Special Report Chemical Sensors for In Vivo Monitoring: Clinical Aspects

Abstract

The origins and purpose of a new European Community Concerted Action on “Chemical Sensors for In Vivo Monitoring” are described: the overall aim is to promote the development and application of chemical sensors for in vivo monitoring. A report is presented on the first Workshop Meeting entitled “Clinical Aspects of In Vivo Sensing”, which addressed the question of the analyte to be sensed, specific and general problems of in vivo sensing, and future prospects.     

Preparation of a mixed-mode hydrophilic interaction/anion-exchange polymeric monolithic stationary phase for capillary liquid chromatography of polar analytes

A novel cationic hydrophilic interaction monolithic stationary phase based on the copolymerization of 2-(methacryloyloxy)ethyltrimethylammonium methyl sulfate (META) and pentaerythritol triacrylate (PETA) in a binary porogenic solvent consisting of cyclohexanol/ethylene glycol was designed for performing capillary liquid chromatography. While META functioned as both the ion-exchange sites and polar ligand provider, the PETA, a trivinyl monomer, was introduced as cross-linker. The monolithic stationary phases with different properties were easily prepared by adjusting the amount of META in the polymerization solution as well as the composition of the porogenic solvent. The hydrophilicity of the monolith increased with increasing content of META in the polymerization mixture. A typical hydrophilic interaction chromatography mechanism was observed when the content of acetonitrile in the mobile phase was higher than 20%. The poly(META-co-PETA) monolith showed very good selectivity for neutral, basic and acidic polar analytes. For polar-charged analytes, both hydrophilic interaction and electrostatic interaction contributed to their retention. Peak tailing of basic compounds was avoided and the efficient separation of benzoic acid derivatives was obtained.     

Multicomponent analyses of chiral samples by use of regression analysis of UV–visible spectra of cyclodextrin guest–host complexes

We report the first combined use of analytical spectroscopy, guest–host chemistry, and multivariate regression analysis for determination of enantiometric composition of multicomponent samples of chiral analytes. Sample solutions containing multicomponent analytes of ephedrine, tryptophan, propranolol, and proline of varying enantiomeric composition with beta-cyclodextrin (BCD) or methyl-beta-cyclodextrin (Me-BCD) as chiral host molecules were investigated using ultraviolet (UV)–visible spectroscopy. The interactions of enantiomers of chiral analytes with chiral hosts resulted in the formation of transient diastereomeric inclusion complexes with varying spectral properties. Multivariate analysis using partial-least-square (PLS) regression was used to correlate subtle changes in the UV–visible spectra of the guest–host complexes with the enantiomeric composition of the calibration samples. These PLS regressions were carefully optimized and then used to predict the enantiomeric composition of multicomponent chiral analytes of validation samples. The results of these validation studies demonstrate the predictive ability of the regression models for determination of future enantiomeric composition of samples. The accuracy of the models to correctly predict the enantiomeric composition of samples, evaluated by use of the root mean square percent relative error (RMS%RE) was analyte and chiral host dependent. In general, better prediction of enantiomeric composition of samples and low RMS%RE values were obtained when Me-BCD was used as the chiral host. The analyses procedure reported here is simple, rapid, and inexpensive. In addition, this approach does not require prior separation of chiral analytes, thus reducing analysis time and eliminating the need for expensive chiral columns.     

Electronic tongue based on an array of metallic potentiometric sensors

An electronic tongue system based on the array of six metallic potentiometric sensors (metallic wires) was developed and utilized for discrimination of foodstuffs: several types of vinegar and fruit juices. Copper, tin, iron, aluminum, brass and stainless steel wires were included in the array and supplemented by pH glass electrode. The response of potentiometric metallic sensors towards various organic acids has been studied and possible sensitivity mechanisms were discussed. Overall potential changes of metallic sensors were exanimate as complex mixed signals influenced by several components presenting in analyte employing chemometric approach. The multisensor array of such a type can be useful for several applications since of simplicity in handling, low cost of sensors and easy measure procedure.     

Determination of polar analytes in aqueous matrices by purge and trap

(not readable) fully autimated purge and trap system has been developed for (not readable) detemination of volatile wine components. The proposed system consists of sampler, a purge and trap instrument, and a GC, (not readable) steps, from the uptake of the infiltrated wine from the sampler (not readable) to the printout of the intergrated chromatograms, proceed(not readable), Typical problems occurring when analyzing polar analytes by the classical purse and trap approach have been specifically addressed. The system has been desiggned to handle such difficult (not readable) analytes. Efforts have been made to improve the reproducibility and the carry-over of these analytes. The measures adopted include: thorough rinsing and subsequent conditioning of the P + T parger; elimination of matrix effects by dilution and high salt (not readable); tight specification of purge relevant parameters; split-inter-(not readable) to improve GC retention time reproducibility.     

Electrical and memory properties of silicon nitride structures with embedded Si nanocrystals

In this work, the electrical and memory behaviour of metal-silicon nitride-silicon structures with an embedded nanocrystalline silicon layer, which either consists of separated silicon nanocrystals, or is a continuous nanocrystalline layer, are presented. The structures were prepared by low-pressure chemical vapour deposition (LPCVD). The effect of the duration of deposition and the structure of the nanocrystalline layer were studied. The writing/erasing behaviour was similar for all the structures, but the retention properties were much worse in the structure with a continuous nanocrystalline layer, than in the structures with separated Si nanocrystals. This indicates that Si nanocrystals play role in charge storage in the studied structures.     

Separation of cationic analytes by nonionic micellar electrokinetic chromatography using polyoxyethylene lauryl ether surfactants with different polyoxyethylene length

Although nonionic micellar electrokinetic chromatography is used for the separation of charged compounds that are not easily separated by capillary zone electrophoresis, the effect of the hydrophilic moiety of the nonionic surfactant has not been studied well. In this study, the separation of ultraviolet‐absorbing amino acids was studied in electrokinetic chromatography using neutral polyoxyethylene lauryl ether surfactants (Adekatol) in the separation solution. The effect of the polyethylene moiety (the number of repeating units was from 6.5 to 50) of the hydrophobic test amino acids (methionine, tryptophan, and tysorine) was studied using a 10 cm effective length capillary. The separation mechanism was based on hydrophobic as well as hydrogen bonding interactions at the micellar surface, which was made of the polyoxyethylene moiety. The length of the polyoxyethylene moiety of the surfactants was not important in nonionic micellar electrokinetic chromatography mode.     

Effect of wavelength of sensitizing light on holographic storage properties in LiNbO3:Fe:Ni crystal

By sensitizing with 514 nm green light, 488 nm blue light and 390 nm ultraviolet light, respectively, recording with 633 nm red light, effect of wavelength of sensitizing light on holographic storage properties in LiNbO₃:Fe:Ni crystal is investigated in detail. It is shown that by shortening the wavelength of sensitizing light gradually, nonvolatile holographic recording properties of oxidized LiNbO₃:Fe:Ni crystal is optimized gradually, 390 nm ultraviolet light is the best as the sensitizing light. Considering the absorption of sensitizing light, to obtain the best performance in two-center holographic recording we must choose a sensitizing wavelength that is long enough to prevent unwanted absorptions (band-to-band, etc.) and short enough to result in efficient sensitization from the deep traps. So in practice a trade-off is always needed. Explanation is presented theoretically.     

Nonvolatile holographic recording in Ti, Fe Co-doped LiTaO3 crystal

Ti, Fe Co-doped LiTaO₃ (LT) crystals have been grown by the Czochralski method from the congruent melts. The absorption spectra of crystal were measured before and after ultraviolet illumination. Holograms have been recorded in doubly doped crystals with continuous-wave laser light by use of two-color method. The maximum value of refractive-index changes 7×10⁻⁵ is achieved.