Potential of far-ultraviolet absorption spectroscopy as a highly sensitive analysis method for aqueous solutions. Part II: monitoring the quality of semiconductor wafer cleaning solutions using attenuated total reflection

Far-ultraviolet (FUV) spectroscopy combined with attenuated total reflection (ATR) is employed for direct measurement of the concentrations of semiconductor wafer cleaning fluids such as SC-1 (aqueous solution of NH(3) and H(2)O(2)) and SC-2 (aqueous solution of HCl and H(2)O(2)). FUV spectra of these aqueous solutions in the 170-200 nm region are highly sensitive to changes in both hydrogen bonding and hydration. Although ATR measurement results in lower absorptivity compared to transmittance measurement, it is possible to increase absorption with greater evanescent wave penetration depth using a low refractive index internal reflection element (IRE). We adopt quartz as an IRE material. Since the refractive index of quartz becomes lower than that of water in the low energy side of an intense absorption band due to the n --> sigma* transition of water, the quartz IRE yields non-total reflection wavelength regions. However, near 175 nm the effective absorptivity of the tail of water's absorption band can be successfully enlarged, making the FUV-ATR technique suitable for measuring the concentrations of the components in the semiconductor wafer cleaning fluids. In the present study we prepared the same cleaning fluids as those used in actual semiconductor fabrication and measured their FUV-ATR spectra in the 150-300 nm wavelength range. It was found that even with the quartz IRE one can measure FUV-ATR spectra under total reflection conditions at 175 nm or above. We created calibration models for predicting both NH(3) and H(2)O(2) in the concentration ranges of 0-10% in SC-1 using multiple linear regression (MLR). The standard deviations of the models were 0.033% and 0.265% for NH(3) and H(2)O(2), respectively. The same procedure was repeated under the same conditions for HCl and H(2)O(2) in SC-2, yielding corresponding values of 0.018% for HCl and 0.178% for H(2)O(2).     

Sensitive detection and identification of organic liquids using the second derivative of surface plasmon resonance near-infrared spectra

Sensitive detection of near-infrared (NIR) spectra of several organic liquids has been carried out by surface plasmon resonance (SPR) NIR spectroscopy. For all the liquids, 50- to 100-fold enhancements of the absorption peaks were obtained in the combination band region 4500-4000 cm(-1) using a gold film with a thickness of 14 nm. The SPR peak shows up as an unnecessary broadband peak or trend in an SPR-NIR spectrum, and it was difficult to separate it from the absorption signals. In order to remove the contribution of SPR from the raw SPR-NIR spectrum, the second-order derivative has been employed. The second derivative of the SPR-NIR spectrum was reasonably comparable to that of the corresponding transmittance spectrum. Two simple algorithms for sample identification from the second-derivative data have been proposed. One is similarity, which directly compares the second-derivative spectrum of an unknown sample with that of a known reference sample. The other is fitness, which is defined as a ratio of the common part of absorption peak wavenumbers of the sample and the reference. Although both methods are unfit for the identification of a minor component in a mixture, a major component can be definitely identified by choosing an informative wavenumber region. It was found that the wavenumber region 4250-4080 cm(-1) is especially useful for the identification of similar molecules such as normal alkanes.     

Application of chitosan solutions gelled by melB tyrosinase to water‐resistant adhesives

An investigation was undertaken on the application of dilute chitosan solutions gelled by melB tyrosinase‐catalyzed reaction with 3,4‐dihydroxyphenethylamine (dopamine). The tyrosinase‐catalyzed reaction with dopamine conferred water‐resistant adhesive properties to the semi‐dilute chitosan solutions. The viscosity of the chitosan solutions highly increased by the tyrosinase‐catalyzed quinone conversion and the subsequent nonenzymatic reactions of o‐quinones with amino groups of the chitosan chains. The viscosity of chitosan solutions highly increased in shorter reaction times by addition of melB tyrosinase. Therefore, in this study, the gelation of a chitosan solution was carried out without poly(ethylene glycol) (PEG), which was added for the gelation of chitosan solutions using mushroom tyrosinase. The highly viscous, gel‐like modified chitosan materials were allowed to spread onto the surfaces of the glass slides, which were tightly lapped together and were held under water. Tensile shear adhesive strength of over 400 kPa was observed for the modified chitosan samples. An increase in either amino group concentration of the chitosan solutions or molecular mass of the chitosan samples used effectively led to an increase in adhesive strength of the glass slides. Adhesive strength obtained by chitosan materials gelled enzymatically was higher than that obtained by a chitosan gel prepared with glutaraldehyde as a chemical crosslinking agent. In addition, the use of melB tyrosinase led to a sharp increase in adhesive strength in shorter reaction times without other additives such as PEG. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Degradation of bisphenol A using sonochemical reactions

The sonochemical degradation of bisphenol A in aqueous solution, a suspected endocrine disruptor, which can cause several damages for humans, animals and the environment, was investigated at different ultrasonic intensities under air atmosphere. Bisphenol A (0.50mM) was completely degraded after 10, 3 and 2h of ultrasonic irradiation at a frequency of 404kHz, and intensities of 3.5, 9.0 and 12.9kW/m(2), respectively. During ultrasonic irradiation, some aromatic intermediates such as 2-(4-hydroxyphenyl)-2-(3,4-dihydroxyphenyl)propane, commonly known as 3-hydroxybisphenol A were detected. Further cleavage of the aromatic rings resulted in other products, like formaldehyde and organic acids, also being detected. The proposed pathways of bisphenol A degradation by ultrasonic irradiation are based on the above-mentioned intermediates. The relationship between bisphenol A degradation and formation of hydrogen peroxide and nitric acid was taken into account, correlating this to the radicals that take part in the degradation process. In order to optimize the performance of the ultrasonic system, additional experiments using Fenton-like reactions were also carried out. However, the addition of iron (II) sulfate (FeSO(4)) did not increase bisphenol A degradation rates. Compared with the system without iron (II) sulfate, the total organic carbon concentration (TOC) was reduced by about 30%, at 404kHz and 9.0kW/m(2).     

Utilization of excess sludge by acetone-butanol-ethanol fermentation employing Clostridium saccharoperbutylacetonicum N1-4 (ATCC 13564)

Clostridium saccharoperbutylacetonicum N1-4 could not grow or produce butanol in excess sludge medium. However, adding glucose to the excess sludge medium resulted in a specific growth rate and butanol productivity of 0.29 h(-1) and 0.55 g/l/h, respectively, and the final butanol production reached 9.3 g/l. Since the content of suspended solids in medium reduced to less than 50% of the initial content during acetone-butanol-ethanol (ABE) fermentation, the sludge was quantitatively decreased by this fermentation employing this strain.     

Classification of intramural metastases and lymph node metastases of esophageal cancer from gene expression based on boosting and projective adaptive resonance theory

Esophageal cancer is a well-known cancer with poorer prognosis than other cancers. An optimal and individualized treatment protocol based on accurate diagnosis is urgently needed to improve the treatment of cancer patients. For this purpose, it is important to develop a sophisticated algorithm that can manage a large amount of data, such as gene expression data from DNA microarrays, for optimal and individualized diagnosis. Marker gene selection is essential in the analysis of gene expression data. We have already developed a combination method of the use of the projective adaptive resonance theory and that of a boosted fuzzy classifier with the SWEEP operator denoted PART-BFCS. This method is superior to other methods, and has four features, namely fast calculation, accurate prediction, reliable prediction, and rule extraction. In this study, we applied this method to analyze microarray data obtained from esophageal cancer patients. A combination method of PART-BFCS and the U-test was also investigated. It was necessary to use a specific type of BFCS, namely, BFCS-1,2, because the esophageal cancer data were very complexity. PART-BFCS and PART-BFCS with the U-test models showed higher performances than two conventional methods, namely, k-nearest neighbor (kNN) and weighted voting (WV). The genes including CDK6 could be found by our methods and excellent IF-THEN rules could be extracted. The genes selected in this study have a high potential as new diagnosis markers for esophageal cancer. These results indicate that the new methods can be used in marker gene selection for the diagnosis of cancer patients.     

Regional difference of water content in human skin studied by diffuse-reflectance near-infrared spectroscopy: consideration of measurement depth

Diffuse reflectance (DF) spectra in the 1250-2500 nm region were measured in vivo for the skin of the forehead, cheek, jaw, elbow, volar forearm, palm, knee, and heel of seven healthy volunteers, using a Fourier transform near-infrared (FT-NIR) spectrophotometer with a fiber-optic probe. Apparent regional differences of water content in the skin, as estimated from the diffuse reflectance NIR spectra, are discussed in relation to the influence of measurement depth. The NIR spectra were collected with or without a 300 microm gap between the fiber-optic probe and the skin surface. For comparison, in vitro NIR spectra of stratum corneum sheets equilibrated at 41, 50, 63, and 81% relative humidity, at 25 degrees C, were also obtained. There was a difference in the ratio of the two water bands centered near 1450 nm and 1900 nm between the contact and non-contact measurements. In addition, regional differences of water content calculated from the peak height of the 1900 nm water band, which was normalized to the peak height of the 2175 nm amide band, were compared. The results of Monte Carlo simulation indicated that the apparent regional differences arise at least in part from differences in the measurement depth due to differences in specular reflection at the skin surface and in the thickness of the stratum corneum.     

Determination of newly installed feeder route considering use of existing feeder

In planning a distribution system for an urban area, when a feeder is newly installed, the route of the feeder must be determined among many candidates, considering investment cost and constraints. However, it is difficult for planners to find the optimal route of the newly installed feeder, because too many candidate routes exist which can be constructed along roads in the service area of the power company, and it must be considered whether the end part of an existing feeder can be used as a part of a newly installed feeder within specified loaded value. In this paper, in order to support planners' decision making in selecting an optimal route for newly installed feeders, the authors have formulated the problem mathematically, and propose a new solution algorithm to find the optimal route by the Dijkstra method. Through numerical examples, the authors demonstrate the validity of the proposed method. © 1999 Scripta Technica, Electr Eng Jpn, 129(3): 40–50, 1999     

Formation and stability of β-structure in biodegradable ultra-high-molecular-weight poly(3-hydroxybutyrate) by infrared, Raman, and quantum chemical calculation studies

Infrared (IR) and Raman spectra were measured for four kinds of ultra-high-molecular-weight poly[(R)-3-hydroxybutyrate] (UHMW-PHB) films: a solvent-cast film, a cold-drawn film, a two-step-drawn film, and a hot-drawn film. Quantum chemical calculations were made for octamer models of UHMW-PHB with a helix conformation (α-form) and a planar zigzag conformation (β-form). Comparison of the results between the Raman spectra of four kinds of films and the quantum chemical calculations of octamer models revealed that only two-step-drawn film yields additional bands at 1735, 966, 935, 908, and 858 cm⁻¹ assignable to the β-structure, suggesting that it contains the β-form as well as the α-form. Detailed comparison of the frequencies and intensities of Raman bands between the observed and calculated values for the β-form indicates that the amount of β-form is relatively small and that the β-structure has a less ordered structure. The infrared and Raman spectra of two-step-drawn film also indicate that it has more amorphous parts than other films. When the two-step-drawn film was further heated up to 130 °C and then cooled down to room temperature, the above additional bands due to the β-form disappeared in the Raman spectra, suggesting that the β-form is less stable than α-form.