The gas-phase affinities of different types of anions X- (halogen anions, oxoanions, and hydrogenated anions) toward a model tetralactam-based macrocycle receptor (1), defined in terms of stability of an anion-receptor complex (1 + X-) against its disintegration, were evaluated by dissociation studies using a mass spectrometry-based methodology and supported by theoretical calculations (density functional theory-PBE0). The gas-phase complex with Cl- was found to be tailor-made for the macrocycle 1, while 1 + SA- (SA- = salicylate anion) and 1 + HSO4- were the weakest ones. Other complexes displayed a relatively low-stability dispersion ( less then 1.2 kcal·mol-1). The 1/εr approach of the electrostatic contribution scaling method was used to predict the stability trends in a dimethyl sulfoxide solvent from the gas-phase binding energy partition using the symmetry-adapted perturbation theory. High deformation energy and differences in solvation energies were suggested to be the main sources of inconsistency in the predicted and experimental stabilities of 1 + F- and 1 + H2PO4- complexes.The hitherto elusive N-hydroxyoxaziridine molecule (c-H2CON(OH)), a chiral, high energy isomer of nitromethane (CH3NO2) and one of the simplest representatives of an oxaziridine, is detected in the gas phase. Electronic structure calculations propose an impending synthesis eventually via addition of carbene (CH2) to the nitrogen-oxygen double bond of nitrous acid (HONO). The oxaziridine ring demonstrates an unusual kinetic stability toward ring opening compared to the isoeletronic cyclopropane (C3H6) counterpart. This system defines a fundamental benchmark to explore the formation and stability of racemic derivatives of strained oxaziridines (c-H2CONH) and changes our perception how we think about fundamental decomposition and isomerization mechanisms in (model compounds of) energetic materials.Herein, a new exonuclease III (Exo III)-powered self-propelled DNA machine was developed for the cascade multilevel signal amplification of nucleic acid and nucleic acid-related analytes. It could be easily and homogeneously operated with the use of an integral DNA hybrid probe as the recognition, amplification, and signaling element, and the Exo III cleavage as a driving force. The DNA hybrid probe was obtained by annealing two hairpin-like DNAs. The target recognition with the 3'-protruding domain of the DNA hybrid probe triggered Exo III cleavage, accompanied by target recycling and alternate generation of a large amount of target substitute and analogy. Simultaneously, the cascade bidirectional Exo III cleavage toward the DNA hybrid probe by the generated target substitute and analogy contributed for the exponential signal amplification toward target recognition event. It could be also extended for the application in protein detection with the thrombin as a protein example by introducing an additional hairpin-like aptamer switch. The proposed Exo III-powered self-propelled DNA amplification strategy showed a linear detection range for target DNA from 0.5 fM to 1 pM and for thrombin from 5 fM to 10 pM. The low detection limit toward target DNA and thrombin could reach about 0.1 fM and 5 fM, respectively, which were superior to most of reported methods. It also exhibited an excellent selectivity toward target detection. Therefore, the developed sensing system exhibits a new, simple and powerful means for amplified detection of nucleic acid and nucleic acid-related analytes, and may hold great potentials in bioanalysis, disease diagnosis and biomedicine.The hydrogenation of N-substituted vinylphosphonates using rhodium complexes derived from P-OP ligands L1, ent-L1, or (R,R)-Me-DuPHOS as catalysts has been successfully accomplished, achieving very high levels of stereoselectivity (up to 99% ee or de). The described synthetic strategy allowed for the efficient preparation of α-aminophosphonic acid derivatives and phosphonopeptides, which are valuable building blocks for the preparation of biologically relevant molecules.Cross-connected buried nanochannels of height ∼728 nm, with micropores of ∼2 μm diameter present at each intersection, are used in this work to numerically and experimentally study droplet-coupled evaporation dynamics at room temperature. The uniformly structured channels/pores, along with their well-defined porosity, allow for computational fluid dynamics simulations and experiments to be performed on the same geometry of samples. A water droplet is placed on top of the sample causing water to wick into the nanochannels through the micropores. After advancing, the meniscus front stabilizes when evaporation flux is balanced with the wicking flux, and it recedes once the water droplet is completely wicked in. Evaporation flux at the meniscus interface of channels/pores is estimated over time, while the flux at the water droplet interface is found to be negligible. When the meniscus recedes in the channels, local contact line regions are found to form underneath the pores, thus rapidly enhancing evaporation flux as a power-law function of time. Temporal variation of wicking flux velocity and pressure gradient in the nanochannels is also independently computed, from which the viscous resistance variation is estimated and compared to the theoretical prediction.An efficient method for visible-light-initiated, nickel-catalyzed Sonogashira C(sp)-C(sp2) coupling has been developed via an energy-transfer mode.  https://www.selleckchem.com/pharmacological_epigenetics.html  Thioxanthen-9-one as a photosensitizer could significantly accelerate the arylation of alkynes with a wide range of (hetero)aryl halides in high yields. The cross-coupling reaction undergoes the stepwise oxidative addition of an arylhalide to nickel(0), transmetalation of the resulting aryl-Ni(II) halide species with Zn(II) acetylide into aryl-Ni(II) acetylide species, energy transfer from the excited state of thioxanthen-9-one to aryl-Ni(II) acetylide, and reductive elimination to the aryl alkyne.Stimuli-responsive microemulsions have recently attracted significant interest due to their unique properties. Here, we developed a novel surfactant-free microemulsion (SFME) in a nontoxic ternary mixture, in which dimethyl sulfoxide (DMSO) was used as an amphisolvent, n-butanol was used as a nonpolar phase, and water was used as a polar phase. The DLS results confirmed the presence of the preouzo zone, and the polarity experiment revealed that the single-phase region can be further divided into oil-in-water, bicontinuous, and water-in-oil subregions. The size of droplets increased upon increasing the water or n-butanol content but decreased with increasing DMSO content. With increasing temperature, the area of the single-phase region increased, accompanied by a decrease in the size of the droplets, and the critical point moved to the corner of n-butanol. No matter in what subregion the formulation was found, decreasing temperature to below the phase-transition temperature (PTT) will induce a transition from monophasic MEs to complete phase separation and vice versa.