A two-dimensional (2D) correlation method generally applicable to various types of spectroscopy, including IR and Raman spectroscopy, is introduced. In the proposed 2D correlation scheme, an external perturbation is applied to a system while being monitored by an electromagnetic probe. With the application of a correlation analysis to spectral intensity fluctuations induced by the perturbation, new types of spectra defined by two independent spectral variable axes are obtained. Such two-dimensional correlation spectra emphasize spectral features not readily observable in conventional one-dimensional spectra. While a similar 2D correlation formalism has already been developed in the past for analysis of simple sinusoidally varying IR signals, the newly proposed formalism is designed to handle signals fluctuating as an arbitrary function of time, or any other physical variable. This development makes the 2D correlation approach a universal spectroscopic tool, generally applicable to a very wide range of applications. The basic property of 2D correlation spectra obtained by the new method is described first, and several spectral data sets are analyzed by the proposed scheme to demonstrate the utility of generalized 2D correlation spectra. Potential applications of this 2D correlation approach are then explored.

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Recently, we reported the isothermal crystallization behaviors of poly(L-lactic acid) (PLLA) from the melt and glassy states, respectively [J. ]. Surprisingly, the quite different infrared (IR) spectral evolutions occur in the two crystallization processes at different temperatures in which the same crystal modification is expected to be formed. To clarify this unusual phenomenon, the crystal modifications and thermal behavior of PLLA samples prepared under different crystallization temperatures are investigated in detail by TEM, WAXD, and FTIR techniques. On the basis of the WAXD and IR data, a new crystal modification named the Ŕ form is proposed for the crystal structure of PLLA samples annealed at temperature below 120°C. Such crystal modification with loose 103 helical chain packing is less thermally stable than the standard R form of PLLA. This assignment can explain all the experiment observations well. Other possible mechanisms for the IR spectral difference of bulk PLLA samples annealed at different temperatures are also discussed.

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A novel concept in vibrational spectroscopy called two-dimensional infrared (2D IR) spectroscopy is described. In 2D IR, a spectrum defined by two independent wavenumbers is generated by a cross-correlation analysis of dynamic fluctuations of IR signals induced by an external perturbation. 2D IR spectra are especially suited for elucidating various chemical interactions among functional groups. Notable features of the 2D IR approach are: simplification of complex spectra consisting of many overlapped peaks; enhancement of spectral resolution by spreading peaks over the second dimension; and establishment of unambiguous assignments through correlation analysis of bands selectively coupled by various interaction mechanisms. The procedure for generating 2D IR correlation spectra and the properties of the 2D spectra are discussed in detail. Examples of 2D IR spectra are presented for atactic polystyrene and the proteinacious component of human stratum corneum to demonstrate the utility of this technique.

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A computationally efficient numerical procedure to generate two-dimensional (2D) correlation spectra from a set of spectral data collected at certain discrete intervals of an external physical variable, such as time, temperature, pressure, etc., is proposed. The method is based on the use of a discrete Hilbert transform algorithm which carries out the time-domain orthogonal transformation of dynamic spectra. The direct computation of a discrete Hilbert transform provides a definite computational advantage over the more traditional fast Fourier transform route, as long as the total number of discrete spectral data traces does not significantly exceed 40. Furthermore, the mathematical equivalence between the Hilbert transform approach and the original formal definition based on the Fourier transform offers an additional useful insight into the true nature of the asynchronous 2D spectrum, which may be regarded as a time-domain cross-correlation function between orthogonally transformed dynamic spectral intensity variations.

Infrared (IR) spectra of new types of bacterial copolyester, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), P(HB-co-HHx) (HHx = 2.5, 3.4, and 12 mol %), and poly(3-hydroxybutyrate) (PHB) were measured over a temperature range of 20 °C to higher temperatures (PHB, 185 °C; HHx = 2.5 mol %, 160 °C; HHx = 3.4 mol %, 160 °C; HHx = 12 mol %, 140 °C) to explore their structure and thermal behavior. The temperature-dependent IR spectral variations were analyzed for the CH stretching, CO stretching, CH3 deformation, and C−O−C stretching vibration regions, and bands characteristic of crystalline and amorphous parts were identified in each region. It has been found from the anomalous frequencies of the CH3 asymmetric stretching bands of the four polymers and the X-ray crystallographic structure of PHB that there is an inter- or intramolecular interaction (C−H···O hydrogen bond) between the CO group in one helical structure and the CH3 group in the other helical structure in PHB and P(HB-co-HHx). The bonding energy of the C−H···O hydrogen bond seems to be smaller than 4 kJ/mol, but considering the heat of fusion (12.5 kJ/mol) of PHB, it is likely that a chain of C−H···O hydrogen bond pairs link two parallel helical structures in the crystalline parts. The temperature-dependent IR spectral variations have shown that the crystallinity of P(HB-co-HHx) (HHx = 12 mol %) decreases gradually from a fairly low temperature (about 60 °C), while the crystallinity of PHB and P(HB-co-HHx) (HHx = 2.5 and 3.4 mol %) remains almost unchanged until just below their melting temperatures. It has also been revealed from the present study that the weakening of the C−H···O interaction starts from just above room temperature and proceeds gradually with increase in temperature, but the collapse of helical structure occurs at a much higher temperature for all the polymers investigated.