Revealing System Dynamics through Decomposition of the Perturbation Domain in Two-Dimensional Correlation Spectroscopy

A technique is presented to simply and effectively decompose the perturbation domain in two-dimensional (2D) correlation maps calculated on a given set of vibrational spectra. Decomposition of the perturbation domain exposes a wealth of kinetic information complementary to the information extracted from conventional 2D correlation spectroscopy. It is shown that the technique produces “perturbation profile maps” that can be utilized in both the interpretation of the conventional 2D correlation maps and the independent kinetic analysis of the given system. Discrimination between spectral features exhibiting similar, but not identical, dynamics is facilitated by the decomposition, and spectral features exhibiting identical dynamics over the perturbation interval are quickly identified. Spectral features exhibiting similar dynamics over only a sub-range of the full perturbation are also identifiable. Interpretation of phase information illuminated in synchronous and asynchronous maps is simplified. Comparison between similar spectral features present in different samples is facilitated with the technique. The simplicity and ease of implementation of the technique make decomposition of the perturbation domain a valuable addition to the tools available in 2D correlation analysis.

[1]  Yan Wang,et al.  Examination of the Effect of Heating on the Secondary Structure of Avidin and Avidin—Biotin Complex by Resolution-Enhanced Two-Dimensional Infrared Correlation Spectroscopy , 2000 .

[2]  C Baldock,et al.  Fourier transform Raman spectroscopy of polyacrylamide gels (PAGs) for radiation dosimetry. , 1998, Physics in medicine and biology.

[3]  C De Wagter,et al.  An investigation of the chemical stability of a monomer/polymer gel dosimeter. , 2000, Physics in medicine and biology.

[4]  A. English,et al.  Two-dimensional infrared correlation spectroscopy as a probe of sequential events in the thermal unfolding of cytochromes c. , 2001, Biochemistry.

[5]  M. Auger,et al.  Investigation of the Temperature Behavior of the Bands Due to the Methylene Stretching Vibrations of Phospholipid Acyl Chains by Two-Dimensional Infrared Correlation Spectroscopy , 2000 .

[6]  Yukihiro Ozaki,et al.  A New Possibility of the Generalized Two-Dimensional Correlation Spectroscopy. 2. Sample−Sample and Wavenumber−Wavenumber Correlations of Temperature-Dependent Near-Infrared Spectra of Oleic Acid in the Pure Liquid State , 2000 .

[7]  H. Ishida,et al.  Quantitative Two-Dimensional Infrared (2D IR) Spectroscopy: Theoretical Development for General and Specific Cases , 1995 .

[8]  Isao Noda.  Progress in 2D correlation spectroscopy , 2001 .

[9]  P. Harrington,et al.  Effects of static spectrum removal and noise on 2D-correlation spectra of kinetic data , 1998 .

[10]  J. Gore,et al.  NMR relaxation enhancement in gels polymerized and cross-linked by ionizing radiation: a new approach to 3D dosimetry by MRI. , 1993, Magnetic resonance imaging.

[11]  I. Noda,et al.  Determination of Two-Dimensional Correlation Spectra Using the Hilbert Transform , 2000 .

[12]  J. Cox,et al.  Two-dimensional fluorescence correlation spectroscopy with modulated excitation. , 2001, Analytical chemistry.

[13]  H. Mantsch,et al.  Two-Dimensional Infrared Correlation Analysis of Protein Unfolding: Use of Spectral Simulations to Validate Structural Changes during Thermal Denaturation of Bacterial CMP Kinases , 2000 .

[14]  J A Mills,et al.  An investigation into the use of polymer gel dosimetry in low dose rate brachytherapy. , 1999, The British journal of radiology.

[15]  J. Battista,et al.  Optical CT reconstruction of 3D dose distributions using the ferrous-benzoic-xylenol (FBX) gel dosimeter. , 1998, Medical physics.

[16]  I. Noda.  Generalized Two-Dimensional Correlation Method Applicable to Infrared, Raman, and other Types of Spectroscopy , 1993 .

[17]  Peter de B. Harrington,et al.  Two-dimensional correlation analysis , 2000 .

[18]  C. Baldock,et al.  13C-NMR, 1H-NMR, and FT-raman study of radiation-induced modifications in radiation dosimetry polymer gels , 2001 .

[19]  M. A. Czarnecki.  Two-Dimensional Correlation Spectroscopy: Effect of Band Position, Width, and Intensity Changes on Correlation Intensities , 2000 .

[20]  Yukihiro Ozaki,et al.  Analysis of Near-Infrared Spectra of Complicated Biological Fluids by Two-Dimensional Correlation Spectroscopy: Protein and Fat Concentration-Dependent Spectral Changes of Milk , 1999 .

[21]  C. De Wagter,et al.  On the accuracy of monomer/polymer gel dosimetry in the proximity of a high-dose-rate 192Ir source. , 2001, Physics in medicine and biology.

[22]  J. Dempsey,et al.  Evaluation of polymer gels and MRI as a 3-D dosimeter for intensity-modulated radiation therapy. , 1999, Medical physics.

[23]  C Duzenli,et al.  Characterization of monomer/crosslinker consumption and polymer formation observed in FT-Raman spectra of irradiated polyacrylamide gels , 2001, Physics in medicine and biology.

[24]  Yukihiro Ozaki,et al.  A New Possibility of the Generalized Two-Dimensional Correlation Spectroscopy. 1. Sample-Sample Correlation Spectroscopy , 2000 .

[25]  C Duzenli,et al.  Effects of crosslinker fraction in polymer gel dosimeters using FT Raman spectroscopy. , 2001, Physics in medicine and biology.

[26]  G Schulze,et al.  Identification and Interpretation of Generalized Two-Dimensional Correlation Spectroscopy Features through Decomposition of the Perturbation Domain , 2003, Applied spectroscopy.

[27]  Y. Ozaki,et al.  Global Phase Angle Description of Generalized Two-Dimensional Correlation Spectroscopy: 1. Theory and its Simulation for Practical Use , 2001 .

[28]  C. Baldock,et al.  The relationship between radiation-induced chemical processes and transverse relaxation times in polymer gel dosimeters. , 2001, Physics in medicine and biology.

[29]  Y. Ozaki,et al.  Two-Dimensional Infrared Spectroscopy and Principle Component Analysis Studies of the Secondary Structure and Kinetics of Hydrogen−Deuterium Exchange of Human Serum Albumin , 2001 .

[30]  Y. Ozaki,et al.  Two-Dimensional/Attenuated Total Reflection Infrared Correlation Spectroscopy Studies on Secondary Structural Changes in Human Serum Albumin in Aqueous Solutions: pH-Dependent Structural Changes in the Secondary Structures and in the Hydrogen Bondings of Side Chains , 2001 .