Pyridinium dichlorophosphinomethylides

Seven new pyridinium dichlorophosphinomethylides 2 have been obtained from dichlorophosphinylation of the pyridinium methylides generated in situ. 2 give 1,3‐bis(alkoxycarbonyl)‐2‐phosphaindolizines 4 through 1,5‐electrocyclization of the intermediate, bis(pyridinium ylidyl)phosphenium chloride 3 which is generated either from disproportionation of 2 or from the reaction of 2 with pyridinium methylide. Formation of 3 has been confirmed by carrying out a crossed reaction. 3‐Substituted 2 forms 4 regiospecifically. Intramolecular 1,5‐cyclocondensation of 2‐methylpyridinium dichlorophosphinomethylide is preferred over its disproportionation. © 2001 John Wiley & Sons, Inc. Heteroatom Chem 12:602–609, 2001     

Elucidating Sequence and Structural Determinants of Carbohydrate Esterases for Complete Deacetylation of Substituted Xylans

Acetylated glucuronoxylan is one of the most common types of hemicellulose in nature. The structure is formed by a β-(1→4)-linked D-xylopyranosyl (Xylp) backbone that can be substituted with an acetyl group at O-2 and O-3 positions, and α-(1→2)-linked 4-O-methylglucopyranosyluronic acid (MeGlcpA). Acetyl xylan esterases (AcXE) that target mono- or doubly acetylated Xylp are well characterized; however, the previously studied AcXE from Flavobacterium johnsoniae (FjoAcXE) was the first to remove the acetyl group from 2-O-MeGlcpA-3-O-acetyl-substituted Xylp units, yet structural characteristics of these enzymes remain unspecified. Here, six homologs of FjoAcXE were produced and three crystal structures of the enzymes were solved. Two of them are complex structures, one with bound MeGlcpA and another with acetate. All homologs were confirmed to release acetate from 2-O-MeGlcpA-3-O-acetyl-substituted xylan, and the crystal structures point to key structural elements that might serve as defining features of this unclassified carbohydrate esterase family. Enzymes comprised two domains: N-terminal CBM domain and a C-terminal SGNH domain. In FjoAcXE and all studied homologs, the sequence motif around the catalytic serine is Gly-Asn-Ser-Ile (GNSI), which differs from other SGNH hydrolases. Binding by the MeGlcpA-Xylp ligand is directed by positively charged and highly conserved residues at the interface of the CBM and SGNH domains of the enzyme.     

12-钨磷酸在AlSBA-15上的固定化及其乙酰化催化活性

12-Tungstophosphoric heteropoly acid(TPA) with a Keggin structure was introduced into Al-incorporated mesoporous molecular sieves(AlSBA-15) by the incipient wetness method.The materials were characterized by X-ray diffraction,nitrogen adsorption,scanning electron microscopy,UV-Vis diffuse reflectance and Raman spectroscopy,which confirmed the Keggin and mesopore structure.Its catalytic activity was evaluated under solvent-free conditions in the liquid phase at 333-383 K for the propionylation of anisole with propionic anhydride.The catalysts used were AlSBA-15,10%,20%,and 40% TPA/AlSBA-15,and 20% TPA/MCM-48.In the propionylation of anisole with propionic anhydride,the substitution occurred predominantly at the para position.The 20% TPA/AlSBA-15 catalyst gave a total product yield of 48% with 98% selectivity towards 4-methoxypropiophenone.The regenerability of the catalyst was also studied and was found to be excellent.     

Rapid analysis of alkylphosphonate drugs by capillary zone electrophoresis using indirect ultraviolet detection

A rapid capillary electrophoretic method for the analysis of three alkylphosphonate drugs (i.e. fosfomycin disodium (FOS), clodronate disodium (CLO) and alendronate sodium (ALN)) was developed by using multiple probe BGE and indirect UV detection. BGE containing 30 mM benzoic acid, 5 mM salicylic acid and 0.5 mM CTAB (pH 3.8), temperature of 30°C, applied voltage of ?30 kV and detection at 220 nm provided baseline separation of all analytes (resolution (R)>2.2) in 3.2 min. EOF reversal by addition of CTAB and negative voltage polarity leading to the co‐EOF flow and short analysis time. Two probe BGE greatly improved peak symmetry. The method showed good linearity (r²>0.999 in ranges of 20–1000 μg/mL for FOS, 100–1000 μg/mL for CLO and 100–750 μg/mL for ALN) repeatablitiy (RSD<2.15%), recovery (99.3–101.1%) and sensitivity (LOD<50 μg/mL). Freshly prepared BGE and sample solutions are essential for the method precision and accuracy. This new method can be utilized for routine analysis of FOS, CLO and ALN in dosage forms because of its efficiency, reliability, speed and simplicity.     

Terbium(III) Chelate as an Efficient Donor for Multiple-Wavelength Fluorescent Acceptors

The emission spectra of the lanthanide chelates enable them to act as a donor for several acceptors emitting at different wavelengths. Fluorescence resonance energy transfer between terbium(III) chelate labeled antibody Fab fragment (donor) and a 17β-estradiol conjugated to Alexa Fluor 488, 555, 594 or 680 (acceptor) was employed to study the functionality of the terbium(III) chelate as an efficient donor for several acceptors emitting from green to far-red. During measurement, the sensitized emission of the acceptor was measured at acceptor specific wavelength. All the tested dyes proved to be efficient acceptors, and they were successfully used in the competitive homogeneous E2 assay. The highest signal to background ratio and the best assay performance was obtained with Alexa Fluor 680, due to the very low donor emission background at the far-red area. In addition, the sensitized emission of both Alexa Fluor 488 and 680 could be measured simultaneously without significant cross talk.     

Functionalization of Fullerenes with Cyclopentadienyl and Anthracenyl Capped Polymeric Building Blocks via Diels–Alder Chemistry

Cyclopentadienyl (Cp) capped polymers [polyethylene glycols (PEGs), = 2 000 g · mol⁻¹], react readily with fullerenes in a 1:1 molar ratio (relative to the amount of fullerenes and Cp‐end groups) at ambient temperature within 5 min in the absence of any catalyst in a Diels–Alder (DA) reaction to provide fullerene‐PEG hybrids. Similarly, anthracenyl capped PEGs react with fullerenes (in a 1:3 molar ratio) in DA reactions to yield the corresponding hybrids, albeit over a period of 1.5 h at 80 °C and a lesser conversion. The efficiency of the transformation is monitored via electrospray ionization mass spectrometry (ESI‐MS), demonstrating that the fullerenes can be transformed into polymer hybrids; most efficiently when Cp‐functional polymer is used as the diene. In addition, the obtained hybrids were subjected to UV/Vis as well as thermogravimetric analysis further underpinning the formation of mono‐substituted C₆₀‐PEG hybrids [wt.‐%^exp 70 ± 5 (PEG), 30 ± 5 (C₆₀), wt.‐%^theo 68 (PEG), 32 (C₆₀)].

     

Identification of hydrolysis products of FeCl3.6H2O by ESI-MS

The hydrolysis reactions of FeCl3 in 0.1 mM aqueous solutions were monitored by electrospray ionisation time-of-flight mass spectrometry (ESI-ToF-MS). In contrast to the other ionisation techniques, electrospray ionisation provides information on the composition of the elemental cores even in water and salt cluster ions. Therefore, the technique facilitates detection of the bonding of the chloride ions in the oxo-hydroxo-iron cores. A variety of mononuclear and polynuclear iron-oxohydroxo-chloride complexes were characterised from the cationic and anionic mass spectra of iron(III) solutions. Oxidation and reduction reactions of iron, as well as competition between OH- and Cl- ions within one iron core, were also observed.     

Factorial design applied to a non-aqueous capillary electrophoresis method for the separation of beta-agonists

The aim of this work was to study the effects of both chemical and instrumental parameters on the separation of beta-agonists (clenbuterol (CLE), salbutamol (SAL) and terbutaline (TER)) by non-aqueous capillary electrophoresis (NACE) method. Due to the number of parameters involved and their interactions, factorial experimental designs (EDs) at two levels was applied to investigate the influence of experimental factors (ionic strength of the background electrolyte (BGE), organic solvent, injection time, voltage and temperature) in sets of several CE responses (resolution, (RS), number of theoretical plate (N), tailing factor (TF) and migration time (tm)). As a compromise between the four responses, the optimum condition was obtained in 18 mM ammonium acetate in methanol (MeOH):acetonitrile (ACN):glacial acetic acid (66:33:1%, v/v/v) using an injection time of 4 s, the voltage and the temperature of 28 kV and 24 degrees C, respectively. The proposed NACE permitted the baseline separation of the three beta-agonists within 10.5 min with good repeatability (%RSD < 3.5%) and linearity (r2 > 0.99). The developed method was applicable for the analysis of the beta-agonists in syrup and tablets and the NACE condition was compatible with a mass spectrometer detector.     

Scale space multiresolution correlation analysis for time series data

We propose a new scale space method for the discovery of structure in the correlation between two time series. The method considers the possibility that correlation may not be constant in time and that it might have different features when viewed at different time scales. The time series are first decomposed into additive components corresponding to their features in different time scales. Temporal changes in correlation between pairs of such components are then explored by using weighted correlation within a sliding time window of varying length. Bayesian, sampling-based inference is used to establish the credibility of the correlation structures thus found and the results of analyses are summarized in scale space feature maps. The performance of the method is demonstrated using one artificial and two real data sets. The results underline the usefulness of the scale space approach when the correlation between the time series exhibit time-varying structure in different scales.     

Biosorption of As3+ Ions Using Ternary Microspheres of Chitosan,Yeast, and Gelatin: A Dynamic and Equilibrium Investigation

Ternary biopolymeric microspheres of chitosan, yeast and gelatin were prepared and characterized by FTIR spectral analysis, particle size measurements, and scanning electron micrograph techniques. The prepared microspheres were investigated for static and dynamic studies of adsorption of As⁺³ ions onto the microspheres surfaces at fixed pH and ionic strength of the aqueous solution.The adsorption data were applied to Langmuir and Freundlich isotherm equations and various static parameters were calculated. The dynamic nature of adsorption was quantified in terms of several kinetic constants such as rate constants for adsorption, Lagergreen rate constant, inter particle diffusion rate constant and pore diffusion coefficient. The influence of various experimental parameters such as solid to liquid ratio, pH, temperature, and chemical composition of biopolymeric microspheres were investigated on the adsorption of arsenic ion and various thermodynamic parameter were also calculated.