 ± 2 mg/cm3. The PTFE-reduced GO (rGO) pellets obtained were tested as a recyclable sorbent for isopropyl alcohol (IPA) in sorption/combustion cycles. It has been shown that the aerogel sorption capacity for IPA increases from 35.6 to 39.3 g/g as a result of alcohol burning off. During the combustion of IPA, the temperature of an individual pellet can exceed 300 °C. When several contingent pellets are burned, the temperature of their heating increases. The fine-pored structure of the near-surface layer of the granule is destroyed during the alcohol burning, the internal structure with larger pores is exposed, and the relative proportion of PTFE on the surface of the granules decreases. It was also shown that the specific surface area of PTFE-rGO increases from 26 to 49 m2/g during cycling.Gene therapy aims to treat patients by altering or controlling gene expression. The field of gene therapy has had increasing success in recent years primarily using viral-based approaches; however, there is still significant interest toward the use of polymeric materials due to their potential as flexible, low-cost scaffolds for gene delivery that do not suffer the mutagenesis and immunogenicity concerns of viral vectors. To address the challenges of efficiency and biocompatibility, a series of zwitterion-like polyethylenimine derivatives (zPEIs) were produced via the succinylation of 2-11.5% of polyethylenimine (PEI) amines. With increasing modification, zPEI polyplexes exhibited decreased serum-protein aggregation and dissociated more easily in the presence of a competitor polyanion when compared to unmodified PEI. Surprisingly, the gene delivery mediated in the presence of serum showed that succinylation of as few as 2% of PEI amines resulted in transgene expression 260- to 480-fold higher than that of unmodified PEI and 50- to 65-fold higher than that of commercial PEI-PEG2k in HEK293 and HeLa cells, respectively. Remarkably, the same zPEIs also produced 16-fold greater efficiency of CRISPR/Cas9 gene knock-in compared to unmodified PEI in the presence of serum. In addition, we show that 2% succinylation does not significantly decrease polymer/DNA binding ability or serum protein interaction to a significant extent, yet this small modification is still sufficient to provide a remarkable increase in transgene expression and gene knock-in in the presence of serum.The highly regio-, diastereo-, and enantioselective dearomatization reaction of 1-substituted 2-naphthols and β,γ-alkynyl-α-imino esters with complete atom economy is disclosed via chiral phosphoric acid catalysis. This protocol provides facile and efficient access to asymmetric construction of a broad range of axially chiral allene-derived naphthalenones bearing quaternary stereocenters in good yields with high diastereoselectivities and enantioselectivities.Two-dimensional (2D) materials have attracted great attention in recent years because of their unique dimensionality and related properties. Chemical vapor deposition (CVD), a crucial technique for thin-film epitaxial growth, has become the most promising method of synthesizing 2D materials. Different from traditional thin-film growth, where strong chemical bonds are involved in both thin films and substrates, the interaction in 2D materials and substrates involves the van der Waals force and is highly anisotropic, and therefore, traditional thin-film growth theories cannot be applied to 2D material CVD synthesis. During the last 15 years, extensive theoretical studies were devoted to the CVD synthesis of 2D materials. This Perspective attempts to present a theoretical framework for 2D material CVD synthesis as well as the challenges and opportunities in exploring CVD mechanisms. We hope that this Perspective can provide an in-depth understanding of 2D material CVD synthesis and can further stimulate 2D material synthesis.Low-dimensional metal halides have attracted considerable attention due to their unique optoelectronic properties. In this study, we report a solid-state synthesis of air-stable all-inorganic Pb-free zero-dimensional (0D) Rb3InCl6 single crystals (SCs). By a heterovalent doping of Cu+ ions, the Rb3InCl6Cu+ SCs featured an efficient blue-violet emission with a greatly enhanced photoluminescence (PL) quantum yield (95%) and an ultralong PL lifetime (13.95 μs). Combined with temperature-dependent PL and density functional theory calculations, we conclude that the efficient electronic isolation, enhanced exciton-phonon coupling, and electronic structure modulation after doping lead to bright blue-violet emission. Furthermore, the SCs exhibited excellent stability, maintaining 90% of the initial PL intensity after being stored in ambient conditions for more than two months. The results provide a new strategy for improving the optoelectronic properties of 0D all-inorganic metal halides, which is promising for potential light-emitting applications.The mechanical environment of a cell is not constant. This dynamic behavior is exceedingly difficult to capture in (synthetic) in vitro matrices. This paper describes a novel, highly adaptive hybrid hydrogel composed of magnetically sensitive magnetite nanorods and a stress-responsive synthetic matrix. Nanorod rearrangement after application of (small) magnetic fields induces strain in the network, which results in a strong (over 10-fold) stiffening even at minimal (2.5 wt %) nanorod concentrations. Moreover, the stiffening mechanism yields a fast and fully reversible response. Brepocitinib cost In the manuscript, we quantitatively analyze that forces generated by the particles are comparable to cellular forces. We demonstrate the value of magnetic stiffening in a 3D MCF10A epithelial cell experiment, where simply culturing on top of a permanent magnet gives rise to changes in the cell morphology. This work shows that our hydrogels are uniquely suited as 3D cell culture systems with on-demand adaptive mechanical properties.Here, we report mode-specific resonance Raman enhancements of ligands covalently bound to the surface of colloidal CdSe nanocrystals (NCs). By the systematic comparison of a set of structural derivatives, the extent of resonance Raman enhancement is shown to be directly related to the molecular symmetry of the bound ligands. link2 The enhancement dependence on molecular symmetry is further discussed in terms of Franck-Condon and Herzberg-Teller contributions and their associated selection rules. We further show that resonance Raman may be used to distinguish between possible surface binding motifs of bidentate ligands under continuous wave excitation. More generally, this work demonstrates the usefulness of resonance Raman as a characterization tool when characterizing adsorbed molecular species on semiconductor NC surfaces.Through its ability to image liquid-phase dynamics at nano/atomic-scale resolution, liquid-cell electron microscopy is essential for a wide range of applications, including wet-chemical synthesis, catalysis, and nanoparticle tracking, for which involved structural features are critical. However, statistical investigations by usual techniques remain challenging because of the difficulty in fabricating substantial liquid cells with appreciable efficiency. Here, we report a general approach for efficiently printing huge numbers of ready-to-use liquid cells (∼9000) within 30 s by electrospinning, with the unique feature of statistical liquid-phase studies requiring only one experimental time slot. link3 Our solution efficiently resolves a complete transition picture of bubble evolution and also the induced nanoparticle motion. We statistically quantify the effect of the electron dose rate on the bubble variation and conclude that the bubble-driven nanoparticle motion is a ballistic-like behavior insignificant to morphological asymmetries. The versatile approach here is critical for statistical research, offering great opportunities in liquid-phase-associated dynamic studies.A copper-catalyzed C-3 functionalization of imidazo[1,2-a]pyridines with 3-indoleacetic acids through an aerobic oxidative decarboxylative process has been developed. The protocol provided a series of 3-(1H-indol-3-ylmethyl)-imidazo[1,2-a]pyridines in moderate to good yields under simple reaction conditions. Importantly, some products exhibited potent antiproliferative activity in cancer cell lines.A mild and efficient protocol for the copper(I)-catalyzed C4-H sulfamidation of 1-naphthylamine derivatives with diphenylsulfonimide (NHSI) was explored at room temperature, affording the desire produces in moderate to good yields. The control experiments indicated that this visible-light-promoted reaction might proceed via a single-electron-transfer process. In addition, preliminary DFT studies for the intermediates in the catalytic cycle were also explored, indicating that the C4 site in the naphthyl ring is the most likely electrophilic reactive site and providing some exact basis for the plausible mechanism.Conjugation-extended carbazolophane donors, dicarbazolophanes (DCzp), were designed and synthesized using a multifold stepwise Pd-catalyzed Buchwald-Hartwig amination/ring cyclization process. Furthermore, elaboration of the DCzp core is possible with the introduction of pendant carbazole derivative groups. This provides a way to tune the optoelectronic properties of the thermally activated delayed fluorescence (TADF) compounds DCzpTRZtBu, dtBuCzDCzpTRZtBu, and dMeOCzDCzpTRZtBu. Solution-processed organic light-emitting diodes (OLEDs) were fabricated and achieved a maximum external quantum efficiency (EQEmax) of 8.2% and an EQE of 7.9% at 100 cd/m2.
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