Glassherndon4378

Dual cinchona quinuclidinium salts with a diphenyl ether linker were synthesized and used as powerful asymmetric phase transfer catalysts in the α-alkylation of imines of glycine and alanine ester with 0.01-0.1 mol% loading (17 examples, 92-99% ee). Skewed conformers of dual quinuclidiniums at TS were proposed to rationalize their high efficiency via DFT calculations.Ultrathin necklace-like Ag2Te nanowires with a diameter of 10 nm and a length of several micrometers are fabricated by a simple solution-based process at low temperature, and the Ag2Te nanowire films are fabricated by a Langmuir-Blodgett technique. A reversible structural phase transition of the nanowire films obtained can be observed, and in addition is also reflected by the electrical properties.The effect of the shear rate on the viscosity and the structure of 1-ethyl-3-methylimidazolium based ionic liquids with three different anions (tetrafluoroborate, dicyanamide, and bis(trifluoromethylsulfonyl)imide) was studied by means of reverse non-equilibrium molecular dynamics (RNEMD) simulations using a polarizable force field. The three liquids display a Newtonian plateau followed by a shear thinning regime at shear rates of the order of GHz. Even though the main features of the liquid structure remains under shear, systematic changes were noticed at the GHz rates, with coordination shells becoming more diffuse as noticed by the reduction in the difference between consecutive maxima and minima in the radial distribution function. Interestingly, these structural changes with the shear rate can be precisely fitted using the Carreau equation, which is a well-known expression for the shear rate dependence of the viscosity. The fitting parameters for different distributions can be used to explain qualitatively the shear thinning behavior of these liquids. In the GHz range, the cations and, in a minor extension, some anions, tend to assume preferentially a parallel orientation with the flux, which contributes to the shear thinning behavior and may have consequences for adhesion in applications as lubricants.In this work, we prepare a PDMS-SiO2-PDA@fabric with high water contact angle (WCA = 155°). Combining dopamine self-polymerization and a sol-gel method, SiO2 is in situ grown on a PDA-modified fabric surface to synergistically construct micro-nano rough structures. Finally, a superhydrophobic fabric is successfully obtained after coating the fabric with a layer of PDMS. The prepared fabric can maintain superhydrophobicity after immersion in various solvents (pH = 1, 3, 5, 7, 9, 11, 13, DMF, ethanol, THF, n-hexane) for 24 h and strong ultraviolet irradiation for 60 min. Thanks to the highly reactive PDA clusters, the stronger interfacial bond between the fabric and SiO2 enables it to withstand 180 min of washing and 159.22 N tensile stress, showing strong adhesion strength. In addition, the modified fabric has excellent self-cleaning properties and is resistant to contamination such as milk, coffee and tea. More importantly, the prepared fabric can selectively repel water and adsorb oil, achieving above 90% oil-water separation efficiency even after 8 cycles.Graphene nanoribbons (GNRs) fabricated using electron beam lithography are investigated using tip-enhanced Raman spectroscopy (TERS) with a spatial resolution of 5 nm under ambient conditions. High-resolution TERS imaging reveals a structurally modified 5-10 nm strip of disordered graphene at the edge of the GNRs. Furthermore, hyperspectral TERS imaging discovers the presence of nanoscale organic contaminants on the GNRs. These results pave the way for nanoscale chemical and structural characterisation of graphene-based devices using TERS.Nano- and micro-scale burnt bridge ratchet motors, which translocate via "guide" molecules that bind to and degrade a field of "fuel" molecules, have recently emerged in several biological and engineering contexts. The capacity of these motors to generate mechanical forces remains an open question. Here, chemomechanical modeling suggests that BBR force scales linearly with the steady-state number of guide-fuel bonds.The complex coacervation of proteins with other macromolecules has applications in protein encapsulation and delivery and for determining the function of cellular coacervates. Theoretical or empirical predictions for protein coacervates would enable the design of these coacervates with tunable and predictable structure-function relationships; unfortunately, no such theories exist. To help establish predictive models, the impact of protein-specific parameters on complex coacervation were probed in this study. The complex coacervation of sequence-specific, polypeptide-tagged, GFP variants and a strong synthetic polyelectrolyte was used to evaluate the effects of protein charge patterning on phase behavior. Phase portraits for the protein coacervates demonstrated that charge patterning dictates the protein's binodal phase boundary. Protein concentrations over 100 mg mL-1 were achieved in the coacervate phase, with concentrations dependent on the tag polypeptide sequence covalently attached to the globular protein domain. In addition to shifting the binodal phase boundary, polypeptide charge patterning provided entropic advantages over isotropically patterned proteins. Together, these results show that modest changes of only a few amino acids in the tag polypeptide sequence alter the coacervation thermodynamics and can be used to tune the phase behavior of polypeptides or proteins of interest.There is a need for a catalyst that can directly convert methane into useful substances. selleck products The use of Ni as a catalyst for the steam reforming of methane has led us to look at Ni nanoclusters as potential candidates for the direct conversion of methane. Fe, Co, Cu, and Zn nanoclusters are also focused on. How the type of C1 fragments (CH4, CH3, CH2, CH, and C) stabilized by the metal nanoclusters as adsorbed species varies with metal species is theoretically investigated. The particle swarm optimization algorithm, which is based on swarm intelligence, as well as density functional theory, is used for this calculation. The Ni nanoclusters are found to preferentially adsorb C as a stable species, the Fe and the Co nanoclusters both CH and CH3, and the Cu nanoclusters CH3; the Zn nanoclusters are found not to chemisorb any C1 fragment. The methane activation capacity can be ranked in the order of Ni > Fe > Co > Cu > Zn. The highest methane activation capacity of Ni is due to the strongest covalent nature of the interaction between Ni and the adsorbed species. The ionicity of the bond between Fe and the adsorbed species is higher than that between Co and the adsorbed species, while the covalent nature of the bonds is comparable for both. The weak methane activation ability of Cu compared to Fe, Co, and Ni is found to be due to the fact that both the covalent and ionic bond strengths between Cu and the adsorbed species are weak. Zn and the adsorbed species form neither ionic nor covalent bonds. These results indicate that the Fe and the Co nanoclusters as well as the Ni may lead to the over-oxidation of methane, whereas the Zn nanoclusters cannot activate methane in the first place; therefore, their application to direct methane conversion catalysts is unlikely. Since the Cu nanoclusters do not adsorb C and CH as stable species, but CH3 stably, the Cu nanoclusters are expected to work as a catalyst for the direct conversion of methane.Herein, we report the encapsulation and release of antimalarial drug quinine (QN) using three nanocarriers, including MCM-41 (1), and its 3-aminopropyl silane (aMCM-41 (2)) and 3-phenylpropyl silane (pMCM-41 (3)) surface functionalized derivatives. The pH and thermal optimization effects on QN adsorption and release from 1, 2 and 3 were investigated.A π-conjugated porous organic polymer (BCzBz) was fabricated employing N,N'-bicarbazole and benzothiadiazole as molecular building units exhibiting broad visible light absorption. The photostable, water-dispersible, and cytocompatible BCzBz was demonstrated as an efficient probe for intracellular reactive oxygen species generation under photoirradiation.Correction for 'The pan-cancer analysis of the two types of uterine cancer uncovered clinical and prognostic associations with m6A RNA methylation regulators' by Zhilin Zou et al., Mol. Omics, 2021, 17, 438-453, DOI 10.1039/d0mo00113a.The study of non-innocent behavior of NHCs (NHCs = N-heterocyclic carbenes) has great implications for NHC-involved catalysis. Herein, we report a new type of NHC-to-azole rearrangement, during which process the carbene backbone and the substituent are both non-innocent. To the best of our knowledge, this work also presents the first example of NHC-to-azole rearrangements for aryl-substituted NHCs.Development of a simple, effective, and practical method for (Z)-selective semihydrogenation of alkynes has been considered necessary for easy-to-access applications at organic laboratory scales. Herein, (Z)-selective semihydrogenation of alkynes was achieved using a copper nanocatalyst which was generated in situ simply by adding ammonia borane to an ethanol solution of copper sulfate. Different types of alkynes including aryl-aryl, aryl-alkyl, and aliphatic alkynes were selectively reduced to (Z)-alkenes affording up to 99% isolated yield. The semihydrogenation of terminal alkynes to alkenes and gram-scale applications were also reported. In addition to eliminating catalyst preparation, the proposed approach is simple and practical and serves as a suitable alternative method to the conventional Lindlar catalyst.In the fabrication of efficient multicomponent semiconductors for photocatalysis, well-defined hierarchical structures and high-quality heterojunctions are still highly desired. A general preparation method was developed for a series of hierarchical TiO2-based heterojunctions with tailored interior space from solid, core-shell and yolk-shell to fully hollow structures.Correction for 'Thermoelectric properties of CZTS thin films effect of Cu-Zn disorder' by E. Isotta et al., Phys. Chem. Chem. Phys., 2021, DOI 10.1039/d1cp01327k.In this article the Raman and Raman Optical Activity (ROA) spectra of a series of enantiomeric twisted anthracenes are presented. The evolution of their vibrational spectra is understood in the context of the variation of π-electron delocalization as a result of the twisting imparted by the belt structure and in terms of the modulation of the resonance Raman/ROA effects which are photonic properties also tuned by anthracene twisting. The Raman/ROA vibrational spectra are simulated by several theoretical approaches to account for their vibrational and electronic properties including the theoretical evaluation of resonance effects. We furthermore incorporate a vibrational and ROA activity dissection analysis as provided in the Pyvib2 program valid to establish correlations among vibrational modes of different molecules with different electronic structures and equivalent vibrational dynamics. This paper is one of the very first attempts to use ROA spectroscopy in π-conjugated molecules with twisted and helical morphologies that contrast with the well-known cases of ROA studies of chiral helicenes in which the impact of π-electron delocalization in the electronic/photonic/vibrational (Raman/ROA) spectra is negligible.