Multiple Degree Reduction and Elevation of Bézier Curves Using Jacobi–Bernstein Basis Transformations

In this article, we find the optimal r times degree reduction of Bézier curves with respect to the Jacobi-weighted L ₂-norm on the interval [0, 1]. This method describes a simple and efficient algorithm based on matrix computations. Also, our method includes many previous results for the best approximation with L ₁, L ₂, and L _∞-norms. We give some examples and figures to demonstrate these methods.     

Ni(0)-promoted activation of Csp2–H and Csp2–O bonds

A dinickel(0)–N₂ complex, stabilized with a rigid acridane-based PNP pincer ligand, was studied for its ability to activate C(sp²)–H and C(sp²)–O bonds. Stabilized by a Ni–μ–N₂–Na⁺ interaction, it activates C–H bonds of unfunctionalized arenes, affording nickel–aryl and nickel–hydride products. Concomitantly, two sodium cations get reduced to Na(0), which was identified and quantified by several methods. Our experimental results, including product analysis and kinetic measurements, strongly suggest that this C(sp²)–H activation does not follow the typical oxidative addition mechanism occurring at a low-valent single metal centre. Instead, via a bimolecular pathway, two powerfully reducing nickel ions cooperatively activate an arene C–H bond and concomitantly reduce two Lewis acidic alkali metals under ambient conditions. As a novel synthetic protocol, nickel(ii)–aryl species were directly synthesized from nickel(ii) precursors in benzene or toluene with excess Na under ambient conditions. Furthermore, when the dinickel(0)–N₂ complex is accessed via reduction of the nickel(ii)–phenyl species, the resulting phenyl anion deprotonates a C–H bond of glyme or 15-crown-5 leading to C–O bond cleavage, which produces vinyl ether. The dinickel(0)–N₂ species then cleaves the C(sp²)–O bond of vinyl ether to produce a nickel(ii)–vinyl complex. These results may provide a new strategy for the activation of C–H and C–O bonds mediated by a low valent nickel ion supported by a structurally rigidified ligand scaffold.

A structurally rigidified nickel(0) complex was found to be capable of cleaving both C(sp²)–H and C(sp²)–O bonds.     

Genetic and expression alterations in association with the sarcomatous change of cholangiocarcinoma cells

Cholangiocarcinoma (CC) is an intrahepatic bile duct carcinoma with a high mortality rate and a poor prognosis. Sarcomatous change/epithelial mesenchymal transition (EMT) of CC frequently leads to aggressive intrahepatic spread and metastasis. The aim of this study was to identify the genetic alterations and gene expression pattern that might be associated with the sarcomatous change in CC. Previously, we established 4 human CC cell lines (SCK, JCK1, Cho-CK, and Choi-CK). In the present study, we characterized a typical sarcomatoid phenotype of SCK, and classified the other cell lines according to tumor cell differentiation (a poorly differentiated JCK, a moderately differentiated Cho-CK, and a well differentiated Choi-CK cells), both morphologically and immunocytologically. We further analyzed the genetic alterations of two tumor suppressor genes (p53 and FHIT) and the expression of Fas/FasL gene, well known CC-related receptor and its ligand, in these four CC cell lines. The deletion mutation of p53 was found in the sarcomatoid SCK cells. These cells expressed much less Fas/FasL mRNAs than did the other ordinary CC cells. We further characterize the gene expression pattern that is involved in the sarcomatous progression of CC, using cDNA microarrays that contained 18,688 genes. Comparison of the expression patterns between the sarcomatoid SCK cells and the differentiated Choi-CK cells enabled us to identify 260 genes and 247 genes that were significantly over-expressed and under-expressed, respectively. Northern blotting of the 14 randomly selected genes verified the microarray data, including the differential expressions of the LGALS1, TGFBI, CES1, LDHB, UCHL1, ASPH, VDAC1, VIL2, CCND2, S100P, CALB1, MAL2, GPX1, and ANXA8 mRNAs. Immunohistochemistry also revealed in part the differential expressions of these gene proteins. These results suggest that those genetic and gene expression alterations may be relevant to the sarcomatous change/EMT in CC cells.     

Engineered 3D tissue models for cell-laden microfluidic channels

Delivery of nutrients and oxygen within three-dimensional (3D) tissue constructs is important to maintain cell viability. We built 3D cell-laden hydrogels to validate a new tissue perfusion model that takes into account nutrition consumption. The model system was analyzed by simulating theoretical nutrient diffusion into cell-laden hydrogels. We carried out a parametric study considering different microchannel sizes and inter-channel separation in the hydrogel. We hypothesized that nutrient consumption needs to be taken into account when optimizing the perfusion channel size and separation. We validated the hypothesis by experiments. We fabricated circular microchannels (r = 400 μm) in 3D cell-laden hydrogel constructs (R = 7.5 mm, volume = 5 ml). These channels were positioned either individually or in parallel within hydrogels to increase nutrient and oxygen transport as a way to improve cell viability. We quantified the spatial distribution of viable cells within 3D hydrogel scaffolds without channels and with single- and dual-perfusion microfluidic channels. We investigated quantitatively the cell viability as a function of radial distance from the channels using experimental data and mathematical modeling of diffusion profiles. Our simulations show that a large-channel radius as well as a large channel to channel distance diffuse nutrients farther through a 3D hydrogel. This is important since our results reveal that there is a close correlation between nutrient profiles and cell viability across the hydrogel. Young Seok Song and Richard L. Lin have contributed equally to this contribution     

Prediction of drug bioavailability in humans using immobilized artificial membrane phosphatidylcholine column chromatography and in vitro hepatic metabolic clearance

This study reports a rapid screening method for the prediction of oral drug bioavailability in humans based on combined immobilized artificial membrane (IAM) chromatographic capacity factor (k_IAM) and in vitro stability in hepatic microsomes. The fraction of drug absorbed (F_a) in humans was predicted for a set of 15 structurally diverse commercial drugs based on k_IAM values using a mobile phase consisting of acetonitrile: Dulbecco's phosphate‐buffered saline. The hepatic intrinsic clearance (CL ) was calculated from in vitro disappearance half‐life, and the oral bioavailability was predicted using in vitro hepatic clearance (CL_h) and F_a. Significant correlations were observed for the relationships between predicted hepatic extraction ratios (ER_h) and actual presystemic metabolism (r = 0.854) and between predicted and observed oral bioavailabilities (r = 0.805; p < 0.01). The IAM capacity factor together with the hepatic microsomal disappearance half‐life may be useful in identifying compounds with high oral absorption potential in early drug discovery processes. Copyright © 2009 John Wiley & Sons, Ltd.     

Analysis of perfluorinated chemicals in sludge: Method development and initial results

A fast, rigorous method was developed to maximize the extraction efficacy for ten perfluorocarboxylic acids and perfluorooctanesulfonate from waste-water-treatment sludge and to quantitate using liquid chromatography, tandem-mass spectrometry (LC/MS/MS). First, organic solvents were tested for extraction efficiency, including acetonitrile (ACN), methanol (MeOH), isopropanol (IPA), tetrahydrofuran (THF), and 50/50 ACN/MeOH (v/v). Among the extractants tested, 50/50 ACN/MeOH yielded the best results for our combined criteria of extraction efficacy and solvent-handling convenience. Second, chemical pretreatment prior to solvent extraction was tested with sodium hydroxide (NaOH), potassium hydroxide (KOH), hydrochloric acid (HCl), and potassium persulfate (K₂S₂O₈). Pretreatment with NaOH and HCl effectively recovered additional PFCs from the sludge, but KOH and K₂S₂O₈ digestion were less effective than no pretreatment. Third, cleanup methods were investigated with solid-phase extraction using HLB (hydrophilic–lipophilic balanced) and WAX (weak-anion exchange) stationary phases, and with ion-pairing. The HLB stationary phase yielded a slight edge over the other two cleanup strategies in terms of recoverable PFCs and chromatographic separation. Finally, the appropriateness of isotopically labeled PFCs for quantitating unlabeled PFCs using isotopic dilution in complex sludge extracts was evaluated by comparison to results obtained with the standard-addition method. A National Institute of Standards and Technology (NIST) domestic sludge (CRM 2781) was analyzed using our finalized method and compared with previously reported results.     

In-line coupling of two-phase single drop microextraction and large volume stacking using an electroosmotic flow pump in nonaqueous capillary electrophoresis

In order to improve the concentration sensitivity of capillary electrophoresis (CE), two sample preconcentration techniques, single drop microextraction (SDME) and large volume stacking using an electroosmotic flow pump (LVSEP), were coupled in-line in a commercial CE instrument. By simple programming of liquid handling sequences, a pentanol drop was prepared at the tip of a fused silica capillary over which a Teflon tube had been sleeved to serve as a hydrophobic support. After extraction of the analytes from an aqueous donor solution into the drop, the entire capillary column was filled with enriched pentanol extract. LVSEP, in which the sample matrix is automatically removed by the EOF, was then carried out using a methanolic run buffer. The overall enrichment factors for the analytes pentachlorophenol (PCP), 3-bromobenzoic acid (3-BBA), and 4-iodobenzoic acid (4-IBA), from a combination of 30 min SDME and LVSEP on a 27 cm capillary, were about 7000, even without agitation of the donor solution. The resulting limits of detection for PCP, 3-BBA, and 4-IBA were 0.7, 0.3 and 0.7 nM, respectively. Since no modification of the existing CE instrument is necessary and a bare capillary is used for LVSEP, this scheme can be adapted quite easily for many CE applications that require high concentration sensitivity.     

Coating of multiwalled carbon nanotubes with polymer nanospheres through microemulsion polymerization

We report a simple and noncovalent method for coating multiwalled carbon nanotubes (MWCNTs) with polyaniline (PANI) nanospheres using a microemulsion polymerization method. In this method, aniline polymerization is performed with MWCNTs in the presence of sodium dodecyl sulfate (SDS), which serves as both a surfactant and a dopant. Morphological, structural, thermal, and electrical properties of MWCNT–PANI nanocomposites were analyzed. The TEM results of the nanocomposites prepared with surfactant reveal that 30–50-nm-diameter PANI nanospheres were coated on the surface of the MWCNTs. Composites prepared without surfactant were found to be in core–sheath-type cable structures. The conductivities of the nanocomposites synthesized through microemulsion polymerization were found to be one order of magnitude higher than both the conductivities of pure PANI and the composites prepared via in situ chemical polymerization without an assisting SDS surfactant. The mechanism for the formation of nanostructured composites is presented.     

Nanoparticle films as a conducting layer for anodic aluminum oxide template-assisted nanorod synthesis

A simple, inexpensive, and robust methodology was developed to fabricate conductive film substrates by mechanically packing nanoparticles (NPs) on one side of anodic aluminum oxide (AAO). Gold, silver NPs, and carbon nanotubes were used as building blocks in the synthesis of conductive film substrates, upon which perpendicular nanorod arrays and colloidal free-standing nanorods were easily constructed. Characterizations by field emission scanning electron microscopy (FE-SEM) and optical dark-field microscopy confirmed the validity of the conductive NP film substrates on the AAO template. This contribution could provide a convenient and low-cost means for the fabrication of various conductive substrates on AAO.     

The oxidative-dissolution behaviors of fission products in a Na<Subscript>2</Subscript>CO<Subscript>3</Subscript>–H<Subscript>2</Subscript>O<Subscript>2</Subscript> solution

This study was carried out to investigate the characteristics of an oxidative-dissolution of fission products (FP) when uranium (U) is dissolved in a Na₂CO₃–H₂O₂ carbonate solution. Simulated FP-oxides which contained 12 components were added to the solution to examine their dissolution behaviors. It was found that H₂O₂ was an effective oxidant to minimize the dissolution of FP. For the 0.5 M Na₂CO₃–0.5 M H₂O₂ solution, such elements as Re, Te, Cs, and MoO₂ were dissolved with yields of 98 ± 2%, 98 ± 2%, 93 ± 2%, and 26 ± 3%, respectively, for 2 h. Among these components, Re, Te, and Cs were completely dissolved within 10–20 min without regard to the concentrations of Na₂CO₃, and H₂O₂ due to their high solubility in the carbonate solution with and without H₂O₂. However, MoO₂ was very slowly dissolved and its yield was 29 ± 3% for 4 h. The pH of the dissolved solution revealed the greatest influence on the dissolution yields of the FP, exhibiting the most effective pH condition in the range of 10–12 in order to create a considerable suppression of the co-dissolution of FP during the oxidative-dissolution of U.