Control experiments and density functional theory studies point to the crucial role of the cooperation between gold and the SPO ligands on the selectivity toward the hydrogenation of the C═O group in benzaldehyde.In this work, two end-charged cyclic peptide nanotubes (CPNTs) embedded in 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine (POPE) were designed to simulate transmembrane ion channels. Density functional theory (DFT) computations at the level of M06-2X/6-31G give different assembling modes of the negatively charged ELWL-CPNT and positively charged RLWL-CPNT as (L-L)(D-L)(D-D)(L-L)(D-D)(L-L)(D-D) and (D-D)(L-L)(D-D)(L-L)(D-D)(L-L)(D-D), respectively. Molecular dynamics (MD) simulations indicate that a charge at a CPNT end obviously affects the structure of the channel water chain and the diffusion behavior of K+. The regions with the highest probability of H-bond defects in the channel water chains are gap5 and gap2 in ELWL/POPE-CPNT and RLWL/POPE-CPNT, respectively. K+ can easily enter either CPNT by desolvation, and behaves more actively in RLWL/POPE-CPNT, shuttling rapidly and frequently between an α-plane zone and an adjacent midplane region. Results of this work reveal that a charge at the end of an ionic channel may significantly alter the transport characteristics of the channel.A general and efficient method for the deconjugative α-alkylation of α,β-unsaturated aldehydes promoted by a synergistic effect between tBuOK and NaH, which considerably increases the reaction rate under mild conditions, is reported. The β,γ-unsaturated aldehyde, resulting from the α-alkylation, is transformed in high yield into the corresponding allyl acetate via a lead(IV) acetate-mediated oxidative fragmentation. This strategy could be used for the construction of the carbon skeleton of a wide variety of alkyl or arylterpenoids.The thermal unimolecular decomposition of 2-methyltetrahydrofuran (2-MTHF) was studied behind reflected shock waves in a single-pulse shock tube over the temperature range of 1179-1361 K and pressure range of 9-17 atm. Methane, ethylene, ethane, 1,3-butadiene, propylene, acetaldehyde, and acetylene were identified as products in the decomposition of 2-MTHF. A reaction scheme was proposed to explain the mechanism for the observed products. The experimentally determined rate coefficients were best fit to an Arrhenius expression for the overall decomposition and is represented as ktotalexp(1179-1361 K) = (3.23 ± 0.59) × 1011 s-1 exp(-51.3 ± 1.4 kcal mol-1/RT). Quantum chemistry methods were used to calculate the energetics and kinetics of various possible unimolecular dissociation pathways involved in the thermal decomposition of 2-MTHF. The initial decomposition of 2-MTHF occurs predominantly via ring-methyl (C-CH3) single bond fission, leading to the formation of tetrahydrofuran (C4H7O) radical, and methyl radical was found to be the major reaction compared to all the possible initial bond fission, ring opening, and molecular elimination channels. The temperature-dependent rate coefficients for the unimolecular dissociation of 2-MTHF were calculated using the RRKM (Rice-Ramsperger-Kassel-Marcus) theory in combination with the CCSD(T)/cc-pVTZ//B3LYP/cc-pVTZ level of electronic structure calculations over the temperature range of 800-1500 K. The computed high-pressure limiting rate coefficients for the initial decomposition of 2-MTHF through C-CH3 single bond fission channel were found to be ∼2 times higher in the temperatures between 800 and 900 K, and above this temperature, they agree well with the values reported in the literature.We present the first examples of tethered silanoxyiodination reactions of allylic alcohols. The products are useful silanediol organoiodide synthons and are formed with high regioselectivity and diastereocontrol. The reaction is scalable greater than 10-fold without loss of yield or selectivity. Furthermore, the products are starting materials for further transformations, including deiodination, C-N bond installation, epoxide synthesis, and desilylation. DFT calculations provide a basis for understanding the exquisite 6-endo selectivity of this silanoxyiodination reaction and show that the observed products are both kinetically and thermodynamically preferred.A palladium-catalyzed annulation reaction of 2-iodobiphenyls with 2-halogenoanilines has been developed. A variety of 2-iodobiphenyls and 2-halogenoanilines can undergo this transformation. Diversified tribenzo[b,d,f]azepine derivatives can be synthesized in moderate to excellent yields according to this method.Ionic liquids are well known for their high gas absorption capacity. It is shown that this is not a solvent constant, but can be enhanced by another factor of 10 by pore confinement, here of the ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate (EmimOAc) in the pores of carbon materials. A matrix of four different carbon compounds with micro- and mesopores as well as with and without nitrogen doping is utilized to investigate the influence of the carbons structure on the nitrogen uptake in the pore-confined EmimOAc. In general, the absorption is most improved for IL in micropores and in nitrogen-doped carbon. This effect is so large that it is already seen in TGA and DSC experiments. Due to the low vapor pressure of the IL, standard volumetric sorption experiments can be used to quantify details of this effect. It is reasoned that it is the change of the molecular arrangement of the ions in the restricted space of the pores that creates additional free volume to host molecular nitrogen.A 3D coordination polymer, [Gd(HCOO)(C2O4)]n was prepared. Its magnetocaloric effect (MCE) (32.7 J K-1 kg-1 at 2 K and 2 T) is significantly larger than that of commercial Gd3Ga5O12 (GGG) (14.6 J kg-1 K-1 at 2 K and 2 T), while its thermal conductivity (9.9 W m-1 K-1 at 3 K) is comparable to that of the commercial GGG (about 10 W m-1 K-1 at 3 K).A nodal-line semimetal (NLSM) is suppressed in the presence of spin-orbit coupling unless it is protected by a nonsymmorphic symmetry. We show that two-dimensional (2D) materials can realize robust NLSMs when vacancies are introduced on the lattice. As a case study we investigate borophene, a boron honeycomb-like sheet. https://www.selleckchem.com/products/rxc004.html While the Dirac cones of pristine borophene are shown to be gapped out by spin-orbit coupling and by magnetic exchange, robust nodal lines (NLs) emerge in the spectrum when selected atoms are removed. We propose an effective 2D model and a symmetry analysis to demonstrate that these NLs are topological and protected by a nonsymmorphic glide plane. Our findings offer a paradigm shift to the design of NLSMs instead of searching for nonsymmorphic materials, robust NLSMs may be realized simply by removing atoms from ordinary symmorphic crystals.