• Bulletin of the Korean Chemical Society
• /
• 제24권9호
• /
• pp.1345-1350
• /
• 2003

Principal component analysis based two-dimensional (PCA-2D) correlation analysis is applied to FTIR spectra of polystyrene/methyl ethyl ketone/toluene solution mixture during the solvent evaporation. Substantial amount of artificial noise were added to the experimental data to demonstrate the practical noise-suppressing benefit of PCA-2D technique. 2D correlation analysis of the reconstructed data matrix from PCA loading vectors and scores successfully extracted only the most important features of synchronicity and asynchronicity without interference from noise or insignificant minor components. 2D correlation spectra constructed with only one principal component yield strictly synchronous response with no discernible a asynchronous features, while those involving at least two or more principal components generated meaningful asynchronous 2D correlation spectra. Deliberate manipulation of the rank of the reconstructed data matrix, by choosing the appropriate number and type of PCs, yields potentially more refined 2D correlation spectra.

• Bulletin of the Korean Chemical Society
• /
• 제26권12호
• /
• pp.2027-2032
• /
• 2005

This paper demonstrates details of thermal behavior of Langmuir-Blodgett (LB) film of poly(tert-butyl methacrylate) (PtBMA) by using the principal component analysis based two-dimensional correlation spectroscopy (PCA2D) through eigenvalue manipulating transformation (EMT). By uniformly lowering the power of a set of eigenvalues associated with the original data, the smaller eigenvalues becomes more prominent and the subtle contribution from minor components is now highlighted much more strongly than the original data. Thus, the subtle difference of thermal behavior of LB film of PtBMA from minor components, which is not readily detectable in the conventional 2D correlation analysis, is much more noticeable than the original data. PCA2D correlation spectra with EMT operation for the temperature-dependent IR spectra of LB film of PtBMA reveal the hidden property of phase transition processes during heating.

• 한국고분자학회:학술대회논문집
• /
• 한국고분자학회 2006년도 IUPAC International Symposium on Advanced Polymers for Emerging Technologies
• /
• pp.355-355
• /
• 2006

In this study, we have applied principal component analysis-based 2D (PCA2D) correlation spectroscopy to the temperature-dependent IR spectra of biodegradable poly(hydroxyalkanoate). PCA2D analysis reveals clearly that there are two components in crystalline band of C=O stretching mode without being hampered by noise. To better understand the thermal behavior of biodegradable poly(hydroxyalkanoate), eigenvalue manipulating transformation (EMT) technique was also employed. By uniformly lowering the power of a set of eigenvalues associated with the original data, the subtle contributions from minor eigenvectors are highlighted. Details of thermal behavior of biodegradable poly(hydroxyalkanoate) studied by PCA2D correlation spectroscopy with EMT will be discussed.

• Bulletin of the Korean Chemical Society
• /
• 제32권7호
• /
• pp.2332-2338
• /
• 2011

In this study, we proposed a new promising idea of utilizing moving window principal component analysis (MWPCA) as a sensitive diagnostic tool to detect the presence of peak position shift. In this approach, the moving window is constructed from a small data segment along the wavenumber axis. For each window bound by a narrow wavenumber region, separate PCA analysis was applied. Simulated spectra with complex spectral feature variations were analyzed to explore the possibility of MWPCA technique. This MWPCA-based detection of the peak shift, potentially coupled with 2D correlation analysis to provide additional verification, may offer an attractive solution.

• 한국근적외분광분석학회:학술대회논문집
• /
• 한국근적외분광분석학회 2001년도 NIR-2001
• /
• pp.1281-1281
• /
• 2001

Near-infrared (NIR) spectra have bean measured for high-density (HDPE), linear low-density (LLDPE), and low-density (LDPE) polyethylene in pellet or thin films. The obtained spectra have been analyzed by conventional spectroscopic analysis methods and chemometrics. By using the second derivative, principal component analysis (PCA), and two-dimensional (2D) correlation analysis, we could separate many overlapped bands in the NIR. It was found that the intensities of some bands are sensitive to density and crystallinity of PE. This may be the first time that such bands in the NIR region have ever been discussed. Correlations of such marker bands among the NIR spectra have also been investigated. This sort of investigation is very important not only for further understanding of vibration spectra of various of PE but also for quality control of PE by vibrational spectroscopy. Figure 1 (a) and (b) shows a NIR reflectance spectrum of one of the LLDPE samples and that of PE, respectively. Figure 2 shows a PC weight loadings plot of factor 1 for a score plot of PCA for the 16 kinds of LLDPE and PE based upon their 51 NIR spectra in the 1100-1900 nm region. The PC loadings plot separates the bands due to the $CH_3$ groups and those arising form the $CH_2$ groups, allowing one to make band assignments. The 2D correlation analysis is also powerful in band enhancement, and the band assignments based upon PCA are in good agreement with those by the 2D correlation analysis.(Figure omitted). We have made a calibration model, which predicts the density of LLDPE by use of partial least square (PLS) regression. From the loadings plot of regression coefficients for the model , we suggest that the band at 1542, 1728, and 1764 nm very sensitive to the changes in density and crystalinity.

• 한국근적외분광분석학회:학술대회논문집
• /
• 한국근적외분광분석학회 2001년도 NIR-2001
• /
• pp.1286-1286
• /
• 2001

Despite extensive theoretical and experimental studies the structure of the protein-solvent interface is subject of many controversy. Understanding the processes that occur in aqueous solution requires understanding of the solvent influence on the structure of protein. The aim of this study is to investigate the applicability of NIR methods in the study of hydration phenomena in protein solutions. Temperature-induced changes in NIR spectra of -lactoglobulin (BLG) in aqueous solutions have been investigated by means of two-dimensional correlation spectroscopy (2DCOS) and principal component analysis (PCA). With the temperature increase the balance of forces between the BLG's interaction with itself and the BLGs interaction with its environment is disrupted leading to BLG unfolding. Significant differences of 2D signals and distinct discrepancies of loading on PC1 and PC2 were observed as a result of temperature increase. In the native folded conformation of BLC, most of the nonpolar amino acids are hidden in the centre of the structure, out of contact with water molecules, while charged groups are outside, in the contact with water. The polar groups promote low density Ih-type structure in the water outside this first hydration shell. When BLG unfolds it assumes a more extended configuration on which the previously buried nonpolar groups are exposed to water and promote the higher density II-type structure outside its first shell. Detailed assignments of bands attributed to the bulk water, different states of the hydrated water and the changed conformation of BLG are proposed.