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Two-dimensional correlation spectroscopy in polymer study.

Park Y, Noda I, Jung YM - Front Chem (2015)

Bottom Line: This review outlines the recent works of two-dimensional correlation spectroscopy (2DCOS) in polymer study. 2DCOS is a powerful technique applicable to the in-depth analysis of various spectral data of polymers obtained under some type of perturbation.The powerful utility of 2DCOS combined with various analytical techniques in polymer studies and noteworthy developments of 2DCOS used in this field are also highlighted.

View Article: PubMed Central - PubMed

Affiliation: Department of Chemistry, Kangwon National University Chunchon, South Korea.

ABSTRACT
This review outlines the recent works of two-dimensional correlation spectroscopy (2DCOS) in polymer study. 2DCOS is a powerful technique applicable to the in-depth analysis of various spectral data of polymers obtained under some type of perturbation. The powerful utility of 2DCOS combined with various analytical techniques in polymer studies and noteworthy developments of 2DCOS used in this field are also highlighted.

No MeSH data available.


Temperature-dependent IR spectra of polystyrene-block-poly(n-pentyl methacrylate) (PS-PnPMA) measured during heating from 100 to 260°C at an interval of 5°C. (Reproduced with permission J. Mol. Struct. 2006, 799, 96–101, Copyright 2006, with permission from Elsevier).
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Figure 10: Temperature-dependent IR spectra of polystyrene-block-poly(n-pentyl methacrylate) (PS-PnPMA) measured during heating from 100 to 260°C at an interval of 5°C. (Reproduced with permission J. Mol. Struct. 2006, 799, 96–101, Copyright 2006, with permission from Elsevier).

Mentions: Jung et al. demonstrated that PCA 2DCOS through EMT technique was performed to more clearly understand the phase behavior of polystyrene-block-poly(n-pentyl methacrylate) (PS-PnPMA) (Jung et al., 2006). PS-PnPMA is a very interesting closed-loop block copolymer, which has a lower disorder-to-order transition (LDOT) temperature and an upper order-to-disorder transition (UODT) temperature. The temperature-dependent IR spectra of PS-PnPMA measured during heating from 100–260°C are shown in Figure 10. In the conventional 2D IR correlation spectra shown in Figure 11, the ordered state is completely different with two disordered states and these two disordered states at lower and higher temperatures are also different (Kim et al., 2006b). To highlight subtle differences of the two disordered states of PS-PnPMA, they applied PCA 2DCOS through EMT method to the temperature-dependent IR spectra. In PCA analysis, the original spectral data set shown in Figure 10 was decomposed into the scores and loading vectors. Synchronous PCA 2D correlation spectra generated from the reconstructed data matrix A* with the three principal components are like the conventional 2D correlation spectra but without noise contribution. Figures 12A–C shows synchronous PCA 2D correlation spectra generated from the EMT-reconstructed spectral data matrix A** obtained by replacing the original eigenvalues with m = 1/2 for disordered state at lower temperature, ordered state, and disordered state at higher temperature, respectively. By lowering the power of a set of eigenvalues associated with the original data, hidden property of phase transition from the contribution of minor but potentially interesting is much more greatly accentuated than conventional 2D correlation spectra. As shown in Figure 12, synchronous spectrum generated from the EMT-reconstructed spectral data matrix of the ordered state is completely different from those in the two disordered states and the clear difference between two disordered states is also observed. In the power spectrum, extracted along the diagonal line of the synchronous 2D correlation spectrum, in the top of Figures 12A,C, intensities of bands from C-C-O stretching, C-H deformation, and C=O stretching of PnPMA change greatly at lower temperature while those from phenyl group in PS change greatly at higher temperature. The distinct difference in two disordered states in the cross correlations of the bands from phenyl group in PS with that from C-C-O group in PnPMA reveals that the conformation of PS-PnPMA and the weak interaction between phenyl group of PS and the side chain of PnPMA in the two disordered states are different. The EMT technique clearly distinguish the very subtle differences of spectra which are not observed in conventional 2D correlation spectra.


Two-dimensional correlation spectroscopy in polymer study.

Park Y, Noda I, Jung YM - Front Chem (2015)

Temperature-dependent IR spectra of polystyrene-block-poly(n-pentyl methacrylate) (PS-PnPMA) measured during heating from 100 to 260°C at an interval of 5°C. (Reproduced with permission J. Mol. Struct. 2006, 799, 96–101, Copyright 2006, with permission from Elsevier).
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4356163&req=5

Figure 10: Temperature-dependent IR spectra of polystyrene-block-poly(n-pentyl methacrylate) (PS-PnPMA) measured during heating from 100 to 260°C at an interval of 5°C. (Reproduced with permission J. Mol. Struct. 2006, 799, 96–101, Copyright 2006, with permission from Elsevier).
Mentions: Jung et al. demonstrated that PCA 2DCOS through EMT technique was performed to more clearly understand the phase behavior of polystyrene-block-poly(n-pentyl methacrylate) (PS-PnPMA) (Jung et al., 2006). PS-PnPMA is a very interesting closed-loop block copolymer, which has a lower disorder-to-order transition (LDOT) temperature and an upper order-to-disorder transition (UODT) temperature. The temperature-dependent IR spectra of PS-PnPMA measured during heating from 100–260°C are shown in Figure 10. In the conventional 2D IR correlation spectra shown in Figure 11, the ordered state is completely different with two disordered states and these two disordered states at lower and higher temperatures are also different (Kim et al., 2006b). To highlight subtle differences of the two disordered states of PS-PnPMA, they applied PCA 2DCOS through EMT method to the temperature-dependent IR spectra. In PCA analysis, the original spectral data set shown in Figure 10 was decomposed into the scores and loading vectors. Synchronous PCA 2D correlation spectra generated from the reconstructed data matrix A* with the three principal components are like the conventional 2D correlation spectra but without noise contribution. Figures 12A–C shows synchronous PCA 2D correlation spectra generated from the EMT-reconstructed spectral data matrix A** obtained by replacing the original eigenvalues with m = 1/2 for disordered state at lower temperature, ordered state, and disordered state at higher temperature, respectively. By lowering the power of a set of eigenvalues associated with the original data, hidden property of phase transition from the contribution of minor but potentially interesting is much more greatly accentuated than conventional 2D correlation spectra. As shown in Figure 12, synchronous spectrum generated from the EMT-reconstructed spectral data matrix of the ordered state is completely different from those in the two disordered states and the clear difference between two disordered states is also observed. In the power spectrum, extracted along the diagonal line of the synchronous 2D correlation spectrum, in the top of Figures 12A,C, intensities of bands from C-C-O stretching, C-H deformation, and C=O stretching of PnPMA change greatly at lower temperature while those from phenyl group in PS change greatly at higher temperature. The distinct difference in two disordered states in the cross correlations of the bands from phenyl group in PS with that from C-C-O group in PnPMA reveals that the conformation of PS-PnPMA and the weak interaction between phenyl group of PS and the side chain of PnPMA in the two disordered states are different. The EMT technique clearly distinguish the very subtle differences of spectra which are not observed in conventional 2D correlation spectra.

Bottom Line: This review outlines the recent works of two-dimensional correlation spectroscopy (2DCOS) in polymer study. 2DCOS is a powerful technique applicable to the in-depth analysis of various spectral data of polymers obtained under some type of perturbation.The powerful utility of 2DCOS combined with various analytical techniques in polymer studies and noteworthy developments of 2DCOS used in this field are also highlighted.

View Article: PubMed Central - PubMed

Affiliation: Department of Chemistry, Kangwon National University Chunchon, South Korea.

ABSTRACT
This review outlines the recent works of two-dimensional correlation spectroscopy (2DCOS) in polymer study. 2DCOS is a powerful technique applicable to the in-depth analysis of various spectral data of polymers obtained under some type of perturbation. The powerful utility of 2DCOS combined with various analytical techniques in polymer studies and noteworthy developments of 2DCOS used in this field are also highlighted.

No MeSH data available.