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  • Dueholm Crews posted an update 2 weeks, 4 days ago

    A series of gold precursor solutions are prepared by dissolving HAuCl4 and its mixtures with K2CO3 of different contents in deionized (DI) water. Neat HAuCl4 predominately forms AuCl4- ions in an aqueous solution. In the presence of K2CO3, AuCl4- ions hydrolyze to form [AuCl4-x(OH)x]- complex ions. Increasing the content of K2CO3 in a gold precursor solution increases the content of [AuCl4-x(OH)x]- complex ions and decreases the content of AuCl4- ions. Poly(4-vinyl pyridine) (P4VP) films of two different molecular weights are deposited on SiOx/Si by spin coating, by which the thicknesses are controlled by polymer weight fractions in butanol. CFTRinh-172 cost Those P4VP films form periodic wrinkles when immersed in aqueous solutions, followed by drying. The surface wrinkling is induced by swelling pressure that overwhelms the mechanical property of the P4VP film. The periodicity and amplitude of wrinkles grown on the P4VP films strongly correlate with initial thickness, AuCl4- ion content, and residual stress.Herein, crack-free photonic crystal templates with enhanced color contrast were first demonstrated by the coassembly of polystyrene (PS) microspheres and graphene oxide (GO). Then, photonic crystal hydrogels (PCHs) with quick responses to temperature and alcohol solution concentration changes were fabricated by photopolymerization of monomers in the gaps of the self-assembled colloidal crystal templates. The structural color of the PCHs changed from yellow to blue within 120 s as the temperature rose from 25 to 40 °C, whereas upon a decrease in temperature from 40 to 25 °C, the structural color changed from blue to yellow. The structural color of the PCHs also shows an obvious response with the concentration of alcohol solution ranging from 40 to 100 wt %. The quick responses of the PCHs’ structural color to changes in temperature and alcohol solution concentration are attributed to the temperature sensitivity of poly(N-isopropylacrylamide) and preferential adsorption and swelling of the alcohol solution for the polymer chains. Furthermore, moxifloxacin (Mox) was loaded into PCHs by hydrogel swelling and exhibited sustained released by increasing the temperature. The sustained release process was facilely monitored by observing the corresponding color changes in real time. The rapid and visible response offers the fabricated PCHs great potential application prospects in the semiquantitative analysis of alcohol concentration and intelligent drug delivery.Compared with itinerant electrons in monolayer transition-metal dichalcogenides, localized electrons exhibit coherent spin precession in transverse magnetic fields B and usually have longer spin relaxation times. Here, we uncover the intrinsic spin dephasing processes of localized electrons whose mechanism remains unclear. Electron spin coherence dynamics are studied by time-resolved Faraday rotation spectroscopy in monolayer MoS2, where four subensembles of localized electrons are found with different g factor values and inhomogeneous broadening. The spin dephasing rates of all four subensembles include a linearly B-dependent part due to g-factor inhomogeneity and a B-independent part dominated by electron-nuclear hyperfine interaction and/or anisotropic exchange interaction. The hyperfine-induced spin dephasing time is ∼30-40 ns, and the anisotropic exchange-induced spin dephasing time is on the order of subnanoseconds. The findings give insight into the coherent spin dynamics of localized electrons in monolayers and the interaction between the electron spin and its environment.The combined catalysis of glucose isomerase (GI), d-psicose 3-epimerase (DPEase), ribitol dehydrogenase (RDH), and formate dehydrogenase (FDH) provides a convenient route for the biosynthesis of allitol from d-glucose; however, the low catalytic efficiency restricts its industrial applications. Here, the supplementation of 0.32 g/L NAD+ significantly promoted the cell catalytic activity by 1.18-fold, suggesting that the insufficient intracellular NAD(H) content was a limiting factor in allitol production. Glucose dehydrogenase (GDH) with 18.13-fold higher activity than FDH was used for reconstructing a cofactor self-sufficient system, which was combined with the overexpression of the rate-limiting genes involved in NAD+ salvage metabolic flow to expand the available intracellular NAD(H) pool. Then, the multienzyme self-assembly system with SpyTag and SpyCatcher effectively channeled intermediates, leading to an 81.1% increase in allitol titer to 15.03 g/L from 25 g/L d-glucose. This study provided a facilitated strategy for large-scale and efficient biosynthesis of allitol from a low-cost substrate.Linking surface structure evolution to the capacity fading of cathode materials has been a problem in lithium ion batteries. Most of the strategies used to solve this problem are focused on the differences between the unaged and aged materials, leading to the loss of intermediate dynamic change information during cycling. Raman spectroscopy is a convenient, nondestructive, and highly sensitive tool for characterizing the surface/near-surface region structure. In this work, we improved an operando Raman system, which is able to record in situ and in real time a series of Raman spectra during charging/discharging cycles and is even able to record very weak Raman peaks without the use of SRES enhancement, which facilitates sample preparation. These series of Raman spectra revealed an inherent correlation between the electrode potential/Li content and the surface structure changes of the as-prepared pure LiMn2O4 film, including the biphase reaction, the evolution of the peroxo O-O bond, and the formation of the Mn3O4 surface phase. They were the first to show that the number of peroxo O-O bonds was decreased with an increasing number of cycles and that this decrease was accompanied by an increase in the Mn3O4 phase. With the help of the data measured by XPS, c-AFM, electrochemical testing equipment, and the calculation based on density functional theory, the causes of the capacity fading of the material are discussed. This work not only showed a direct correlation between the surface structure evolution and the capacity fading of the LiMn2O4 but also could provide an alternative operando Raman system that could be widely used for the in situ characterization of battery electrode materials.Boron neutron capture therapy (BNCT) is a radiation therapy for cancer. In BNCT, the internalization of boron-10 atoms by cancer cells induces cell death through the generation of α particles and recoiling lithium-7 nuclei when irradiated with low-energy thermal neutrons. In this study, we aimed to construct exosomes [extracellular vesicles (EVs)]-based drug delivery technology in BNCT. Because of their pharmaceutical advantages, such as controlled immune responses and effective usage of cell-to-cell communication, EVs are potential next-generation drug delivery carriers. In this study, we successfully developed polyhedral borane anion-encapsulated EVs with modification of hexadeca oligoarginine, which is a cell-penetrating peptide, on the EV membrane to induce the actin-dependent endocytosis pathway, macropinocytosis, which leads to efficient cellular uptake and remarkable cancer cell-killing BNCT activity. The simple and innovative technology of the EV-based delivery system with “cassette” modification of functional peptides will be applicable not only for BNCT but also for a wide variety of therapeutic methodologies.Fast and accurate structure prediction is essential to the study of peptide function, molecular targets, and interactions and has been the subject of considerable efforts in the past decade. In this work, we present improvements to the popular simplified PEP-FOLD technique for small peptide structure prediction. PEP-FOLD originality is threefold (i) it uses a predetermined structural alphabet, (ii) it uses a sequential algorithm to reconstruct the tridimensional structures of these peptides in a discrete space using a fragment library, and (iii) it assesses the energy of these structures using a coarse-grained representation in which all of the backbone atoms but the α-hydrogen are present, and the side chain corresponds to a unique bead. In former versions of PEP-FOLD, a van der Waals formulation was used for non-bonded interactions, with each side chain being associated with a fixed radius. Here, we explore the relevance of using instead a generalized formulation in which not only the optimal distance of inrstanding on folded structures, even when less precise than AlphaFold2. With their strong physical influence, the revised structural library and coarse-grained potential offer, however, the means for a deeper understanding of the nature of folding and open a solid basis for studying flexibility and other dynamical properties not accessible to IA structure prediction approaches.Riboswitches are noncoding RNA that regulate gene expression by folding into specific three-dimensional structures (holo-form) upon binding by their cognate ligand in the presence of Mg2+. Riboswitch functioning is also hypothesized to be under kinetic control requiring large cognate ligand concentrations. We ask the question under thermodynamic conditions, can the riboswitches populate structures similar to the holo-form only in the presence of Mg2+ and absence of cognate ligand binding. We addressed this question using thiamine pyrophosphate (TPP) riboswitch as a model system and computer simulations using a coarse-grained model for RNA. The folding free energy surface (FES) shows that with the initial increase in Mg2+ concentration ([Mg2+]), the aptamer domain (AD) of TPP riboswitch undergoes a barrierless collapse in its dimensions. On further increase in [Mg2+], intermediates separated by barriers appear on the FES, and one of the intermediates has a TPP ligand-binding competent structure. We show that site-specific binding of the Mg2+ aids in the formation of tertiary contacts. For [Mg2+] greater than physiological concentration, AD folds into a structure similar to the crystal structure of the TPP holo-form even in the absence of the TPP ligand. The folding kinetics shows that TPP AD populates an intermediate due to the misalignment of two arms present in the structure, which acts as a kinetic trap, leading to larger folding timescales. The predictions of the intermediate structures from the simulations are amenable for experimental verification.Biomedical applications of graphene in tumor and bacterial treatment have become cutting-edge fields due to its unique physical and chemical properties. However, a mechanistic understanding of the interactions and reactions between graphene-based material and biological systems such as lipid membranes remains elusive, especially at the molecular level. By using the unique field-induced droplet ionization mass spectrometry and cryogenic electron microscopy methodologies, we reveal the oxidation products of monolayer lipid membranes at the air-water interface and the change in the morphology of bilayer lipid membranes in an aqueous solution caused by the incorporation of graphene oxide bearing π-conjugated carbon radicals [hydrated graphene oxide (hGO)]. We discovered that hGO is an efficient source of hydroxyl radicals and that it is not only the incorporation of the hGO sheets but also the irregular packing of the lipid oxides from the hydroxyl radical oxidation that causes the structural distortions of the liposomes.