Do-Hyeon Yang

Nanoassembled thin film gas sensors. III. Sensitive detection of amine odors using TiO2/poly(acrylic acid) ultrathin film quartz crystal microbalance sensors.

Quartz crystal microbalance (QCM) gas sensors based on the alternate adsorption of TiO(2) and polyacrilic acid (PAA) were developed for the sensitive detection of amine odors. Individual TiO(2) gel layers could be regularly assembled with a thickness of approximately 0.3 nm by the gas-phase surface sol-gel process (GSSG). The thickness of the poly(acrylic acid) (PAA) layer is dependent on its molecular weight, showing different thicknesses of approximately 0.4 nm for PAA(25) (Mw 250,000) and 0.6-0.8 nm for PAA(400) (Mw 4,000,000). The QCM sensors showed a linear response to ammonia in the concentration range 0.3-15 ppm, depending on the deposition cycle of the alternate TiO(2)/PAA layer. The ammonia binding is based on the acid-base interaction to the free carboxylic acid groups of PAA and the limit of detection (LOD) of the 20-cycle TiO(2)/PAA(400) film was estimated to be 0.1 ppm when exposed to ammonia. The sensor response was very fast and stable in a wide relative humidity (rH) range of 30-70%, showing almost the same frequency changes at a given concentration of ammonia. Sensitivity to n-butylamine and ammonia was higher than to pyridine, which is owing to the difference of molecular weight and basicity of the amine analytes. The alternate TiO(2)/PAA(400) films have a highly effective ability to capture amine odors, and the ambient ammonia concentration of 15 ppm could be condensed up to approximately 20,000 ppm inside the films.

Films based on bacteriorhodopsin in sol-gel matrices

The bacteriorhodopsin film in gelatin matrixes which are used as sensitive elements of integrated optic and fibre-optic sensors of various vapor and gases components will not be able to carry out the chemical control of aqueous solutions. In the given paper the results of technological development of obtaining the bacteriorhodopsin (bR) films in a sol-gel matrix are represented. The films are obtained in a broad thickness range (from 0.5 to 20 microns) with various bR concentrations and photosensitize additives. The optimal technological conditions of obtaining of uniform films with given optical parameters are defined. The surface morphology and cross section of the obtained films was studied using an AFM and SEM. The films have a reasonable surface roughness (~ 100 nm) and a uniform distribution of the purple membrane fragments in the nanostructured sol-gel glass matrix along the films surface and thickness. The transmission spectrums have the characteristic for bR the absorption band, the value of which depends on bR concentration and technological features of the films deposition. The investigated photosensitive properties of the obtained films and influence on them of chemical components of aqueous solutions, allow recommending the thin bR films in sol-gel matrixes for creation of planar waveguides in the role of components of the chemical sensors of liquid solutions.

Self-assembly and imprinting of macrocyclic molecules in layer-by-layered TiO2 ultrathin films

Alternate TiO2 gel ultrathin films assembled with a macrocyclic carboxylic acids of tetrakis-4-carboxyphenyl porphine (TCPP) or tetra-4-carboxylphthalocyanine cobalt (II) (Co-TCPc) were prepared by the surface sol-gel process. To confirm the film growth and imprinting effect, quartz crystal microbalance (QCM) and UV-vis spectroscopy measurements were employed. The binding of TCPP was 1.2-14.3 times more selective compared to structurally related macrocyclic guest molecules. Among other findings, tetrakis-4-carboxymethyloxyphenyl porphine (TCMOPP) that has a spacer (-O-CH2-) between the phenyl rings and carboxylic acid moieties of TCPP showed a significantly lower binding efficiency equal to 0.07, regardless of its similar molecular structure to the template molecule. Structural difference of porphyrin and phthalocyanine analogs could be also selectively discriminated: the TCPP imprinted film showed ca. 13 times higher selectivity for recognition of TCPP itself from the mixture of TCPP and Co-TCPc. Characterization by AFM demonstrated that the TiO2/TCPP film has highly uniform surface and ultrathin thickness, while both TEM and SEM studies confirmed the immobilized structures of TCPP inside the film.

Landmine detection: Improved binding of 2,4-dinitrotoluene in a γ-CD/metal oxide matrix and its sensitive detection via a cyclic surface polarization impedance (cSPI) method

Highly sensitive and selective detection of 2,4-DNT, a representative explosive, was achieved by the synergic effect of molecular imprinting and host (cyclodextrin)-guest interaction in ultrathin layers of TiO(2) and SiO(2) gel; the detection limit using cSPI measurements reached nM concentration.