Notes

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A strategy to obtain chiral silica using an achiral stereoregular polymer with polyhedral oligomeric silsesquioxane (POSS) side chains is described herein. The preferred helical conformation of the POSS-containing polymer could be achieved by mixing isotactic polymethacrylate-functionalized POSS (it-PMAPOSS) and a chiral dopant. The array structure of POSS molecules, which are placed along the helical conformation, is memorized even after removing the chiral dopant at high temperatures, leading to a chiral silica compound with exclusive optical activity after calcination.Deciphering the origins of the chemistry that supports life has frequently centered on determining prebiotically plausible paths that produce the molecules found in biology. What has been less investigated is how the energy released from the breakdown of foodstuff is coupled to the persistence of the protocell. To gain better insight into how such coupled chemistry could have emerged prebiotically, we probed the reactivity of the ribodinucleotide NAD+ with small organic molecules that were previously identified as potential constituents of protometabolism. We find that NAD+ is readily reduced nonenzymatically by α-keto acids, such as pyruvate and oxaloacetate, during oxidative decarboxylation. In the presence of FAD and a terminal electron acceptor, the consumption of α-keto acids by NAD+ initiates a plausible prebiotic electron transport chain. The observed reactivity suggests that components of the RNA world were capable of initiating the chemistry needed to capture the energy released from catabolism to drive anabolism.The complexes [RhX(COD)]2 (X = Cl, Br; COD = 1,5-cyclooctadiene) form cocrystals with σ-hole iodine donors. X-ray diffraction studies and extensive theoretical considerations indicate that the d z 2-orbitals of two positively charged rhodium(I) centers provide sufficient nucleophilicity to form a three-center halogen bond (XB) with the σ-hole donors. The two metal centers function as an integrated XB acceptor, providing assembly via a metal-involving XB.Photoresponsive polymers have attracted extensive attention due to their tunable functionalities and advanced applications; thus, it is significant to develop facile in situ synthesis strategies, extend polymers family, and establish various applications for photoresponsive polymers. Herein, we develop a catalyst-free spontaneous polymerization of dihaloalkynes and disulfonic acids without photosensitive monomers for the in situ synthesis of photoresponsive polysulfonates at room temperature in air with 100% atom economy in high yields. The resulting polysulfonates could undergo visible photodegradation with strong photoacid generation, leading to various applications including dual-emissive or 3D photopatterning, and practical broad-spectrum antibacterial activity. The halogen-rich polysulfonates also exhibit a high and photoswitched refractive index and could undergo efficient postfunctionalizations to further expand the variety and functionality of photoresponsive heteroatom-containing polyesters.For common hydrogenation chemistries that occur at high temperatures (where H2 is adsorbed and activated at the same surface which the substrate must also adsorb for reaction), there is often little consensus on how the reactions (e.g., hydro(deoxy)genation) actually occur. We demonstrate here that an electrocatalytic palladium membrane reactor (ePMR) can be used to study hydrogenation reaction mechanisms at ambient temperatures, where the catalyst does not necessarily undergo structural reorganization. The ePMR uses electrolysis and a hydrogen-selective palladium membrane to deliver reactive hydrogen to a catalyst surface in an adjacent compartment for reaction with an organic substrate. This process forms the requisite metal-hydride surface for hydrogenation chemistry, but at ambient temperature and pressure, and without a H2 source. We demonstrate the utility of this analytical tool by studying the hydrogenation of benzaldehyde at palladium nanocubes with dimensions of 13-24 nm. This experimental design enabled us to resolve that the alcohol product forms at the facial sites, whereas the hydrodeoxygenation step occurs at edge sites. These observations enabled us to develop the first site-specific definition of how a carbonyl species undergoes hydro(deoxy)genation.Here, reduced graphene oxide (r-GO) nanosheets were embedded in an organosilica network to assemble an ultrathin hybrid membrane on the tubular ceramic substrate. With the organosilica nanocompartments inside the r-GO stacks and the intensified polymerization, r-GO sheets endow the as-prepared hybrid membranes with high H2 and CO2 separation performance. The resulting selectivities of H2/CH4 and CO2/CH4 are found to be 223 and 55, respectively, together with gas permeance of approximately 2.5 × 10-7 mol·m-2·s-1·Pa-1 for H2 and 6.1 × 10-8 mol·m-2·s-1·Pa-1 for CO2 at room temperature and 0.2 MPa. To separate larger molecules from H2, the H2/C3H8 and H2/i-C4H10 selectivities are as high as 1775 and 2548, respectively. Moreover, at 150 °C and 0.2 MPa, the hybrid membrane retains high separation performances with ideal selectivities higher than 200 and 30 for H2/CH4 and CO2/CH4, respectively, which are attractive for gas separation and purification of practical applications.The amphiphile PS-750-M generates stable, phosphine ligand-free, and catalytically active ultrasmall Pd(II) nanoparticles (NPs) from Pd(OAc)2, preventing their precipitation, polymerization, and oxidation state changes. PS-750-M directly interacts with Pd(II) NP surfaces, as confirmed by high-resolution mass spectrometry and IR spectroscopy, resulting in their high stability. The Pd cations in NPs are most likely held together by hydroxides and acetate ions. The NPs were characterized by HRTEM, revealing their morphology and particle size distribution, and by HRMS and IR, providing evidence for NP-amphiphile interaction. The NP catalytic activity was examined in the context of oxidative Mizoroki-Heck-type couplings in water at room temperature. Hot filtration, hot extraction, and three-phase tests indicate heterogeneous catalysis occurring at the micellar interface rather than homogeneous catalysis occurring in the solution. NMR studies indicate that the catalytic activity stems from metal cation-π interactions of the styrene along with transmetalation by the arylboronic acid, followed by insertion and β-H elimination to furnish the coupled product along with the reoxidation of Pd by benzoquinone to complete the catalytic cycle. This method is very mild and sustainable, both in terms of NP synthesis and subsequent catalysis, and shows broad substrate scope while circumventing the need for organic solvents for this important class of couplings.Ring-shaped Re(I) multinuclear complexes (Re(I) rings) in which Re(I)-diimine-biscarbonyl complexes are connected to each other through bisphosphine bridging ligands exhibit very suitable photophysical and electrochemical properties as redox photosensitizers. We developed two approaches for synthesizing Re(I) rings connected with a Ru(II) complex cyclization of a linear Re(I) trinuclear complex connected with a Ru(II) complex and Mizoroki-Heck coupling of a ring-shaped Re(I) trinuclear complex and a Ru(II) complex. Photophysical measurements of these heteromultinuclear complexes and comparisons with their model complexes indicated that they exhibit efficient light-harvesting abilities, where energy transfer from the excited ring-shaped Re(I) trinuclear complex unit to the Ru(II) complex unit proceeds efficiently.A series of D-π-A + pyridinium compounds, in which D = -NPh2 and A+ = -PyMe+ are linked by various amounts of linear phenyl spacers, were strategically designed and synthesized. Their characterization revealed the presence of excited-state intramolecular charge transfer (ESICT) that triggers a corresponding response from the counterion. In medium and strong polar solvents, the fast solvent relaxation occurring after ESICT overwhelms the counterion effect, showing typical emission solvatochromism. In weakly polar solvents, ESICT induces counteranion migration for electrostatic stabilization, the time scale of which is dependent on the radius of the counteranion, the length of the π-linker, and the viscosity of the solvent. In low-viscosity organic solvents such as toluene, counteranion migration occurs within several tens to hundreds of picoseconds, resulting in a time-dependent continuous emission that can be resolved from the spectral temporal evolution. Concrete evidence for this is provided by the chemical synthesis of a D-π-A + pyridinium-sulfur trioxide- zwitterion, where anion migration is restricted due to its internally locked ion pair. As a result, only a single emission band can be observed. These comprehensive studies prove that the ion migration process may be significant for a wide range of ESICT-type ionic fluorophores. Such an ionic movement, triggered by optically pumped ESICT of the D-π-A + dyad, is similar to the molecular machine driven by the redox reaction, but with a facile access and fast response.Naturally occurring metals, such as calcium, catalytically activate the intermonomer β-glycosidic bonds in long chains of cellulose, initiating reactions with volatile oxygenates for renewable applications. In this work, the millisecond kinetics of calcium-catalyzed reactions were measured via the method of the pulse-heated analysis of solid and surface reactions (PHASR) at high temperatures (370-430 °C) to reveal accelerated glycosidic ether scission with a second-order rate dependence on the Ca2+ ions. First-principles density functional theory (DFT) calculations were used to identify stable binding configurations for two Ca2+ ions that demonstrated accelerated transglycosylation kinetics, with an apparent activation barrier of 50 kcal mol-1 for a cooperative calcium-catalyzed cycle. The agreement of the mechanism with calcium cooperativity to the experimental barrier (48.7 ± 2.8 kcal mol-1) suggests that calcium enhances the reactivity through a primary role of stabilizing charged transition states and a secondary role of disrupting native H-bonding.Amorphous silica-aluminas (ASAs) are important solid catalysts and supports for many industrially essential and sustainable processes, such as hydrocarbon transformation and biorefining. www.selleckchem.com/btk.html However, the wide distribution of acid strength on ASAs often results in undesired side reactions, lowering the product selectivity. Here we developed a strategy for the synthesis of a unique class of ASAs with unvarying strength of Brønsted acid sites (BAS) and Lewis acid sites (LAS) using double-flame-spray pyrolysis. Structural characterization using high-resolution transmission electron microscopy (TEM) and solid-state nuclear magnetic resonance (NMR) spectroscopy showed that the uniform acidity is due to a distinct nanostructure, characterized by a uniform interface of silica-alumina and homogeneously dispersed alumina domains. The BAS population density of as-prepared ASAs is up to 6 times higher than that obtained by classical methods. The BAS/LAS ratio, as well as the population densities of BAS and LAS of these ASAs, could be tuned in a broad range.
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