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Two complementary catalytic protocols for the isomerization of stereoisomeric mixtures of vinylcyclopropanes are described. A commercially available cationic rhodium complex provides access to conjugated dienoates in high yield with excellent stereocontrol. The combination of a bisphosphine ligand and a ruthenium precatalyst affords cross-conjugated dienoates via a formal 1,3-ring opening. The products are obtained with moderate to high stereoselectivity. The ability of each type of dienoate to engage in [4 + 2] cycloaddition reactions has been demonstrated.A novel protocol for asymmetric synthesis of hydroquinazolines bearing C4-tetrasubstituted stereocenters has been achieved through kinetic resolution of 2-amido α-tertiary benzylamines via chiral phosphoric acid catalyzed intramolecular dehydrative cyclizations. This method gave access to both α-tertiary benzylamines and hydroquinazolines with broad scope and high enantioselectivities. An intriguing restricted rotation of the C-N bond was observed for hydroquinazoline products bearing C4-tetrasubstituted stereocenters.Electrophilic nitropyridines react with sulfonyl-stabilized carbanions to give products of C-H alkylation via vicarious nucleophilic substitution. The process consists of formation of the Meisenheimer-type adduct followed by base-induced β-elimination of the sulfinic acid (e.g., PhSO2H). Mechanistic studies reveal that in the latter step alkyl substituent and adjacent nitro group tend to planarize for effective stabilization of benzyl anion, and thus, adduct of hindered isopropyl carbanion remains stable toward elimination for steric reasons.In this study, we developed a method for etherification via aromatic substitution at the ipso-position of an electron-withdrawing group (EWG) that exists at the meta-position of another EWG. To heighten the reactivity of the substitution reaction, we added a t-BuOK solution in tetrahydrofuran (THF) to a mixture of an aromatic substrate, an alcoholic nucleophile, and 18-crown-6-ether in dimethylformamide (DMF), which proved to be a particularly effective sequence. Under the conditions we established, aromatic substrates that are difficult to use for substitution reactions such as aryl fluorides activated with either a bromide or a chloride substituent were aptly converted to corresponding ether products at 25 °C. This reaction would potentially be useful to link an alcohol to an additional functional group through further chemical transformations via the use of a residual bromide or chloride substituent.Nanoplasmonic systems combined with optically active two-dimensional materials provide intriguing opportunities to explore and control light-matter interactions at extreme subwavelength length scales approaching the exciton Bohr radius. Here, we present room- and cryogenic-temperature investigations of a MoSe2 monolayer on individual gold dipole nanoantennas. By controlling nanoantenna size, the dipolar resonance is tuned relative to the exciton achieving a total tuning of ∼130 meV. Differential reflectance measurements performed on &gt;100 structures reveal an apparent avoided crossing between exciton and dipolar mode and an exciton-plasmon coupling constant of g = 55 meV, representing g/(ℏωX) ≥ 3% of the transition energy. This places our hybrid system in the intermediate-coupling regime where spectra exhibit a characteristic Fano-like shape. We demonstrate active control by varying the polarization of the excitation light to programmably suppress coupling to the dipole mode. We further study the emerging optical signatures of the monolayer localized at dipole nanoantennas at 10 K.The adsorption of an NO molecule on a cationic iridium-doped rhodium cluster, Rh5Ir+, was investigated by infrared multiple photon dissociation spectroscopy (IRMPD) of Rh5IrNO+·Arp complexes in the 300-2000 cm-1 spectral range, where the Ar atoms acted as a messenger signaling IR absorption. Complementary density functional theory (DFT) calculations predicted two near-isoenergetic structures as the putative global minimum one with NO adsorbed in molecular form in the on-top configuration on the Ir atom in Rh5Ir+, and one where NO is dissociated with the O atom bound to the Ir atom in the on-top configuration and the N atom on a hollow site formed by three Rh atoms. A comparison between the experimental IRMPD spectrum of Rh5IrNO+ and calculated spectra indicated that NO mainly adsorbs molecularly on Rh5Ir+, but evidence was also found for structures with dissociatively adsorbed NO. The estimated fraction of Rh5IrNO+ structures with dissociatively adsorbed NO is approximately 10%, which was higher than that found for Rh6+, but lower than that for Ir6+. The DFT calculations indicated the existence of an energy barrier in the NO dissociation pathway that is exothermic with respect to the reactants, which was considered to prevent NO from dissociating readily on Rh5Ir+. The height of the barrier is lower than that for NO dissociation over Rh6+, which is attributed to the higher binding energy of atomic O to the Ir atom in Rh5Ir+ than to a Rh atom in Rh6+.The detection of charge trap ionization induced by resonant excitation enables spectroscopy on single Er3+ ions in silicon nanotransistors. In this work, a time-resolved detection method is developed to investigate the resonant excitation and relaxation of a single Er3+ ion in silicon. The time-resolved detection is based on a long-lived current signal with a tunable reset and allows the measurement under stronger and shorter resonant excitation in comparison to time-averaged detection. Specifically, the short-pulse study gives an upper bound of 23.7 μs on the decay time of the 4I13/2 state of the Er3+ ion. The fast decay and the tunable reset allow faster repetition of the single-ion detection, which is attractive for implementing this method in large-scale quantum systems of single optical centers. The findings on the detection mechanism and dynamics also provide an important basis for applying this technique to detect other single optical centers in solids.Among the members of the rapidly growing nanozyme family, plasmonic nanozymes stand out because of their unique localized surface plasmon resonance (LSPR) characteristics and tunable catalytic activity. We prepared a plasmonic nanozyme of Au gold nanoparticles (AuNPs) and Cu metal-organic framework nanosheets (Cu-MOFNs). The Cu-MOFNs have peroxidase-like activity, while AuNPs present unique LSPR characteristics. We found that the as-prepared AuNPs/Cu-MOFNs composite presents 1.6-fold faster reaction kinetics under LSPR excitation compared to that in the dark. [https://www.selleckchem.com/products/ml323.html selleckchem] Investigations of energy levels, radical capture, and dark-field scattering spectroscopy revealed that LSPR of AuNPs as well as matched energy levels can facilitate efficient hot electron transfer, which could readily cleave the chemical bond of the substrate and accelerate the reaction kinetics. On the basis of these results, we achieved enhanced antibacterial therapy and wound healing using plasmonic AuNPs/Cu-MOFNs. This study spotlights the superiority of plasmonic nanozymes in improving the enzyme-like performance of nanozymes.A Ni-mediated decarboxylative silylation of alkynyl cyclic carbonates used as versatile propargylic surrogates is reported affording a wide range of highly substituted 2,3- and 3,4-allenol products in good yields. The formal cross-coupling between a tentative intermediate Ni(allenyl) and the silyl reagent was further extended to enantiospecific conversions providing access to chiral allene synthons. This protocol marks the first Ni-catalyzed propargylic silylation proceeding through an SN2' manifold.A newly developed phosphine ligand with a C2-cyclohexyl group on the indole ring was successfully applied in a chemoselective Sonogashira coupling reaction with excellent chemoselectivity, affording an inversion of the conventional chemoselectivity order of C-Br &gt; C-Cl &gt; C-OTf. This study also provided an efficient approach to the synthesis of polycyclic aromatic hydrocarbons (PAHs) and the natural product analogue trimethyl-selaginellin L by merging of chemoselective Sonogashira and Suzuki-Miyaura coupling reactions.Although examples of colloidal crystal analogues to metal alloys have been reported, general routes for preparing 3D analogues to random substitutional alloys do not exist. Here, we use the programmability of DNA (length and sequence) to match nanoparticle component sizes, define parent lattice symmetry and substitutional order, and achieve faceted crystal habits. We synthesized substitutional alloy colloidal crystals with either ordered or random arrangements of two components (Au and Fe3O4 nanoparticles) within an otherwise identical parent lattice and crystal habit, confirmed via scanning electron microscopy and small-angle X-ray scattering. Energy dispersive X-ray spectroscopy reveals information regarding composition and local order, while the magnetic properties of Fe3O4 nanoparticles can direct different structural outcomes for different alloys in an applied magnetic field. This work constitutes a platform for independently defining substitution within multicomponent colloidal crystals, a capability that will expand the scope of functional materials that can be realized through programmable assembly.In a recent report on the synthetic approach to the novel substance class of 1-alkylidene/arylidene-1,2,4-triazolinium salts, a reaction mechanism suggesting a regioselective outcome was proposed. This hypothesis was tested via a combined NMR and density functional theory (DFT) approach. To this end, three experiments with 13C-labeled carbonyl reactants were monitored in situ by solution-state NMR. In one experiment, an intermediate as described in the former mechanistic proposal was observed. However, incorporation of 13C isotope labels into multiple sites of the heterocycle could not be reconciled with the "regioselective mechanism". It was found that an unproductive reaction pathway can lead to 13C scrambling, along with metathetical carbonyl exchange. According to DFT calculations, the concurring reaction pathways are connected via a thermodynamically controlled cyclic 1,3-oxazetidine intermediate. The obtained insights were applied in a synthetic study including aliphatic ketones and para-substituted benzaldehydes. The mechanistic peculiarities set the potential synthetic scope of the novel reaction type.The interactions between ectodomains of cell surface proteins are vital players in many important cellular processes, such as regulating immune responses, coordinating cell differentiation, and shaping neural plasticity. However, while the construction of a large-scale protein interactome has been greatly facilitated by the development of high-throughput experimental techniques, little progress has been made to support the discovery of extracellular interactome for cell surface proteins. Harnessed by the recent advances in computational modeling of protein-protein interactions, here we present a structure-based online database for the extracellular interactome of cell surface proteins in humans, called EXCESP. The database contains both experimentally determined and computationally predicted interactions among all type-I transmembrane proteins in humans. All structural models for these interactions and their binding affinities were further computationally modeled. Moreover, information such as expression levels of each protein in different cell types and its relation to various signaling pathways from other online resources has also been integrated into the database.