DBU-Promoted [4 + 4] Domino Cycloaddition of Ynones with Benzylidenepyrazolones To Access Eight-Membered Cyclic Ethers

An efficient DBU-promoted [4 + 4] domino annulation reactions of ynones and benzylidenepyrazolones has been developed. This process resulted finally in the formation of eight-membered cyclic ethers in moderate to good yields. The easy availability of starting materials and the simple cyclization procedure make this approach suitable for the preparation of a wide range of useful oxocino [2,3-<i>c</i>] pyrazoles

XRD data of raw lotus fibers and lotus fibers after being treated with hydrogen peroxide

XRD data of raw lotus fibers and lotus fibers after being treated with hydrogen peroxid

DBU-Promoted [4 + 4] Domino Cycloaddition of Ynones with Benzylidenepyrazolones To Access Eight-Membered Cyclic Ethers

An efficient DBU-promoted [4 + 4] domino annulation reactions of ynones and benzylidenepyrazolones has been developed. This process resulted finally in the formation of eight-membered cyclic ethers in moderate to good yields. The easy availability of starting materials and the simple cyclization procedure make this approach suitable for the preparation of a wide range of useful oxocino [2,3-<i>c</i>] pyrazoles

Supplementary Material for RSC Open Science 23.6.2017

Supplementary Material for RSC Open Science 23.6.201

Molecular Mechanism of Wide Photoabsorption Spectral Shifts of Color Variants of Human Cellular Retinol Binding Protein II

Color variants of human cellular retinol binding protein II (hCRBPII) created by protein engineering were recently shown to exhibit anomalously wide photoabsorption spectral shifts over ∼200 nm across the visible region. The remarkable phenomenon provides a unique opportunity to gain insight into the molecular basis of the color tuning of retinal binding proteins for understanding of color vision as well as for engineering of novel color variants of retinal binding photoreceptor proteins employed in optogenetics. Here, we report a theoretical investigation of the molecular mechanism underlying the anomalously wide spectral shifts of the color variants of hCRBPII. Computational modeling of the color variants with hybrid molecular simulations of free energy geometry optimization succeeded in reproducing the experimentally observed wide spectral shifts, and revealed that protein flexibility, through which the active site structure of the protein and bound water molecules is altered by remote mutations, plays a significant role in inducing the large spectral shifts

Regio- and Diastereoselective Construction of Spirocyclopenteneoxindoles through Phosphine-Catalyzed [3 + 2] Annulation of Methyleneindolinone with Alkynoate Derivatives

A phosphine-catalyzed [3 + 2] annulation of isatin-derived α,β-unsaturated ketones with alkynoates for the synthesis of cyclopentene spiro-oxindole skeletons has been developed. This reaction afforded the desired products in high to excellent yields (up to 99%) with high regioselectivity and moderate to high diastereoselectivities (up to 20:1). This strategy allows facile diastereoselective preparation of biologically important spiro-(cyclopentene) oxindoles containing three contiguous stereocenters, including the quaternary stereogenic center joining the two rings

Molecular Mechanism of Wide Photoabsorption Spectral Shifts of Color Variants of Human Cellular Retinol Binding Protein II

Color variants of human cellular retinol binding protein II (hCRBPII) created by protein engineering were recently shown to exhibit anomalously wide photoabsorption spectral shifts over ∼200 nm across the visible region. The remarkable phenomenon provides a unique opportunity to gain insight into the molecular basis of the color tuning of retinal binding proteins for understanding of color vision as well as for engineering of novel color variants of retinal binding photoreceptor proteins employed in optogenetics. Here, we report a theoretical investigation of the molecular mechanism underlying the anomalously wide spectral shifts of the color variants of hCRBPII. Computational modeling of the color variants with hybrid molecular simulations of free energy geometry optimization succeeded in reproducing the experimentally observed wide spectral shifts, and revealed that protein flexibility, through which the active site structure of the protein and bound water molecules is altered by remote mutations, plays a significant role in inducing the large spectral shifts

Photolysis versus Photothermolysis of N₂O on a Semiconductor Surface Revealed by Nonadiabatic Molecular Dynamics

Identifying photolysis and photothermolysis during a photochemical reaction has remained challenging because of the highly non-equilibrium and ultrafast nature of the processes. Using state-of-the-art ab initio adiabatic and nonadiabatic molecular dynamics, we investigate N2O photodissociation on the reduced rutile TiO2(110) surface and establish its detailed mechanism. The photodecomposition is initiated by electron injection, leading to the formation of a N2O– ion-radical, and activation of the N2O bending and symmetric stretching vibrations. Photothermolysis governs the N2O dissociation when N2O– is short-lived. The dissociation is activated by a combination of the anionic excited state evolution and local heating. A thermal fluctuation drives the molecular acceptor level below the TiO2 band edge, stabilizes the N2O– anion radical, and causes dissociation on a 1 ps timescale. As the N2O– resonance lifetime increases, photolysis becomes dominant since evolution in the anionic excited state activates the bending and symmetric stretching of N2O, inducing the dissociation. The photodecomposition occurs more easily when N2O is bonded to TiO2 through the O rather than N atom. We demonstrate further that a thermal dissociation of N2O can be realized by a rational choice of metal dopants, which enhance p–d orbital hybridization, facilitate electron transfer, and break N2O spontaneously. By investigating the charge dynamics and lifetime, we provide a fundamental atomistic understanding of the competition and synergy between the photocatalytic and photothermocatalytic dissociation of N2O and demonstrate how N2O reduction can be controlled by light irradiation, adsorption configuration, and dopants, enabling the design of high-performance transition-metal oxide catalysts

Additional file 2: of Time series model for forecasting the number of new admission inpatients

Predicted values. The table showed the predicted monthly and daily new admission inpatients from three models. (XLS 54 kb

Additional file 1: of Time series model for forecasting the number of new admission inpatients

Original data. The table showed the original data including the number of daily (1/4/2016–2/10/2016) and monthly (1/2010–10/2016) new admission inpatients. (XLS 33 kb