Chiral recognition and separation of beta2-amino acids using non-covalently molecularly imprinted polymers

Non-covalently molecularly imprinted polymers (MIPs) for beta2-amino acids were prepared for the first time. N-(2-chlorobenzyloxycarbonyl)-(R)-beta2-homophenylalanine (N-2-ClZ-(R)-beta2-HPhe) was imprinted with methacrylic acid (MAA) and/or 4-vinylpyridine (4-VPy) as the functional monomers, with ethylene glycol dimethacrylate (EDMA) as the cross-linker. The MIPs made with different ratios of MAA:4-VPy were studied in HPLC mode. The results show that MIPs made with 4-VPy yielded the best chiral separation factor (alpha= 1.86) for the template molecule. The importance for an efficient separation of pi-stacking interactions between the MIPs and the template molecule is demonstrated. Racemates of Z-alpha-amino acids and beta-amino acid analogues of the template were either not or poorly resolved by the MIPs, thus demonstrating the close three-dimensional complementarity of the MIPs' recognition sites with the template.     

Real-time optical reconstruction of the diffused 3D object using phase information calculated by Continuous Wavelet Transform

We propose the real time optical reconstruction of a three-dimensional (3D) object from a digitally recorded hologram. Phase distribution of the recorded hologram is numerically calculated by 1-dimensional Continuous Wavelet Transform (1D-CWT) for digital reconstruction with phase only information. Also, the phase distribution of 1D-CWT transferred to the spatial light modulator (SLM) is used to obtain optically reconstructed image. It is observed that an efficient real-time analysis can be achieved, if phase of 1D-CWT is used. In the same time, optically reconstructed 3D objects obtained by only phase information are about three times brighter than bleached hologram intensity's. So the minimum power loss can be obtained. Numerical and experimental results are presented.     

Stress Inhomogeneity in Powder Specimens Tested in the Jenike Shear Cell: Myth or Fact?

In the mechanical characterization of powders using the direct shear testers such as the Jenike shear cell, the existence of a uniform or well‐defined stress field in a powder specimen is assumed. This assumption has not been subjected to any serious scrutiny in the literature. In this study, the normal stress variation in a silica powder was locally determined by locating a pressure‐sensitive TekScan pad at the bottom section of a Jenike shear cell. A computer simulation of the consolidation and pre‐shearing stages of the Jenike test procedure was performed using the Discrete Element Method (DEM). The paper presents both experimental and computational evidence for the existence of a complex stress field in the powder specimen, thus clearly invalidating the long‐standing stress homogeneity assumption in the direct shear testing of powders. The implications of the stress inhomogeneity in terms of the accuracy of the material properties extracted from the Jenike test are also presented.     

Selective extraction of triazine herbicides based on a combination of membrane assisted solvent extraction and molecularly imprinted solid phase extraction

A selective extraction technique based on the combination of membrane assisted solvent extraction and molecularly imprinted solid phase extraction for triazine herbicides in food samples was developed. Simazine, atrazine, prometon, terbumeton, terbuthylazine and prometryn were extracted from aqueous food samples into a hydrophobic polypropylene membrane bag containing 1000μL of toluene as the acceptor phase along with 100mg of MIP particles. In the acceptor phase, the compounds were re-extracted onto MIP particles. The extraction technique was optimised for the type of organic acceptor solvent, amount of molecularly imprinted polymers particles in the organic acceptor phase, extraction time and addition of salt. Toluene as the acceptor phase was found to give higher triazine binding onto MIP particles compared to hexane and cyclohexane. Extraction time of 120min and 100mg of MIP were found to be optimum parameters. Addition of salt increased the extraction efficiency for more polar triazines. The selectivity of the technique was demonstrated by extracting spiked cow pea and corn extracts where clean chromatograms were obtained compared to only membrane assisted solvent extraction or only molecularly imprinted solid phase extraction. The study revealed that this combination may be a simple way of selectively extracting compounds in complex samples.     

Development of an improved method for trace analysis of chloramphenicol using molecularly imprinted polymers

A confirmatory method is described for the determination of the illegal antibiotic chloramphenicol using a specifically developed molecularly imprinted polymer (MIP) as the sample clean-up technique. The newly developed MIP was produced using an analogue to chloramphenicol as the template molecule. Using an analogue of the analyte as the template avoids a major traditional drawback associated with MIPs of residual template leeching or bleeding. The MIP described was used as a solid-phase extraction phase for the extraction of chloramphenicol from various sample matrices including honey, urine, milk and plasma. A full analytical method with quantification by LC-MS/MS is described. The method was fully validated according to the European Union (EU) criteria for the analysis of veterinary drug residues.     

Analysis of permethrin isomers in composite diet samples by molecularly imprinted solid-phase extraction and isotope dilution gas chromatography–ion trap mass spectrometry

Determination of an individual's aggregate dietary ingestion of pesticides entails analysis of a difficult sample matrix. Permethrin-specific molecularly imprinted polymer (MIP) solid-phase extraction cartridges were developed for use as a sample preparation technique for a composite food matrix. Vortexing with acetonitrile and centrifugation were found to provide optimal extraction of the permethrin isomers from the composite foods. The acetonitrile (with 1% acetic acid) was mostly evaporated and the analytes reconstituted in 90:10 water/acetonitrile in preparation for molecularly imprinted solid-phase extraction. Permethrin elution was accomplished with acetonitrile and sample extracts were analyzed by isotope dilution gas chromatography–ion trap mass spectrometry. Quantitation of product ions provided definitive identification of the pesticide isomers. The final method parameters were tested with fortified composite food samples of varying fat content (1%, 5%, and 10%) and recoveries ranged from 99.3% to 126%. Vegetable samples with incurred pesticide levels were also analyzed with the given method and recoveries were acceptable (81.0–95.7%). Method detection limits were demonstrated in the low ppb range. Finally, the applicability of the MIP stationary phase to extract other pyrethroids, specifically cyfluthrin and cypermethrin, was also investigated.     

Asymptotic expansions of multiply scattered surface currents

We have recently uncovered the convergence characteristics of multiple scattering iterations for “two-dimensional” as well as “three-dimensional scalar (acoustics)” scattering models in the high-frequency regime. As we have demonstrated, a most distinctive property of these latermodels, compared to their two-dimensional counterparts, is the dependence of corresponding asymptotic expansions on the relative angle of rotation between the principal axes of the successive reflection points of the optical rays. Concerning the case of fully “three-dimensional vector (electromagnetic)” scattering problems, here we show that the vectorial nature of the problem, in turn, gives rise to new additional complex structure. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Analysis of multiple scattering iterations for high-frequency scattering problems. II: The three-dimensional scalar case

In this paper, we continue our analysis of the treatment of multiple scattering effects within a recently proposed methodology, based on integral-equations, for the numerical solution of scattering problems at high frequencies. In more detail, here we extend the two-dimensional results in part I of this work to fully three-dimensional geometries. As in the former case, our concern here is the determination of the rate of convergence of the multiple-scattering iterations for a collection of three-dimensional convex obstacles that are inherent in the aforementioned high-frequency schemes. To this end, we follow a similar strategy to that we devised in part I: first, we recast the (iterated, Neumann) multiple-scattering series in the form of a sum of periodic orbits (of increasing period) corresponding to multiple reflections that periodically bounce off a series of scattering sub-structures; then, we proceed to derive a high-frequency recurrence that relates the normal derivatives of the fields induced on these structures as the waves reflect periodically; and, finally, we analyze this recurrence to provide an explicit rate of convergence associated with each orbit. While the procedure is analogous to its two-dimensional counterpart, the actual analysis is significantly more involved and, perhaps more interestingly, it uncovers new phenomena that cannot be distinguished in two-dimensional configurations (e.g. the further dependence of the convergence rate on the relative orientation of interacting structures). As in the two-dimensional case, and beyond their intrinsic interest, we also explain here how the results of our analysis can be used to accelerate the convergence of the multiple-scattering series and, thus, to provide significant savings in computational times.     

Preparation of stable colloidal suspensions of superdisintegrants via wet stirred media milling

Superdisintegrants are cross-linked polymers that can be used as dispersants for fast release of drug nanoparticles from nanocomposite microparticles during in vitro and in vivo dissolution.Currently available superdisintegrant particles have average sizes of approximately 5-130 μm,which are too big for drug nanocomposite applications.Hence,production of stable superdisintegrant suspensions with less than5 μm particles is desirable.Here,we explore the preparation of colloidal suspensions of anionic and nonionic superdisintegrants using a wet stirred media mill and assess their physical stability.Sodium starch glycolate(SSG) and crospovidone(CP) were selected as representative anionic and nonionic superdisintegrants,and hydroxy propyl cellulose(HPC) and sodium dodecyl sulfate(SDS) were used as a steric stabilizer and a wetting agent/stabilizer,respectively.Particle sizing,scanning electron microscopy,and zeta potential measurements were used to characterize the suspensions.Colloidal superdisintegrant suspensions were prepared reproducibly.The extensive particle breakage was attributed to the swelling-induced softening in water.SSG suspensions were stable even in the absence of stabilizers,whereas CP suspensions required HPC-SDS for minimizing particle aggregation.These findings were explained by the higher absolute(negative) zeta potential of the suspensions of the anionic superdisintegrant(SSG) as compared with those of the nonionic superdisintegrant(CP).     

Analysis of multiple scattering iterations for high-frequency scattering problems. I: the two-dimensional case

We present an analysis of a recently proposed integral-equation method for the solution of high-frequency electromagnetic and acoustic scattering problems that delivers error-controllable solutions in frequency-independent computational times. Within single scattering configurations the method is based on the use of an appropriate ansatz for the unknown surface densities and on suitable extensions of the method of stationary phase. The extension to multiple-scattering configurations, in turn, is attained through consideration of an iterative (Neumann) series that successively accounts for further geometrical wave reflections. As we show, for a collection of two-dimensional (cylindrical) convex obstacles, this series can be rearranged into a sum of periodic orbits (of increasing period), each corresponding to contributions arising from waves that reflect off a fixed subset of scatterers when these are transversed sequentially in a periodic manner. Here, we analyze the properties of these periodic orbits in the high-frequency regime, by deriving precise asymptotic expansions for the “currents” (i.e. the normal derivative of the fields) that they induce on the surface of the obstacles. As we demonstrate these expansions can be used to provide accurate estimates of the rate at which their magnitude decreases with increasing number of reflections, which defines the overall rate of convergence of the multiple-scattering series. Moreover, we show that the detailed asymptotic knowledge of these currents can be used to accelerate this convergence and, thus, to reduce the number of iterations necessary to attain a prescribed accuracy.