Design of Supramolecular Cyclodextrin Complex Sensors for Ion and Molecule Recognition in Water

The design and function of novel supramolecular fluoroionophore/cyclodextrin (CyD) complex sensors for ion and molecule recognition in water are reviewed. For the crown ether fluoroionophore/-CyD complex, the dimerization of the fluoroionophore inside the -CyD is found to be selectively promoted by alkali metal ion binding, thereby resulting in metal-ion-selective pyrene dimer emission in water. This supramolecular function is successfully utilized in the design of a podand fluoroionophore/-CyD complex for sensing toxic lead ion in water. The boronic acid fluoroionophore/-CyD complex binds sugars and produces increased fluorescence emission in water. The response mechanism appears to be due to the suppression of the photoinduced electron transfer (PET) from pyrene donor to trigonal phenylboronic acid acceptor. This is a novel emission function provided by the boronic acid fluoroionophore/-CyD complex sensors in water.     

Synthesis of a new PET/layered niobate hybrid material

A new organic/inorganic hybrid material was prepared by the polymerization of bis(hydroxyethyl) terephthalate (BHET) with a layered niobate compound, H₄Nb₆O₁₇, modified by 11-aminoundecanoic acid (AUA). The hybrid polymer films of BHET with H₄Nb₆O₁₇/AUA exhibited favorable characteristics, particularly of being optically clear, indicating the exfoliation and homogeneous dispersion of H₄Nb₆O₁₇ into the PET/niobate hybrid.     

Photoinduced deformation of amphiphilic azo polymer colloidal spheres

Photoinduced shape deformation of colloidal spheres made of an amphiphilic azo polymer has been demonstrated in this work. The polymer contains the donor-and-acceptor-type azobenzene chromophores and can form uniform colloidal spheres by dropwise adding water into its THF solution. When the colloidal spheres obtained were exposed to the interfering p-polarized Ar+ laser beams (150 mW/cm2), the colloidal spheres changed to prolates (i.e., "rugby-balls"), "spindles", and finally "rods", depending on the irradiation times. The elongated direction of the spheres was observed to be the same as the polarization direction of the laser beam. The average major-to-minor ratio of the ellipsoids could be easily adjusted by controlling the irradiation time. The deformation effect observed in this work can offer a new way to prepare nonspherical colloids from colloidal spheres and will shed new light on the correlation between the photodriven shape deformation and photoinduced surface relief gratings for the same type of polymers.     

1H-imidazo[4,5-b] pyrazines. II. 2-carboxylic acid derivatives

Methods for the preparations of 1H-imidazo[4,5-b]pyrazine-2-carboxylic acid and derivatives are reported.     

Preparation of polymer-supported phosphine from ferrocene for palladium-catalyzed Suzuki-Miyaura cross-coupling reactions

Polymer-supported phosphine ligand 3b derived from ferrocene was prepared,and applied in palladium-catalyzed Suzuki- Miyaura reactions.A range of aryl bromides can couple with phenylboronic acid to obtain corresponding biaryls in excellent yields. The recycling of the polymer-bound catalyst was tested without adding palladium.     

有机试剂结构与性质的研究XII有机试剂的pKa与改进的Swain－Lupton参数

有机试剂的ｐＫ０ａ是其重要的物化参数，它是有机试剂酸碱性的度量，决定其配合物的稳定性．根据Ｓｗａｉｎ－Ｌｕｐｔｏｎ的工作，每个取代基的效应可用两个参数：场／诱导效应参数与共振效应参数来描述．本文应用Ｈａｎｓｃｈ改进的参数值研究了ｐＫａ与取代基常数的相关性，建立了下式．ｐＫａ＝ｐＫ０ａ＋ｒ１Ｆ＋ｒ２Ｒ     

Chemosensors for the marine toxin saxitoxin

Eleven anthracylmethyl crown ethers have been synthesized and evaluated as fluorescence sensors for the marine toxin saxitoxin. Fluorescence enhancement data are consistent with a 1:1 binding complex for all crowns. The binding constants are in the range of 10(4) M(-)(1) in ammonium phosphate buffer (pH 7.1) in 80% ethanol solvent. Selectivity for sensing saxitoxin versus several organic analytes has been demonstrated for the first time. Possible modes of binding are presented, and relevance to saxitoxin monitoring programs are discussed.     

An approach to comparative analysis of chromatographic fingerprints for assuring the quality of botanical drugs

The present study was focused on developing the chemometric methods for analysis of the chromatographic fingerprint to control the quality of botanical drugs, which has gained attention in Asia and other countries. We developed a novel approach to generate a set of fingerprint features, called Fisher components (FCs) that were extracted from the chromatographic fingerprint. The method greatly reduces the dimensionality of the fingerprint vector, and the resulting FCs still retain most discriminatory information of the original fingerprint. Choosing an example of relevance to contemporary botanical drugs, we applied the FCs to a set of Shenmai injection samples. We successfully identified the manufacturers of the samples using two classifiers, linear discriminant analysis (LDA) and k-Nearest Neighbor (k-NN) based on the FCs. We also applied a similarity assessment together with the visual analysis using the FCs to exam the products from different manufacturers. We found that the lot-to-lot consistency of products can be accurately determined using the FCs. Finally, we demonstrated that the application of chemometric methods for chromatographic fingerprinting offers reliability to detect suspected fraud samples. In summary, we demonstrated that the presented approaches could be useful to determine the identity, consistency, and authenticity of Shenmai injection through chromatographic fingerprinting. The methods are equally applicable to other botanical drugs.     

Unified gas and supercritical fluid chromatography on 50 μm i.d. Columns

A unified approach to sequential gas and supercritical fluid Chromatography using 50 μm i.d. open tubular columns is described. Sample introduction is performed by means of a rotary injection valve. In order that linear velocities can be optimized independently, a second rotary valve in the chromatographic oven is used to direct the flow of column eluate to the flame ionization detector through either fused silica tubing in GC, or a frit restrictor in SFC. Applications of sequential GC-SFC on a 50 μm i.d. open tubular column are demonstrated, and comparisons made between sequential GC-SFC on 50 and 100 μm i.d. columns.     

Stabilization and characterization of colloidal gas aphron dispersions

Colloidal gas aphrons (CGAs) are finding increasing application in water processing, bioseparation, bubble-entrained floc flotation, separation of oil from sand, etc. This article proposes an effective method of encapsulation to stabilize the CGA bubbles with silicic sol solution for their characterization. The stabilized CGA bubbles can keep shapes and sizes for at least 12 h; even the bubbles smaller than 25 mum can also be stabilized and exist for very long times. Effects of concentration and pH of silicic sol solution on CGA stabilization were studied. The optimal ranges of concentration and pH of silicic sol solution are 0.15-0.25 mol/dm(3) and 7-10, respectively. The bubble distortion behavior in disturbance and size distribution of CGAs were examined by using the stabilization method and photographic techniques.