FTIR microscopy and confocal Raman microscopy for studying lateral drug diffusion from a semisolid formulation.

Fourier transform infrared (FTIR) microscopy was applied to obtain information on lateral drug diffusion of dithranol in artificial acceptor membranes. Lateral (2D) drug distribution into an artificial membrane was investigated on an area of 300microm x 1000microm with a lateral resolution of 25microm x 25microm by integrating a specific IR band located at 1430cm(-1). The concentration profiles show a heterogeneous distribution of dithranol particles resulting in non-uniform drug diffusion. Use of the FTIR microscope either in the transmission or in the reflection mode was restricted to a thickness of the DDC membrane <15microm. The third dimension (depth profile) was analysed by means of confocal Raman microscopy (CRM). In an artificial membrane, the depth range from a minimum of 1.5microm up to a maximum of 49microm was analysed for dithranol distribution.

Photothermal imaging in 3D surface analysis of membrane drug delivery.

Various methods exist for research into the penetration process in the human nail plate and for investigation of dermal drug delivery. Application of spectroscopic methods in this scientific field is gaining importance. However, no method meets all demands of the large variety of applications. An alternative optical technique for the characterisation of samples is the photothermal spectroscopy. Photoacoustic techniques, photothermal radiometry, and photothermal beam deflection spectroscopy (PDS) are non-destructive analytical techniques that take advantage of the so-called photoacoustic and photothermal phenomena. PDS, in conjunction with an appropriate scanner, allows for depth profiling and is a promising technique for studies of three-dimensional drug diffusion into artificial and biological membranes. The objective of this article is to demonstrate the use of PDS imaging for pharmaceutical applications and drug delivery studies, with two experiments being used as examples: the follow-up of lateral dithranol penetration into an artificial membrane and depth-resolved measurement of the distribution of a model drug within a keratin membrane from bovine hoof.

Determination of light-absorbing layers at inner capillary surface by cw excitation crossed-beam thermal-lens spectrometry.

A thermal-lens spectrometric unit suitable for selective quantitative measurements of light-absorbing layers adsorbed onto the inner surface of a quartz glass capillary is described. The quantitative description of the thermal-lens signal generated in a quartz glass capillary with a light-absorbing layer at the inner surface of capillary is developed, which is based on the description for the thermal-lens experiment in the layered solids presented elsewhere. The accuracy of calculations is demonstrated by the comparison of predicted results with the experimental data and those predicted by the conventional theory. The data achieved prove the accuracy of calculations both for the time dependent thermal-lens signal and for the lock-in amplifier signal under variation of the spectrometer configuration for capillaries having an adsorbed layer. The proposed technique is used for the investigation of chromate/2,10-ionene and 4-aminoazobenzene adsorption at capillary walls. The estimates of the minimum light absorption detectable at capillary walls are at a level of 1 x 10(-5) abs. units; the linear range of the thermal-lens signal from the inner surface layer no less than three orders of magnitude is predicted.

Optical methods for measurements of skin penetration.

Fourier transform infrared photoacoustic (PAS), photothermal deflection (PDS) and Raman spectroscopy belong to the modern innovative noninvasive analytical tools that are beginning to be recognized as highly potential techniques for the noninvasive study of biological tissues and human skin under in vivo conditions. They can be applied to obtain information regarding the molecular composition of the skin down to several hundred micrometers below the skin surface. All three methods allow depth-resolved investigations. While PAS and PDS use a frequency modulation of the excitation beam to reach deeper regions in the sample, the principle of confocal Raman microspectroscopy (CRM) is a movement of the specimen in the focal plane. In consideration of depth measurements PAS and PDS complete the applicable spectrum of CRM, since Raman microscopy requires particular transparent materials.

Photothermal deflection determination of iron(II) with ferrozine with sorption preconcentration on Silufol plates.

Photothermal deflection spectroscopy was applied to the selective detection of iron(II) chelate with ferrozine by its sorption preconcentration on Silufol plates. The linearity range was 1 x 10(-11) - 6 x 10(-8) mol cm(-2) of chelate at the plate surface, which corresponded to 1 x 10(-9) -4 x 10(-6) M of chelate in solution. The limits of detection and quantification are 8 x 10(-12) and 2.5 x 10(-11) mol cm(-2) at the plate from 15 microL of test solution (0.5 nM and 1.5 nM in solution, respectively), and the absolute detection limit is 8 fmol in the whole spot applied to a plate. Characteristics and features of photothermal deflection detection are discussed.

Indirect thermal lens detection for capillary electrophoresis.

Thermal lens detection with a 325.0nm He-Cd excitation laser is used for thermooptical indirect detection in combination with the capillary electrophoretic separation of organic anions. The optimization of indirect thermooptical detection is discussed. With Mordant Yellow 7 (an azo dye) chosen as a probe ion limits of detection for 1-heptane-, 1-pentane-, 1-butane-, 1-propanesulfonic, and acetic acid at a level of nx10(-7)M were achieved with a separation electrolyte containing 50muM of the probe ion and 5mM Tris pH 9.90. A further increase in the detection sensitivity (twofold decrease in the limit of detection ) was obtained with a separation electrolyte containing a volume fraction of 20% acetonitrile.

Investigation of ionene adsorption on quartz surfaces by thermal-lens spectrometry.

Thermal-lens spectrometry was used for the investigation of the adsorption of ionene to quartz surfaces. The thermooptical analysis of the surface makes it possible to distinguish the modified surface from a clean quartz surface and to provide sensitive direct concentration measurements of the light absorbing co-adsorbed substance. The co-adsorption of chromate ions and 2,10-ionene from aqueous solutions to quartz surfaces was investigated and the desorption procedure proposed.

Capillary electrophoretic determination of dithiocarbamates and ethyl xanthate.

A simple and sensitive capillary electrophoretic method was developed for the separation and determination of sodium methyldithiocarbamate (metham), manganese ethylenebisdithiocarbamate (maneb) and ethyl xanthate in boric acid buffer by direct UV absorbance detection at lambda = 254 nm. The separation is dependent on pH and nature of the buffer. The detection limits (S/N = 3) are 1.7 x 10(-6) mol/L for ethyl xanthate, 1.3 x 10(-6) mol/L for metham and 2.1 x 10(-6) mol/L for maneb. The method has been successfully applied to the analysis of wheat samples spiked with maneb and in a commercial sample.

Capillary electrophoretic determination of zinc dimethyldithiocarbamate (Ziram) and zinc ethylenebisdithiocarbamate (Zineb).

A simple and sensitive capillary electrophoretic method was developed for the separation and determination of Ziram and Zineb in boric acid buffer by direct UV absorbance detection at lambda=254 nm. The separation is dependent on pH and nature of the buffer. The detection limits (S/N=3) are 1.88x10(-6) mol/l (0.57 mug/ml) and 2.48x10(-6) mol/l (0.68 mug/ml) for Ziram and Zineb, respectively. The method was successfully applied to the analysis of wheat samples spiked with Ziram and Zineb.

Capillary electrophoretic determination of ferric dimethyldithiocarbamate as iron(III) chelate of EDTA.

A simple and sensitive capillary electrophoretic method with UV detection has been developed for the determination of Ferbam (ferric dimethyldithiocarbamate) in boric acid buffer after its acidic decomposition and complexation with EDTA as Fe-EDTA- complex. The determination is dependent on the pH and the nature of the buffer solutions. In this method the detection limit (S/N = 3) is 1.8 x 10(-6) mol/L (0.7 mg/kg) of Ferbam. The relative standard deviation for the analysis of 50 microg/ml was found to be 2.9%. The method was successfully applied for the analysis of wheat grain samples spiked with Ferbam. The applicability of capillary electrophoresis as a useful tool for the analysis of Ferbam is demonstrated.

A review of capillary electrophoretic separations and their studies by nuclear magnetic resonance.

Capillary electrophoresis as a microvolume separation technique is receiving increased recognition for its use in the separation of inorganic and organic compounds due to its short analysis time and small sample volume in the nanoliter and picoliter ranges. The combination of capillary electrophoresis, one of the most-often employed chromatographic separation techniques, and studies by nuclear magnetic resonance (NMR) spectroscopy is finding an increased number of applications in pharmaceutical, biomedical, and polymer research. This paper discusses the applications of capillary electrophoresis for the separation of various analytes and their studies by NMR.

Miniaturized thermal lens device for capillary electrophoresis.

In this paper we will report on the combination of a miniaturized fiber optic modified photothermal sensor (size 2 x 2 x 2 cm) to capillary electrophoresis (CE) as detection device. The properties and the performances of the thermal lens detector, based on a double beam absorption scheme, were studied in a capillary electrophoresis system with different types of toxic pollutants, e.g. pesticides. A tunable Argon ion laser, which emits between 364 and 514 nm, was adapted to a commercial injection and high voltage CE system. The miniaturization of the thermal lens detector head with optical waveguides allows the combination with typical CE systems, therefore pesticides in microliter volumes can be treated. The detector performance is demonstrated with the monitoring of pesticides in capillaries with various diameter. The limit of detection is one of two orders of magnitude better than conventional absorption detector.

Trace analysis of pollutants in water using the photothermal interferometry as HPLC detector.

A new procedure including high performance liquid chromatography in combination with photothermal interference spectroscopy as detection device (HPLC/PIS) has been proposed, optimized and its figures of merit for pesticide residue analysis are shown. The flowing sample under study is set in one arm of a Mach-Zehnder interferometer, and its refractive index is modulated by a periodically chopped continuous wave argon ion laser. As chopper, an acousto optical modulator has been introduced to switch the excitation laser beam between different lines (457 nm, 488 nm, 514 nm) simultaneously. Thus a multi component analysis can be realized either by using an HPLC-system in front of the PIS device or by a multi line Ar(+)-laser, directly. The limit of detection of the HPLC/PIS system reached 71 microg/l of the pesticide di-nitro-ortho-cresol (DNOC).