Catalytic Asymmetric 1,6‐Conjugate Addition of para‐Quinone Methides: Formation of All‐Carbon Quaternary Stereocenters

Described herein is a general and mild catalytic asymmetric 1,6‐conjugate addition of para‐quinone methides (p‐QMs), a class of challenging reactions with previous limited success. Benefiting from chiral Brønsted acid catalysis, which allows in situ formation of p‐QMs, our reaction expands the scope to general p‐QMs with various substitution patterns. It also enables efficient intermolecular formation of all‐carbon quaternary stereocenters with high enantioselectivity.     

Integral equation formulation for buoyancy-driven convection problems

An integral equation formulation for buoyancy-driven convection problems is developed and illustrated. Buoyancy-driven convection in a bounded cylindrical geometry with a free surface is studied for a range of aspect ratios and Nusselt numbers. The critical Rayleigh number, the nature of the cellular motion, and the heat transfer enhancement are computed using linear theory. Green's functions are used to convert the linear problem into linear Fredholm integral equations. Theorems are proved which establish the properties of the eigenvalues and eigenfunctions of the linear integral operator which appears in these equations.     

Distinguishing Ontario ginseng landraces and ginseng species using NMR-based metabolomics

The use of ¹H-NMR-based metabolomics to distinguish and identify unique markers of five Ontario ginseng (Panax quinquefolius L.) landraces and two ginseng species (P. quinquefolius and P. ginseng) was evaluated. Three landraces (2, 3, and 5) were distinguished from one another in the principal component analysis (PCA) scores plot. Further analysis was conducted and specific discriminating metabolites from the PCA loadings were determined. Landraces 3 and 5 were distinguishable on the basis of a decreased NMR intensity in the methyl ginsenoside region, indicating decreased overall ginsenoside levels. In addition, landrace 5 was separated by an increased amount of sucrose relative to the rest of the landraces. Landrace 2 was separated from the rest of the landraces by the increased level of ginsenoside R_b1. The Ontario P. quinquefolius was also compared with Asian P. ginseng by PCA, and clear separation between the two groups was detected in the PCA scores plot. The PCA loadings plot and a t-test NMR difference plot were able to identify an increased level of maltose and a decreased level of sucrose in the Asian ginseng compared with the Ontario ginseng. An overall decrease of ginsenoside content, especially ginsenoside R_b1, was also detected in the Asian ginseng’s metabolic profile. This study demonstrates the potential of NMR-based metabolomics as a powerful high-throughput technique in distinguishing various closely related ginseng landraces and its ability to identify metabolic differences from Ontario and Asian ginseng. The results from this study will allow better understanding for quality assessment, species authentication, and the potential for developing a fully automated method for quality control.

Simplified liquid chromatographic determination of glyphosate and metabolite residues in environmental water using post-column fluorogenic labelling

Glyphosate and its metabolite aminomethylphosphonic acid in environmental water can be preconcentrated with an anion-exchange column, eluted with potassium citrate solution and determined directly by liquid chromatography with a post-column reactor and a fluorescence detector. The limit of detection and average recovery are 1 μg 1^?1 and 89.3% for glyphosate and 0.4 μg l^?1 and 86.3% for the metabolite.     

Direct patterning of composite biocompatible microstructures using microfluidics

This study demonstrates a versatile and fast method for patterning three-dimensional (3D) monolithic microstructures made of multiple (up to 24 demonstrated) types of materials, all spatially aligned, inside a microchannel. This technique uses confocal scanning or conventional fluorescence microscopy to polymerize selected regions of a photocurable material, and microfluidics to automate the delivery of a series of washes and photocurable reagents. Upon completion of lithographic cycles, the aligned 3D microstructures are suitable for microfluidic manipulation and analysis. We demonstrated the fabrication of composite 3D microstructures with various geometries, size scales (up to 1 mm2), spatial resolution (down to 3 microm), and materials. For a typical multi-cycle process, the total fabrication time was tens of minutes, compared to tens of hours for conventional methods. In the case of 3D hydrogels, a potential use is the direct patterning of inhomogeneous 3D microenvironments for studying cell behavior.     

Surface complexation mechanism and modeling in Cr(III) biosorption by a microalgal isolate, Chlorella miniata

The mechanism involved in the removal of Cr(III) by a green microalgal isolate, Chlorella miniata, was examined based on a series of batch experiments and microscopic analyses, and a mathematical model was proposed. Results showed that Cr(III) biosorption increased with the increase of pH from 2.0 to 4.5, and no significant changes in biosorption outside this pH range. Langmuir isotherm indicated that the maximum Cr(III) sorption capacity of Chlorella miniata was 14.17, 28.72, and 41.12 mg g(-1) biomass at pH 3.0, 4.0, and 4.5, respectively. Results from desorption studies, SEM (scanning electron microscopy), TEM (transmission electron microscopy), and EDX (energy-dispersive X-ray spectroscope) analyses confirmed that surface complexation was the main process involved in Cr(III) biosorption. Potentiometric titration revealed that carboxyl (pKa1 = 4.10), phosphonate (pKa2 = 6.36) and amine (pKa3 = 8.47) functional groups on the surface of Chlorella miniata were the possible sites for Cr uptake, and their average amounts were 0.53, 0.39, and 0.36 mmol g(-1) biomass, respectively. A surface complexation model further indicated that carboxyl group played the main role in Cr(III) complexation, with a binding constant of K11 = 1.87 x 10(-4) and K12 = 6.11 x 10(-4) for Cr3+ and Cr(OH)2+, respectively. This model also suggested that the hydroxy species was more easily to complex with the cell surface of Chlorella miniata.