Photocatalytic TiO2 particles confer superior antibacterial effects in a nutrition-rich environment: an in vitro study.

Titanium dioxide (TiO(2)) is known to confer photocatalytic bactericidal effects under ultraviolet (UV) irradiation. Few reports are available, however, on the clinical applications of TiO(2) particle mixtures. Our objective in the present research was to evaluate the in vitro bactericidal effects of a TiO(2) particle mixture in a nutrition-rich biological environment. A bacterial suspension of Staphylococcus aureus and epidermidis 3 x 10(3) CFU/mL was added to a TiO(2) particle mixture (0.038 mg/mL) containing mainly sodium percarbonate and citric acid. To simulate a biological environment, 40 microL of 10% bovine serum albumin was added and the culture temperature was maintained at 37 degrees C. The resulting product was irradiated by UV light and the bacterial survival rate was calculated for each time of UV irradiation. In the control sample treated with distilled water + UV, the bacteria survived at a high rate even after 180 min. In the TiO(2) mixture + UV sample, meanwhile, the bacterial survival rate dropped to 43.8% and 6.0% of the baseline values in S. aureus and S. epidermidis, respectively, after 60 min of UV irradiation. The photocatalytic antibacterial action of the TiO(2) particle mixture was high even in a protein-rich biological environment.

The bactericidal efficacy of a photocatalytic TiO(2) particle mixture with oxidizer against Staphylococcus aureus.

By proving the bactericidal effects of a low-concentration titanium dioxide (TiO(2)) particle mixture against Staphylococcus aureus, we hope to ultimately apply a mixture of this type as part of a clinical treatment regimen. A bacterial suspension of S. aureus 1 x 10(5) CFU/ml was added dropwise to a TiO(2) particle mixture (19 ppm TiO(2)) and irradiated by ultraviolet (UV) light. The colony-forming units were counted and the bacterial survival rate was calculated. In the control sample, the bacterial survival rate was 83.3% even after 120 min. In the TiO(2) mixture + UV sample, the bacteria count dropped sharply, reaching 17.3% of the baseline value at 30 min and 0.4% at 60 min. TiO(2) particles dispersed in water mixtures are known to elicit highly efficient UV absorption and greater bonding to bacteria. A reaction of the TiO(2) with another oxidizer altered the aqueous pH and accelerated the photocatalytic chemical reaction. The TiO(2) particle mixture showed high antibacterial action against S. aureus even at a low concentration.

Photocatalytic bactericidal action of fluorescent light in a titanium dioxide particle mixture: an in vitro study.

Traditional titanium dioxide (TiO(2)) has photocatalytic bactericidal properties only under ultraviolet (UV) irradiation, which restricts its use in clinical treatment regimens. In this study, we evaluated the photocatalytic bactericidal effects of an aqueous system of TiO(2) particles irradiated by fluorescent light (FL) on Staphylococcus aureus. A TiO(2) particle mixture containing 19 ppm (0.019 mg/mL) of TiO(2) was prepared. A bacterial solution of 1 x 10(5) CFU/mL was added one drop at a time to the TiO(2) mixture. The resulting product was then irradiated with FL. The bacterial survival rate decreased steadily in the TiO(2) mixture group, reaching 76.7% after 30 min of FL irradiation and 10.9% after 60 min. After 60 to 180 min, the bacterial survival ratio of the TiO(2) mixture group was significantly lower than that of the control group (P < 0.05). The present study indicates that treating the surfaces of surgical devices and the surgical field with a TiO(2) particle mixture can create a nearly sterile environment that can be maintained throughout surgery, even at low luminous intensities.

Fabrication of well-defined microdomains composed of aldehyde- and carboxy-terminated self-assembled monolayers.

Coplanar microdomains consisting of two organosilane self-assembled monolayers (SAMs) terminated with chemically reactive functional groups (e.g., aldehyde-[CHO] and carboxy-[COOH] groups) were prepared on Si substrates covered with native oxide (SiO2/Si). A SAM of triethoxysilylundecanal (TESUD) molecules was prepared by chemical vapor deposition on the SiO2/Si surfaces. A few of these samples were exposed to 172 nm vacuum-ultraviolet (UV) radiation for 5-60 min at 10(5) Pa. Various experimental techniques including water-contact angle measurements, ellipsometry, attenuated total reflection Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and atomic force microscopy confirmed that CHO terminal groups of the SAM have been photochemically converted to COOH groups. Based on this result, site-selective photoirradiation of the TESUD-SAM with the same radiation source was performed using a photomask. Lateral force microscopy images revealed that well-ordered microstructures of 5 x 5 microm2 square-shaped features are formed on the substrate. The difference in chemical reactivity was characterized by fluorescence microscopy using specific bonding between biotin hydrazide and streptavidin-conjugated quantum dots (QDs). The fluorescence microscopy images revealed that biotin hydrazide immobilized site-selectively on the masked CHO-terminated regions and not on the vacuum-UV irradiated regions. However, the latter regions showed chemical reactivity to biotin hydrazide after activation treatments using N-hydroxysuccinimide and 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride, and well-defined QDs patterns can be obtained within these regions. This suggests that the surface CHO groups of the vacuum-UV irradiated regions were transformed to COOH groups, and the activation treatments lead to the formation of active N-hydroxysuccinimidyl esters, which are reactive toward amine groups of biotin hydrazide.

Ion-exclusion/adsorption chromatography of dimethylsulfoxide and its derivatives for the evaluation to quality-test of TiO(2)-photocatalyst in water.

Ion-exclusion/adsorption chromatography of dimethylsulfoxide (DMSO) and its derivatives, i.e., methanesulfinic acid (MSI), methanesulfonic acid (MSA) and sulfuric acid (SA), was developed in order to clear the decomposition mechanism of DMSO on quality-test of TiO(2)-photocatalyst in water. The separation was achieved by the adsorption effect for DMSO and ion-exclusion effect for MSI, MSA and SA under optimum conditions, using a weakly acidic cation-exchange resin column with 20mM succinic acid as the eluent. In this system, DMSO and MSI with UV at 195nm and MSA and SA with conductivity detection were consecutively determined by single injection and single separation column. This method was used to monitor the artificial decomposition of DMSO induced by a photocatalyst. The concentration of DMSO by active oxygens (e.g., OH radical) generated from surface of photocatalyst was found to be decreased through the stoichiometric reaction in the order of MSI, MSA and SA.

Vacancy ion-exclusion/adsorption chromatography of aliphatic amines on a polymethacrylate-based weakly basic anion-exchange column.

Vacancy ion-exclusion/adsorption chromatography has been applied to investigate the separation behavior of five aliphatic amines (ethylamine, propylamine, butylamine, pentylamine and hexylamine) on a polymethacrylate-based weakly basic anion-exchange column (Tosoh TSKgel DEAE-5PW). This system is consisted of analytes as a mobile phase and water as an injected sample. In the vacancy ion-exclusion/adsorption chromatography, the elution order was as follows: ethylamine < propylamine < butylamine < pentylamine < hexylamine, depending on their hydrophobicity. The retention times of the amines were decreased with decreasing their concentrations in the mobile phase. The retention times and resolutions of the amines were increased by adding a basic compound (e.g., lithium hydroxide or heptylamine) and by increasing the pH of mobile phase (pH > 11). This was because the dissociations of amine samples in the mobile phase were suppressed and thus the hydrophobic adsorption effects were enhanced. The linearity of calibration graphs could be obtained from the peak areas of the amine samples injected to the 0.05, 0.5 and 5 mM of amine mobile phase at pH 11 by heptylamine. The detection limits of aliphatic amines as injected samples were around 1 microM for five aliphatic amines at three different amine mobile phases. From these results, the retention behaviors of aliphatic amines on vacancy ion-exclusion/adsorption chromatography were concluded to be governed by the hydrophobic adsorption effect.

Highly sensitive determination of hydrazine ion by ion-exclusion chromatography with ion-exchange enhancement of conductivity detection.

An ion-exclusion chromatography method with ion-exchange enhancement of conductivity was developed for the selective separation and sensitive determination of hydrazine ion from alkali/alkaline earth metal cations and ammonium ion. Hydrazine ion was separated by ion-exclusion/penetration effect from other cations on a weakly basic anion-exchange column in the OH- form (TSKgel DEAE-5PW). Moreover, two different ion-exchange resin columns were inserted between the separating column and conductimetric detector in order to improve the sensitivity of hydrazine ion. The first enhancement column packed with a strongly basic anion-exchange resin in the SO4(2-) form (TSKgel SAX) for hydrazine ion can convert from N2H5OH to (N2H5)2SO4. Moreover, the second enhancement column packed with a strongly acidic cation-change resin in the H+ form (TSKgel SCX) can convert to H2SO4. As a result, the sensitivity of hydrazine ion using two conductivity enhancement columns could be 26.8-times greater than using the separating column alone. This method was effectiveness also for the enhancement of ammonium ion (6.1-times) and sodium ion (1.2-times). The calibration graph of hydrazine ion detected as H2SO4 was linear over the concentration range of 0.001-100 ppm (r2 = 0.9988). The detection limit of hydrazine ion in this system was 0.64 ppb. Therefore, hydrazine ion in real boiler water sample could be accurately determined, avoiding the interference of other cations.

Determination of some aliphatic carboxylic acids in anaerobic digestion process waters by ion-exclusion chromatography with conductimetric detection on a weakly acidic cation-exchange resin column.

The determination of seven aliphatic carboxylic acids, formic, acetic, propionic, isobutyric, n-butyric, isovaleric and n-valeric acids in anaerobic digestion process waters was examined using ion-exclusion chromatography with conductimetric detection. The analysis of these biologically important carboxylic acids is necessary as a measure for evaluating and controlling the process. The ion-exclusion chromatography system employed consisted of polymethacrylate-based weakly acidic cation-exchange resin columns (TSKgel OApak-A or TSKgel Super IC-A/C). weakly acidic eluent (benzoic acid), and conductimetric detection. Particle size and cation-exchange capacity were 5 microm and 0.1 meq./ml for TSKgel OApak-A and 3 microm and 0.2 meq./ml for TSKgel Super IC-A/C, respectively. A dilute eluent (1.0-2.0 mM) of benzoic acid was effective for the high resolution and highly conductimetric detection of the carboxylic acids. The good separation of isobutyric and n-butyric acids was performed using the TSKgel Super IC-A/C column (150 mm x 6.0 mm i.d. x 2). The simple and good chromatograms were obtained by the optimized ion-exclusion chromatography conditions for real samples from mesophilic anaerobic digestors, thus the aliphatic carboxylic acids were successfully determined without any interferences.

Ion-exclusion chromatography with conductimetric detection of aliphatic carboxylic acids on a weakly acidic cation-exchange resin by elution with benzoic acid-beta-cyclodextrin.

In this study, an aqueous solution consisting of benzoic acid with low background conductivity and beta-cyclodextrin (beta-CD) of hydrophilic nature and the inclusion effect to benzoic acid were used as eluent for the ion-exclusion chromatographic separation of aliphatic carboxylic acids with different pKa values and hydrophobicity on a polymethacrylate-based weakly acidic cation-exchange resin in the H+ form. With increasing concentration of beta-cyclodextrin in the eluent, the retention times of the carboxylic acids decreased due to the increased hydrophilicity of the polymethacrylate-based cation-exchange resin surface from the adsorption of OH groups of beta-cyclodextrin. Moreover, the eluent background conductivity decreased with increasing concentration of beta-cyclodextrin in 1 mM benzoic acid, which could result in higher sensitivity for conductimetric detection. The ion-exclusion chromatographic separation of carboxylic acids with high resolution and sensitivity was accomplished successfully by elution with a 1 mM benzoic acid-10 mM cyclodextrin solution without chemical suppression.

Vacancy ion-exclusion chromatography of haloacetic acids on a weakly acidic cation-exchange resin.

A new and simple approach is described for the determination of the haloacetic acids (such as mono-, di- and trichloroacetic acids) usually found in drinking water as chlorination by-products after disinfection processes and acetic acid. The new approach, termed vacancy ion-exclusion chromatography, is based on an ion-exclusion mechanism but using the sample solution as the mobile phase, pure water as the injected sample, and a weakly acidic cation-exchange resin column (TSKgel OApak-A) as the stationary phase. The addition of sulfuric acid to the mobile phase results in highly sensitive conductivity detection with sharp and well-shaped peaks, leading to excellent and efficient separations. The elution order was sulfuric acid, dichloroacetic acid, monochloroacetic acid, trichloroacetic acid, and acetic acid. The separation of these acids depends on their pKa values. Acids with lower pKa values were eluted earlier than those with higher pKa, except for trichloroacetic acid due to a hydrophobic-adsorption effect occurring as a side-effect of vacancy ion-exclusion chromatography. The detection limits of these acids in the present study with conductivity detection were 3.4 microM for monochloroacetic acid, 0.86 microM for dichloroacetic acid and 0.15 microM for trichloroacetic acid.

Vacancy ion-exclusion chromatography of aromatic carboxylic acids on a weakly acidic cation-exchange resin.

Determination of aromatic carboxylic acids by conventional ion-exclusion chromatography is relatively difficult and methods generally rely on hydrophobic interaction between the solute and the resin. To overcome the difficulties in determining aromatic carboxylic acids a new approach is presented, termed vacancy ion-exclusion chromatography, which is based on use of the sample as mobile phase and an injection of aqueous 10% methanol onto a weakly acidic cation-exchange column (TSKgel OApak-A). Highly sensitive conductivity detection occurred with sharp and well-shaped peaks, leading to very efficient separations. The effects of sulfuric acid concentration added to the mobile phase, flow-rate, and column temperature on the retention volume of tested aromatic carboxylic acids was investigated. Retention times were found to be affected by the concentration of the analytes in the mobile phase and to some extent also by the addition of an organic modifier such as methanol to the injected water sample. Separation of sulfuric acid (SA), naphthalenetetracarboxylic acid (NTCA), phthalic acid (PA) and benzoic acid (BA) was satisfactory using this new approach. Detection limits were 0.66, 0.67, 0.42 and 0.86 microM and detector responses were linear in the range 1-100, 1-80, 2.5-100 and 10-40 microM, for SA, NTCA, PA and BA, respectively. Precision for retention times was 0.36% and for peak areas was 1.5%.

Qualitative analysis of some carboxylic acids by ion-exclusion chromatography with atmospheric pressure chemical ionization mass spectrometric detection.

A simple, selective and sensitive method for the determination of carboxylic acids has been developed. A mixture of formic, acetic, propionic, valeric, isovaleric, isobutyric, and isocaproic acids has been separated on a polymethacrylate-based weak acidic cation-exchange resin (TSK gel OA pak-A) based on an ion-exclusion chromatographic mechanism with detection using UV-photodiode array, conductivity and atmospheric pressure chemical ionization mass spectrometry (APCI-MS). A mobile phase consisting of 0.85 mM benzoic acid in 10% aqueous methanol (pH 3.89) was used to separate the above carboxylic acids in about 40 min. For LC-MS, the APCI interface was used in the negative ionization mode. Linear plots of peak area versus concentration were obtained over the range 1-30 mM (r2=0.9982) and 1-30 mM (r2=0.9958) for conductimetric and MS detection, respectively. The detection limits of the target carboxylic acids calculated at S/N=3 ranged from 0.078 to 2.3 microM for conductimetric and photometric detection and from 0.66 to 3.82 microM for ion-exclusion chromatography-APCI-MS. The reproducibility of retention times was 0.12-0.16% relative standard deviation for ion-exclusion chromatography and 1.21-2.5% for ion-exclusion chromatography-APCI-MS. The method was applied to the determination of carboxylic acids in red wine, white wine, apple vinegar, and Japanese rice wine.

Vacancy ion-exclusion chromatography of carboxylic acids on a weakly acidic cation-exchange resin.

In this preliminary study, a new approach to ion-exclusion chromatography is proposed to overcome the relatively poor conductivity detection response which occurs in ion-exclusion chromatography when acids are added to the eluent in order to improve peak shape. This approach, termed vacancy ion-exclusion chromatography, requires the sample to be used as eluent and a sample of water to be injected onto a weakly acidic cation-exchange column (TSKgel OApak-A). Vacancy peaks for each of the analytes appear at the retention times of these analytes. Highly sensitive conductivity detection is possible and sharp, well-shaped peaks are produced, leading to efficient separations. Retention times were found to be affected by the concentration of the analytes in the eluent, and also by the presence of an organic modifier such as methanol in the eluent. Detection limits for oxalic, formic, acetic, propionic, butyric and valeric acids were 0.1, 0.2, 0.3, 0.3, 0.4 and 0.5 microM, respectively, and linear ranges for some acids extended over two orders of magnitude. Precision values for retention times were 0.21% and for peak areas were <1.90%. The vacancy ion-exclusion chromatography method was found to give detection responses four to 10 times higher than conventional ion-exclusion chromatography using sulfuric acid eluent and two to five times higher than conventional ion-exclusion chromatography using benzoic acid eluent.