47 research outputs found
Solvation Structure of Surface-Supported Amine Fragments: A Molecular Dynamics Study
Amine-grafted
silica gel is an efficient heterogeneous catalyst for the Knoevenagel
condensation and draws much attention in green chemistry for applications
like heavy metal adsorption and CO<sub>2</sub> fixation. Despite its
successful usage in diverse areas, fundamental questions remain on
how the silica substrate affects the local chemical environment of
the tethered amines. In this work, we use all-atom molecular dynamics
simulation to investigate the solvation structures of two primary
amines tethered onto a silica surface at different pHs of aqueous
solutions. The atomic density profiles in the solvation shell are
analyzed with a spherical harmonics expansion method for both isolated
and silica-supported amines in different aqueous environments. The
simulation results provide direct evidence for the strong influence
of the silica surface on the hydration structure that is often ignored
in the theoretical analysis of surface reactions. The surface effect
becomes less prominent on the tethered amine as the alkyl chain length
increases
Mechanistic Insights into the Pore Confinement Effect on Bimolecular and Monomolecular Cracking Mechanisms of <i>N</i>‑Octane over HY and HZSM‑5 Zeolites: A DFT Study
Bimolecular and monomolecular
cracking mechanisms of alkanes simultaneously
occur and have a competitive relationship, which strongly influences
the product distribution. In this work, the density functional theory
(DFT) calculation is first carried out to elucidate two cracking mechanisms
in HZSM-5 and HY zeolites. It is found that the overall apparent reaction
barrier for the monomolecular cracking reaction at 750 K in the HZSM-5
zeolite is 5.30 kcal/mol, much lower than that (23.12 kcal/mol) for
bimolecular cracking reaction, indicating that the monomolecular mechanism
is predominant in the HZSM-5 zeolite. In contrast, the bimolecular
mechanism is predominant in the HY zeolite because of a lower apparent
reaction barrier energy barrier (6.95 kcal/mol) for bimolecular cracking
reaction than that (24.34 kcal/mol) for the monomolecular cracking
reaction. Moreover, the intrinsic reason for the different mechanisms
is further elucidated. The confinement effect can effectively decrease
the energy barrier when the size of transition states is comparable
to the pore size of zeolite. The insights in this work will be of
great significance to the understanding of confinement on catalytic
cracking mechanism and to the design of highly efficient cracking
catalysts
Chemical and Radiation Stability of Ionic Liquids: A Computational Screening Study
Using
a variety of density functional theory (DFT) methods, we present a
systematic computational screening effort to analyze the chemical
and radiation stability for a large number of anions and cations that
constitute room-temperature ionic liquids (RTILs). We compute various
electronic properties such as the HOMO–LUMO gap, the ionization
potential, and the electron affinities for a large library of ions (42
cations and 42 anions). The theoretical analysis provides the most comprehensive characterization of the
chemical and radiation stability of individual ions in RTILs to date.
Our calculations reveal that cation stability is closely related to
constituent alkyl chain length and branching, whereas the anion stability
is mostly dictated by ion size and electronegativity. Furthermore,
these calculations show that the ωB97XD functional is the
most internally consistent for predicting the chemical and radiation stability.
These calculations establish a chemical stability database and a theoretical
procedure for further experimental and computational studies of RTILs
Growth Mechanism of Highly Branched Titanium Dioxide Nanowires via Oriented Attachment
Understanding fundamental crystal nucleation and growth
mechanisms
is critical for producing materials with controlled size and morphological
features and uncovering structure–function relationships in
these semiconducting oxides. Under hydro-solvothermal conditions,
uniform branched and spherulitic TiO<sub>2</sub> rutile nanostructures
were formed via (101) twins. On the basis of detailed, high-resolution
scanning electron microscopy and transmission electron microscopy
analyses, we propose a mechanism of branched growth and the (101)
twin formation via oriented attachment and subsequent transformation
from anatase to rutile
Correlation between PLK4 expression and clinicopathologic parameters in HCC.
a<p>Chi-square test;</p>b<p>patients were divided according to the median age; AFP, alpha-fetoprotein; HBsAg, hepatitis B surface antigen; PLK4, polo-like kinase 4.</p
Univariate analysis of different prognostic factors in 246 HCC patients.
<p>CI, confidence interval; HR, hazard ratio; AFP, alpha-fetoprotein; HBsAg, hepatitis B surface antigen; PLK4,polo-like kinase4.</p
The expression of PLK4 in HCC by IHC.
<p>The micrographs showed negative (<b>A</b>), weak (<b>B</b>), moderate (<b>C</b>), strong (<b>D</b>) staining of PLK4 in tumor tissues, as well as strong (<b>E</b>) staining of normal liver tissues. (Left panel: magnification ×40; Right panel: magnification ×400.) <b>F.</b> Reproducibility of the measurement in all 246 patients was calculated by the Wilcoxon matched paired test.</p
Analysis of PLK4 protein expression in relation to overall survival and disease-free survival of subclassified HCC patients.
<p>In term of overall survival and disease-free survival, subgroup analysis indicated that PLK4 had prognostic role when classified by the following variables: tumor size (A–B), AFP (C–D), stage (III–IV) (E–F) (log-rank test).</p
The mRNA and protein expression of PLK4 in HCC by qRT-PCR and western blot. A.
<p>Down-regulated expression of PLK4 mRNA was detected by qRT-PCR in 13 out of 20 HCC cases. The relative PLK4 mRNA expression was indicated by histogram (T, tumor tissue; N, the corresponding adjacent non-tumor liver tissues). <b>B.</b> The PLK4 mRNA levels was significantly decreased in HCC as determined by the Wilcoxon matched paired test. <b>C.</b> Decreased expression of PLK4 protein was shown by western blot in 15 out of 20 HCC tumor tissues. The relative PLK4 protein expression was shown. GAPDH was used as loading control. <b>D.</b> Intensity of PLK4 normalized to GAPDH was indicated Wilcoxon matched paired test.</p
Multivariate analysis of overall and disease-free survival rates of HCC patients.
<p>β, Regression coefficient; SE, standard error; CI, confidence interval; AFP, alpha-fetoprotein; PLK4, polo-like kinase4.</p