Crucial role of three-center hydrogen bonding in a challenging chiral molecular recognition

The enantio-discrimination of beta-chiral primary ammonium ions is achieved by a rational approach that utilizes three-center (bifurcated) hydrogen bonding. The extraction experiments on various selected guests reveal that the bifurcated H-bonding plays a crucial role for the chiral discrimination. The X-ray data obtained for an inclusion complex substantiate such interactions. Using the bifurcated H-bonding, the chiral molecular recognition with our C(3)-symmetric tripodal oxazoline receptors is extended generally toward ammonium ions of alpha-, beta-, and alpha,beta-chiral amines. Simple molecular models, evoking the bifurcated H-bonding, explain the chiral discrimination modes.     

Photovoltaic performance of flexible Cu(In,Ga)Se2 thin-film solar cells with varying Cr impurity barrier thickness

We report the effect of Cr impurity barrier on Cu(In,Ga)Se₂ (CIGS) thin-film solar cells prepared on flexible substrates. The Cr films with varying the thickness (t_Cr) were deposited on stainless steel substrates using direct-current magnetron sputtering. The solar cell performance was improved by increasing t_Cr since the diffusion of Fe impurities from the substrate to CIGS was suppressed. Although the elemental composition, grain size, and strain of CIGS film showed little change with varying Fe content, the fill factor and the short-circuit current density increased as decreasing Fe. The Fe increased the series resistance, shunt paths, and saturation current density. The reduction of Fe caused a steeper bandgap grading in CIGS which enhances current collection due to higher electric fields in bulk CIGS. CIGS solar cells with 1000 nm-thick Cr barrier showed the best conversion efficiency of 9.05%.     

A point mutant of apolipoprotein A-I, V156K, exhibited potent anti-oxidant and anti-atherosclerotic activity in hypercholesterolemic C57BL/6 mice

In our previous study, two point mutants of apolipoprotein A-I, designated V156K and A158E, revealed peculiar characteristics in their lipid-free and lipid-bound states. In order to determine the putative therapeutic potential of these mutants, several in vitro and in vivo evaluations were conducted. In the lipid-free state, V156K showed more profound antioxidant activity against LDL oxidation than did the wildtype (WT) or A158E variants in an in vitro assay. In the lipid-bound state, V156K-rHDL showed an enhanced cholesterol delivery activity to HepG2 cells in a time-dependent manner, as compared to WT-rHDL, A158E-rHDL, and R173C-rHDL. We assessed the physiological activities of the mutants in circulation, using hypercholesterolemic mice (C57BL6/J). Palmitoyloleoyl phosphatidylcholine (POPC)-rHDL preparations containing each of the apoA-I variants were injected into the mice at a dosage of 30 mg of apoA-I/kg of body weight. Forty eight hours after injection, the sera of the V156K-rHDL injected group showed the most potent antioxidant abilities in the ferric acid removal assay. The V156K-rHDL- or R173C-rHDL-injected mice showed no atherosclerotic lesions and manifested striking increases in their serum apo-E levels, as compared to the mice injected with WT-rHDL or A158E-rHDL. In conclusion, V156K-rHDL exhibited the most pronounced antioxidant activity and anti-atherosclerotic activity, both in vitro and in vivo. These results support the notion that HDL-therapy may prove beneficial due to its capacity to induce accelerated cholesterol excretion, as well as its enhanced antioxidant and anti-inflammatory effects and lesion regression effect.     

Removal of nanoparticles on silicon wafer using a self-channeled plasma filament

The effective removal of nanoparticles from a silicon wafer surface was demonstrated using the self-channeled plasma filament excited by a femtosecond (130?fs) Ti:sapphire laser (?? _p=790?nm). The photoinduced self-channeled plasma filament in air reached a length of approximately 110?C130?mm from the first focal spot with diameters ranging from 40 to 50???m at input intensities of more than 1.0×10¹⁴?W/cm². By the scan of wafer using the X?CY?CZ stage during self-channeled plasma filament, the removal variation of nanoparticles on surface was observed in situ before and after the plasma filament occurred. The cleaning efficiency was strongly dependent on the gap distance between the plasma filament and the surface. The removal efficiency of nanoparticles reached 96?% with no damage to the surface when the gap was 150???m.     

The M-CSF receptor in osteoclasts and beyond

Colony-stimulating factor 1 receptor (CSF1R, also known as c-FMS) is a receptor tyrosine kinase. Macrophage colony-stimulating factor (M-CSF) and IL-34 are ligands of CSF1R. CSF1R-mediated signaling is crucial for the survival, function, proliferation, and differentiation of myeloid lineage cells, including osteoclasts, monocytes/macrophages, microglia, Langerhans cells in the skin, and Paneth cells in the intestine. CSF1R also plays an important role in oocytes and trophoblastic cells in the female reproductive tract and in the maintenance and maturation of neural progenitor cells. Given that CSF1R is expressed in a wide range of myeloid cells, altered CSF1R signaling is implicated in inflammatory, neoplastic, and neurodegenerative diseases. Inhibiting CSF1R signaling through an inhibitory anti-CSF1R antibody or small molecule inhibitors that target the kinase activity of CSF1R has thus been a promising therapeutic strategy for those diseases. In this review, we cover the recent progress in our understanding of the various roles of CSF1R in osteoclasts and other myeloid cells, highlighting the therapeutic applications of CSF1R inhibitors in disease conditions.Subject terms: Osteoimmunology, Cell signalling, Targeted bone remodelling, Differentiation     

Multi-nozzle electrohydrodynamic inkjet printing of silver colloidal solution for the fabrication of electrically functional microstructures

In this paper, multi-nozzle electrohydrodynamic (EHD) inkjet printing of a colloidal solution containing silver nanoparticles in a fully controlled fashion is reported. For minimizing interaction, i.e. cross-talk, between neighboring jets, the distance between the nozzles was optimized numerically by investigating the magnitude of the electric field strength around the tip of each nozzle. A multi-nozzle EHD inkjet printing head consisting of three nozzles was fabricated and successfully tested by simultaneously printing electrically conductive lines of a colloidal solution containing silver nanoparticles onto a glass substrate. The printed results show electrical resistivity of 5.05×10⁻⁸ Ω m, which is almost three times larger than that of bulk silver. These conductive microtracks demonstrate the feasibility of the multi-nozzle EHD inkjet printing process for industrial fabrication of microelectronic devices.     

Investigation of Substituent Effects on Proton and Carbon-13 Chemical Shifts of 4-Substituted Trans-Stilbenes

Proton and carbon-13 chemical shifts of para-substituted stilbenes have been measured. ¹H-¹H, ¹H-¹³C COSY spectra were obtained to analyze unambiguously the chemical shifts of protons and carbons. A long range coupling between 2-H and α-H was observed in a ¹H-¹H COSY spectrum. The observed chemical shifts have been correlated with Hammett substituent parameters. Among ethenyl protons and carbons, all but the chemical shifts of α-H show good correlation with both dual substituent parameters and single substituent parameters. In addition to this finding, the excellent linear correlations of C-l, and 4′-H of 4-substituted trans-stilbenes are also reported. Besides the correlations of chemical shifts with Hammett parameters, a good correlation between the chemical shifts and the calculated charges of position C-4′ are reported.     

Supercritical fluid chromatography tandem-column method development in pharmaceutical sciences for a mixture of four stereoisomers

A tandem-column method using Chiralpak AD-H and Chiralcel OD-H columns was achieved for baseline separation of a mixture of chiral pharmaceutical compounds (i.e., four stereoisomers) via supercritical fluid chromatography (SFC) with a mobile phase consisting of 90% liquid carbon dioxide and 10% ethanol:isopropanol (50:50 v/v). On the contrary, this mixture (mixture A) could not be baseline separated by SFC conditions explored with individual Chiralpak AD-H and Chiralcel OD-H columns. The effects of various mobile phases on elution order, capacity factor, selectivity, and resolution were determined with mixture A on the individual aforementioned columns to develop the tandem-column method.     

Enantioselective separation of racemic secondary amines on a chiral crown ether-based liquid chromatography stationary phase

The first general enantioselective separation of racemic secondary amines on a crown ether-based liquid chromatography chiral stationary phase (CSP) is presented. The CSP is based on (+)- or (-)-(18-crown-6)-2,3,11,12-tetracarboxylic acid covalently bonded to silica gel. A mobile phase containing methanol, acetonitrile, triethylamine and acetic acid was employed in these separations of secondary amines with crown ether CSPs. The separation mechanism is believed to be the secondary amine forming a complex which includes crown ether coordination and electrostatic interaction of the positively charged amine with a carboxylate anion of the immobilized crown ether.