Capillary electrophoresis for the analysis of paralytic shellfish poisoning toxins in shellfish: Comparison of detection methods

Paralytic shellfish toxins (PSTs) are produced by marine and freshwater microalgae and accumulate in shellfish including mussels, oysters, and scallops, causing possible fatalities when inadvertently consumed. Monitoring of PST content of shellfish is therefore important for food safety, with currently approved methods based on HPLC, using pre‐ or postcolumn oxidation for fluorescence detection (HPLC‐FLD). CE is an attractive alternative for screening and detection of PSTs as it is compatible with miniaturization and could be implemented in portable instrumentation for on‐site monitoring. In this study, CE methods were developed for C⁴D, FLD, UV absorption detection, and MS—making this first report of C⁴D and FLD for PSTs detection. Because most oxidized toxins are neutral, MEKC was used in combination with FLD. The developed CZE‐UV and CZE‐C⁴D methods provide better resolution, selectivity, and separation efficiency compared to CZE‐MS and MEKC‐FLD. The sensitivity of the CZE‐C⁴D and MEKC‐FLD methods was superior to UV and MS, with LOD values ranging from 140 to 715 ng/mL for CZE‐C⁴D and 60.9 to 104 ng/mL for MEKC‐FLD. With the regulatory limit for shellfish samples of 800 ng/mL, the CZE‐C⁴D and MEKC‐FLD methods were evaluated for the screening and detection of PSTs in shellfish samples. While the CZE‐C⁴D method suffered from significant interferences from the shellfish matrix, MEKC‐FLD was successfully used for PST screening of a periodate‐oxidized mussel sample, with results confirmed by HPLC‐FLD. This confirms the potential of MEKC‐FLD for screening of PSTs in shellfish samples.     

The zero-one law for a complete orthonormal system

A complete orthonormal system of functions $\Theta ={\left\{{\theta }_n\right\}}_{n=1}^{\infty }\text{,}{\theta }_n\in L_{[0\text{,}1]}^{\infty }$ is constructed such that ${\sum }_{n=1}^{\infty }{a}_n{\theta }_n$ converges almost everywhere on $[0\text{,}1]$ if ${\left\{a_n\right\}}_{n=1}^{\infty }\in l^2$ and ${\sum }_{n=1}^{\infty }{a}_n{\theta }_n$ diverges a.e. for any ${\left\{a_n\right\}}_{n=1}^{\infty }?l^2$. We also show that for any complete ONS ${\left\{f_n\right\}}_{n=1}^{\infty }$ of functions defined on $[0\text{,}1]$ there exists a fixed non decreasing subsequence ${\left\{n_k\right\}}_{k=1}^{\infty }$ of natural numbers such that for any $f\in L_{[0\text{,}1]}^0$ and some sequence of coefficients ${\left\{b_n\right\}}_{n=1}^{\infty }$,

$\sum _{n=1}^{n_k}{b}_n{f}_n\to f\text{a.e. when}k\to \infty \text{.}$

To cite this article: K. Kazarian, C. R. Acad. Sci. Paris, Ser. I 339 (2004).     

Shifted Jacobi multiplier sequences and transplantation between sine and cosine series

It is shown that the multiplier norm of a shifted Jacobi multiplier sequence can be estimated by the (same) multiplier norm of the original sequence uniformly with respect to the shift. Muckenhoupt’s transplantation theorem for Jacobi series is used essentially, for which also a functional analytic understanding is given in terms of the minimality of the Jacobi system in weighted L ^p -spaces.      

Application of principal component analysis to the thermal characterization of silanized nanoparticles obtained at supercritical carbon dioxide conditions

Samples resulting from reaction of TiO₂ with octyltriethoxysilane, developed using a supercritical carbon dioxide procedure, have been studied by infrared and Raman spectroscopies and thermogravimetric analysis. Different reaction conditions have been applied to the preparation of samples in order to study the influence of experimental factors on the sample properties. Vibrational techniques have first been used to verify the presence of silanized structures on the surface of TiO₂ through the detection of specific bands characteristic of the Si-O-Si cross-linking. Thermogravimetric profiles consisting of weight loss values as a function of temperature have been analyzed by principal component analysis to extract information about the characteristics of the linkage between silane and TiO₂ as well as the thermal stability of the prepared materials. The mathematical treatment of data has provided conclusions on the properties of the samples and analogies and differences with respect to the commercial material.     

Nondestructive three-dimensional analysis of layered polymer structures with chemical imaging

Three-dimensional (3D) chemical information was obtained by means of a combination of two-dimensional attenuated total reflection Fourier transform infrared (ATR-FT-IR) imaging with a focal plane array detector and variable angle depth profiling. Since the penetration depth of the evanescent wave in ATR spectroscopy is not limited by diffraction, it was possible to resolve thin sandwiched polymer layers nondestructively within a stack of polymer layers. Chemical images were obtained from layers of different thickness of the laminate by moving a custom-made aperture to specific positions on the condenser lens of the ATR accessory. Sequences of absorption images detect the successive appearance of thin, buried layers of polybutylmethacrylate (d(PBMA) = 400 nm) and polycarbonate (d(TMPC) = 300 nm) in different depths of the stack of polymer layers. The depth resolution of variable-angle ATR-FT-IR imaging is sufficiently high to detect surface roughness at the interface between different polymer layers. Two different stacks of polymers with reordered sandwich-layers were imaged simultaneously, demonstrating the potential of variable angle ATR-FT-IR for 3D-imaging of a sample with xyz-heterogeneity, which can be a powerful analytical technique for materials science and biomedical research.     

High-speed monitoring of the crystallinity change in poly(lactic acid) during photodegradation by using a newly developed wide area NIR imaging system (Compovision)

We aimed to achieve wide area rapid monitoring of the crystallinity change in poly(lactic acid) (PLA) during photodegradation caused by ultraviolet (UV) light by using a newly developed near-infrared (NIR) camera (Compovison). Several kinds of PLA samples with different crystallinities and their blends with poly[(3)-(R)-hydroxybutyrate] were prepared. Their two-dimensional NIR spectra in the 1,000–2,350-nm region were measured by Compovision at a 5-min interval during photolysis. An intensity decrease of the band in the 1,900-1,925-nm region due to the second overtone of the C = O stretching vibration of PLA was observed during photolysis. This suggests that an anhydride carbonyl is produced during photolysis. The NIR image of the crystallinity change monitored by the band at 1,917 nm in the standard normal variate spectra clearly shows the inhomogeneity of crystal evolution. A logarithmic increase was observed for all identified areas in the PLA film; however, the time to reach the maximum crystallinity was slightly different according to the initial crystallinity of the sample. It is likely that the initial crystallinity of the sample influences the degradation speed more than the degradation amount. These imaging results have provided fundamental chemical insights into the photolytic process for PLA, and at the same time they have demonstrated that the two-dimensional spectral data obtained by Compovision are useful for process monitoring of polymers.     

High-throughput study of poly(ethylene glycol)/ibuprofen formulations under controlled environment using FTIR imaging

Simultaneous analysis of many samples under identical conditions improves the effectiveness of research and accelerates product design. A novel spectroscopic imaging approach using a multichannel detector has been developed for parallel analysis of pharmaceutical formulations under controlled environments. Samples of formulations of ibuprofen in poly(ethylene glycol) have been prepared with ibuprofen concentrations ranging from 0 to 100% using a microdroplet deposition approach. The concentration of ibuprofen in PEG at which dimerization of ibuprofen molecules can be avoided has been determined via simultaneous measurement of all samples using in situ FTIR spectroscopic imaging. FTIR spectra from all samples have been analyzed to assess the molecular state of the drug and the degree of polymer swelling as a function of drug concentration. The effect of elevated temperature on the stability of all formulations was also studied. This high-throughput approach identified the concentration range for stable formulations and provided evidence that hydrogen bonding between ibuprofen and the polymer is responsible for enhanced stability at higher temperatures. This high-throughput imaging approach, based on a miniature sampling system, significantly reduces the experimental time by allowing many (potentially a few thousand) experiments to be run in parallel and increases the accuracy by minimizing variations between experiments.     

Some ramifications of a theorem of Boas and Pollard concerning the completion of a set of functions in

About fifty years ago, R. P. Boas and Harry Pollard proved that an orthonormal system that is completable by the adjunction of a finite number of functions also can be completed by multiplying the elements of the given system by a fixed, bounded, nonnegative measurable function. In subsequent years, several variations and extensions of this theorem have been given by a number of other investigators, and this program is continued here. A mildly surprising corollary of one of the results is that the trigonometric and Walsh systems can be multiplicatively transformed into quasibases for .

     

Subsystems of the Schauder system that are quasibases for

We show that if is a subsystem of the Faber-Schauder system, and if is complete in , then is a quasibasis for each space , . Although it follows from the work of Ul'yanov that each element of can be represented by a Schauder series that converges unconditionally to the function, in the metric of the space, it proves to be the case that none of the aforementioned systems is an unconditional quasibasis for any of the -spaces herein considered.