165 research outputs found
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 N<sub>2</sub>O 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
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