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Furthermore, the results of this study demonstrate the potential of MIET for simultaneous imaging of two close-by membranes and thus three-dimensional reconstruction of the cell shape.Highly stable antioxidant dispersions were designed on the basis of ring-opened ellagic acid (EA) intercalated into MgAl-layered double hydroxide (LDH) nanoparticles. The morphology of the composite was delicately modified with ethanolic washing to obtain EtOH-EA-LDH with a high specific surface area. The colloidal stability was optimized by surface functionalization with positively charged polyelectrolytes. Polyethyleneimine (PEI), protamine sulfate (PS) and poly(acrylamide-co-diallyl dimethyl ammonium chloride) (PAAm-co-DADMAC) was adsorbed onto the surface of the oppositely charged EtOH-EA-LDH leading to charge neutralization and overcharging at appropriate doses. Formation of adsorbed polyelectrolyte layers provided remarkable colloidal stability for the EtOH-EA-LDH. Modification with PEI and PAAm-co-DADMAC outstandingly improved the resistance of the particles against salt-induced aggregation with a critical coagulation concentration value above 1 M, while only limited stability was achieved by covering the nanoparticles with PS. The high antioxidant activity of EtOH-EA-LDH was greatly preserved upon polyelectrolyte coating, which was proved in the scavenging of radicals in the test reaction applied. Hence, an active antioxidant nanocomposite of high drug dose and remarkable colloidal stability was obtained to combat oxidative stress in systems of high electrolyte concentrations.In this article, we describe calculations on the absorption spectrum of cobalt(ii) porphyrin, using density functional (DFT) and multireference n-electron valence perturbation (NEVPT) theories. selleck With these calculations, we describe the lowest-energy states of doublet and quartet spin multiplicities, the excited states that originate the Q and B bands of porphyrins, some higher-energy π-π* excitations and charge-transfer states, HOMO-LUMO gaps, and ionisation potentials. Results undoubtedly show that the position of B band is essentially independent on the DFT functional, while the Q band is better described by pure functionals, and these bands do not depend on the initial state of the transition (whether doublet or quartet) as well. However, other excitation energies, orbital energies, and ionisation potentials strongly depend on the functional, in some cases varying more than 2 eV. Based on these results we conclude that one should not use the UV-Vis spectrum of metalloporphyrins to benchmark density functionals, mainly those properties related to coordination with the metallic ion. Furthermore, the results show that functionals that yield correct spectra may be based on an incorrect ground state description. Moreover, we reinforce that one must be skeptical about the reference chosen to benchmark electronic structure calculations, such as DFT functionals and active spaces for multireference calculations.A carbon-dioxide-responsive organic-inorganic nanocomposite membrane based on a through-hole anodic aluminum oxide (AAO) template was constructed. The composite was prepared via a surface-initiated reversible addition-fragmentation chain-transfer (SI-RAFT) polymerization strategy to achieve the grafting of poly(methyl methacrylate-co-2-(diethylamino)ethyl methacrylate) brushes on the AAO membrane. The grafted polymer chain length could be controlled based on the feed ratio between the free chain transfer agent (CTA) and reactive monomer, e.g., methyl methacrylate and 2-(diethylamino)ethyl methacrylate, resulting in a membrane that features adjustable water permeability. Importantly, the membrane pore size and surface wettability could be switched from hydrophobic to hydrophilic upon the introduction of carbon dioxide and nitrogen gases. This allowed for the nanocomposite membrane to be utilized for controlled water flux and oil/water emulsion separation. The simple fabrication methodology as well as sustainable gaseous stimulus will be useful for the construction of future smart membranes.We use a variety of computational methods to characterize and compare the hydrogen atom transfer (HAT) and epoxidation reaction pathways for oxidation of cyclohexene by an iron(iv)-oxo complex. Previous B3LYP calculations have led to predictions that both alcohol (from the HAT route) and epoxide should be formed in similar amounts, which was not in agreement with experiment where only the HAT product was observed. We show here that ab initio calculations which can take both static and dynamic correlation into account are needed to explain the experimentally observed dominance of the HAT process. Since these systems do not have very strong multireference character we have also tested different flavours of local coupled cluster methods. We suggest that further improvements are necessary before they can provide highly accurate results for these systems.In organic synthesis, transition-metal and photoredox-catalysis-based reaction systems are emerging trends for the construction of C-S bonds. Many review articles have recently appeared in this field; however, we present herein an overview of metal-free C-S coupling reactions using thiols or disulfides as sulfur surrogates. The oxidants we have considered include peroxides, tert-butyl nitrite (TBN), DDQ, iodine reagents, and molecular oxygen. In addition, selective electrochemical oxidative transformations are also covered with mechanistic details.An efficient and concise catalyst-free one-pot synthetic protocol for obtaining dihydroisoquinoline derivatives has been developed via the three-component condensation of isoquinolines with β-keto acids and sulfonyl chlorides. This transformation involving decarboxylative dearomatization worked well under mild and water-mediated conditions. The protocol tolerates diverse functional groups, furnishing the dihydroisoquinoline products in good to excellent yields.Communication is one of the most remarkable behaviors in the living world. It is an important prerequisite for building an artificial cell which can be considered as alive. Achieving complex communicative behaviors leveraging synthetic particles will likely fill the gap between artificial vesicles and natural counterpart of cells and allow for the discovery of new therapies in medicine. In this review, we highlight recent endeavors for constructing communication with synthetic particles by revealing the principles underlying the communicative behaviors. Emergent progress using active particles to achieve communication is also discussed, which resembles the dynamic and out-of-equilibrium properties of communication in nature.
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