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A series of natural circular dichroism (CD) and absorption spectra for films of α-aliphatic amino acids--such as alanine, aminobutyric acid, norvaline, norleucine, valine, leucine, and isoleucine--in the vacuum ultraviolet (VUV) region were observed with the absolute values of optical constants at the undulator-based CD beamline TERAS BL5. Preliminary predictions of some CD spectra were also performed, based on quantum-chemical calculations using the crystal structure. Although the absorption spectra show similar features to each other, significant differences between the CD spectra were found, especially in the 7-8 eV region. The CD spectra of aliphatic amino acids with branched alkyl groups in the side-chain--such as valine, leucine, and isoleucine--exhibit strong negative CD peaks in this energy region. In contrast, the corresponding CD peaks were weak or absent in the spectra of amino acids with straight alkyl groups. Our simple calculation, and the absorption spectra of alkanes, suggest that this difference partly originates from the contribution of the alkyl group. Clear discrepancies between the CD spectra of these amino acids in solutions and those in the solid state were also observed; this is probably caused by the different molecular structures in each state. Our results clearly indicated that CD spectra in the VUV region were very sensitive to the conformations of chiral molecules.

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Natural circular dichroism (CD) spectra in the extreme ultraviolet (EUV) region down to a wavelength of 80 nm have been observed for the first time, using an alanine thin film deposited on sodium salicylate coated glass as a sample. Calibrated EUV-CD spectra of L-alanine exhibited a large negative peak at around 120 nm and a positive CD signal below 90 nm, which were roughly predicted by theoretical calculations. A CD measurement system with an Onuki-type polarizing undulator was used to obtain the EUV-CD spectra. This CD system, the development of which took five years, can be used to observe even weak natural CD spectra. The polarization characteristics of this system were also evaluated in order to calibrate the recorded CD spectra.

We have developed an improved circular dichroism (CD) and linear dichroism (LD) simultaneous measurement system for the vacuum ultraviolet (VUV) region by polarization modulation techniques using a four-period Onuki-type crossed undulator as a polarized light source. The system has been constructed at the VUV beamline BL-5 in the electron storage ring TERAS, at AIST. Our improvements, in particular the adoption of an optical chopper as the detection method of incident light, have resulted in a flat baseline and a consequent simplification of the Mueller matrix calculation for our optical system. Based on the Mueller matrix calculation, we have successfully measured real VUV-CD and LD spectra of leucine films for wavelengths down to 160 nm with absolute optical constants. The obtained spectra show good consistency with spectra measured by conventional methods.

Polarization modulation spectroscopy using an Onuki-type undulator is a useful technique for circular dichroism study in the vacuum-ultraviolet region. We have been developing the vacuum-ultraviolet circular dichroism (vuv-CD) spectroscopy in TERAS BL5 beamline at AIST. This paper describes recent improvements in our instrumentation and methods of analysis to achieve precise and absolute measurements. The CD signal is usually accompanied by experimental artifacts, and elimination of all possible artifacts is the key issue for making reliable measurements. After improving beamline optical system, light flux monitor, and undulator operation method, the base line shift of the CD spectrum is suppressed less than 3x10(-4). Sample manipulation and data processing procedures are also described and absolute CD spectrum can be obtained even for linear anisotropic sample. These progresses lead to more quantitative comparison of experimental with calculation on vuv-CD spectrum.

We observed the natural circular dichroism NCD of amino acid films in the soft X-ray region for the first time [1]. Based on the success, a new generation of detection system is now under preparation. Vacuum ultraviolet NCD of amino acid films was measured successfully using a polarizing undulator [2] installed at the TERAS electron storage ring at AIST, Tsukuba, Japan. A result of NCD measurement for alanine films is described in detail.