Dependence of the closed-shell repulsive interaction on the overlap of the electron densities

The relationship between the closed-shell repulsive interactions and overlap of the electron densities is investigated. It is found that the repulsive interactions vary in almost direct proportion to the absolute size of the density overlaps.     

Fragmentation of wastewater sludge floc by planar ice front

Floc size has substantial impact on sludge dewaterability, which might be increased or reduced after freezing and thawing. It is commonly assumed that floc size would be increased by low-speed freezing, with a planar ice front rejecting most flocs ahead of it to form large aggregates. We demonstrate in this work that an advancing planar ice front can not only engulf an activated sludge floc of size 3030 mum, but also fragment it. During floc freezing, when the ice engulfed a thin layer of floc, the latter would be pulled apart vertically by the action of the former. This particular portion of floc was then axially elongated and fixed in the frozen layer, with accumulated force pushing upward. In the present test the floc's vertical length was increased by over 92% and its width decreased by 37% over freezing. The force measurement and floc morphology tracking revealed that the force gradient that pulled apart the floc was 0.0027 N/m. The floc under investigation was fragmented at the point where the normal stress acting on the interior network exceeded 8 Pa.     

Calcium/poly(9,9-dioctylfluorene) interaction: a theoretical study

The geometric and electronic structures of poly(9,9-dioctylfluorene) (PFO) oligomer interacting with Ca atoms were studied using M?ller-Plesset perturbation theory. A weak interaction with little charge transfer and with a relatively long Ca-C distance (about 4.0 Angstrom) was found when only one Ca atom was attached to a PFO unit. However, when two Ca atoms were adsorbed at a PFO unit, a strong interaction with a shorter Ca-C distance (about 2.67 Angstrom) took place with considerable charge transfer from the Ca atom to the PFO, resulting in significant deformation in the backbone of the PFO oligomer. In the latter case, the frontier orbitals of the PFO were modified. However, the deformed PFO and its modified frontier orbitals could be recovered when oxygen was added, which is in good agreement with experimental observation.     

Nucleation and growth mechanism of Pd/Pt bimetallic clusters in sodium bis(2-ethylhexyl)sulfosuccinate (AOT) reverse micelles as studied by in situ X-ray absorption spectroscopy

We report in situ X-ray absorption spectroscopy (XAS) investigations on the formation of palladium-platinum (Pd/Pt) bimetallic clusters at the early stage within the water-in-oil microemulsion system of water/AOT/n-heptane. The reduction of palladium and platinum ions and the formation of corresponding clusters are monitored as a function of dosage of reducing agent, hydrazine (N(2)H(5)OH). Upon successive addition of the reducing agent, hydrazine (N(2)H(5)OH), five distinguishable steps are observed in the formation process of Pd/Pt clusters at the early stage. Both in situ X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analysis for both the Pd K-edge and Pt L(III)-edge revealed the formation of Pd/Pt bimetallic clusters. A corresponding structural model is proposed for each step to provide a detailed insight into the nucleation and growth mechanism of Pd/Pt bimetallic clusters. We also discussed the atomic distribution of Pd and Pt atoms in Pd/Pt bimetallic clusters based on the calculated XAS structural parameters.     

A reliable synthesis of 2- and 6-amino-β-cyclodextrin and permethylated-β-cyclodextrin

A new, reliable method for the introduction of an amine group at positions 2 or 6 of β-cyclodextrin and permethyl-β-cyclodextrin is described. It involves selective tosylation followed by azide substitution and almost quantitative reduction with triphenylphosphine followed by hydrolysis of the phosphinimine intermediate.     

De Novo Design and Synthesis of a γ‐Turn Peptidomimetic Scaffold and Its Application as JNK3 Allosteric Ligand

As a way to develop a neuroprotective agent for the JNK3‐JIP1‐binding site, peptidomimetics of JIP‐1 as JNK3 allosteric regulators have been examined. The study consisted of in silico scaffold hopping, molecular docking, solution and solid‐phase peptide syntheses, and K_d measurements using surface plasmon resonance. As a peptidomimetic of JIP1, heptamer mimetic 16 (K_d=2.72 μm ) displayed a higher affinity than decamer JIP1 (K_d=23.6 μm ). The high affinity of 16 implies that the characteristic γ‐turn mimetic structure, “”Φ‐X‐Φ“ hydrophobic motif in 16 , increased its affinity toward the JIP‐site of JNK3.     

Sensitive and Multiplexed On‐chip microRNA Profiling in Oil‐Isolated Hydrogel Chambers

Although microRNAs (miRNAs) have been shown to be excellent indicators of disease state, current profiling platforms are insufficient for clinical translation. Here, we demonstrate a versatile hydrogel‐based microfluidic approach and novel amplification scheme for entirely on‐chip, sensitive, and highly specific miRNA detection without the risk of sequence bias. A simulation‐driven approach is used to engineer the hydrogel geometry and the gel‐reaction environment is chemically optimized for robust detection performance. The assay provides 22.6 fM sensitivity over a three log range, demonstrates multiplexing across at least four targets, and requires just 10.3 ng of total RNA input in a 2 hour and 15 minutes assay.     

Profiling of phospholipids in lipoproteins by multiplexed hollow fiber flow field-flow fractionation and nanoflow liquid chromatography–tandem mass spectrometry

This study describes a coupled analytical method to carry out the systematic profiling of phospholipids (PLs) in high-density lipoproteins (HDL) and low-density lipoproteins (LDL) from human blood plasma. HDL and LDL of healthy human plasma samples were separated by size and collected on a semi-preparative scale using multiplexed hollow fiber flow field-flow fractionation (MxHF5). Phospholipid mixtures contained in the resulting HDL and LDL fractions were analyzed by shotgun nanoflow liquid chromatography–tandem mass spectrometry (nLC–ESI-MS–MS). We utilized a dual scan method for the separation and simultaneous characterization of complicated PL mixtures by nLC–ESI-MS–MS, such that phosphatidylcholine (PC) and phosphatidylethanolamine (PE) molecules were detected in positive ion mode in a first LC run. In a second LC run, phosphatidylinositol (PI), phosphatidylglycerol (PG), and phosphatidic acid (PA) were detected in negative ion mode. In this study, a total of 56 PLs from HDL and 52 PLs from LDL particles were characterized by their molecular structures from data dependent collision-induced dissociation (CID) experiments, and their relative abundances were compared.