X-ray ptychographic and fluorescence microscopy using virtual single-pixel imaging based deconvolution with accurate probe images.

Simultaneous measurement of X-ray ptychography and fluorescence microscopy allows high-resolution and high-sensitivity observations of the microstructure and trace-element distribution of a sample. In this paper, we propose a method for improving scanning fluorescence X-ray microscopy (SFXM) images, in which the SFXM image is deconvolved via virtual single-pixel imaging using different probe images for each scanning point obtained by X-ray ptychographic reconstruction. Numerical simulations confirmed that this method can increase the spatial resolution while suppressing artifacts caused by probe imprecision, e.g., probe position errors and wavefront changes. The method also worked well in synchrotron radiation experiments to increase the spatial resolution and was applied to the observation of S element maps of ZnS particles.

Development and application of a tender X-ray ptychographic coherent diffraction imaging system on BL27SU at SPring-8.

Ptychographic coherent diffraction imaging (CDI) allows the visualization of both the structure and chemical state of materials on the nanoscale, and has been developed for use in the soft and hard X-ray regions. In this study, a ptychographic CDI system with pinhole or Fresnel zone-plate optics for use in the tender X-ray region (2-5 keV) was developed on beamline BL27SU at SPring-8, in which high-precision pinholes optimized for the tender energy range were used to obtain diffraction intensity patterns with a low background, and a temperature stabilization system was developed to reduce the drift of the sample position. A ptychography measurement of a 200 nm thick tantalum test chart was performed at an incident X-ray energy of 2.500 keV, and the phase image of the test chart was successfully reconstructed with approximately 50 nm resolution. As an application to practical materials, a sulfur polymer material was measured in the range of 2.465 to 2.500 keV including the sulfur K absorption edge, and the phase and absorption images were successfully reconstructed and the nanoscale absorption/phase spectra were derived from images at multiple energies. In 3 GeV synchrotron radiation facilities with a low-emittance storage ring, the use of the present system will allow the visualization on the nanoscale of the chemical states of various light elements that play important roles in materials science, biology and environmental science.

Chiroptical study of α-aliphatic amino acid films in the vacuum ultraviolet region.

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.

First observation of natural circular dichroism spectra in the extreme ultraviolet region using a polarizing undulator-based optical system and its polarization characteristics.

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.

Accurate and quick calibration method for polarization-modulation spectroscopy using an ac-modulated polarizing undulator.

An accurate calibration method in which an ac-modulated polarizing undulator is used for polarization modulation spectroscopy such as circular dichroism (CD) and linear dichroism (LD) has been proposed and successfully applied to vacuum ultraviolet (vuv) CD and LD spectra measured at beamline BL-5B in the electron storage ring, TERAS, at AIST. This calibration method employs an undulator-modulation spectroscopic method with a multireflection polarimeter, and it uses electronic and optical elements identical to those used for the CD and LD measurements. This method regards the polarimeter as a standard sample for the CD and LD measurements in the vuv region in which a standard sample has not yet been established. The calibration factors for the CD and LD spectra are obtained over a wide range of wavelengths, from 120 to 230 nm, at TERAS BL-5B. The calibrated CD and LD spectra measured at TERAS exhibit good agreement with the standard spectra for wavelengths greater than 170 nm; the mean differences between the standard and calibrated CD and LD spectra are approximately 7% and 4%, respectively. This method enables a remarkable reduction in the experimental time, from approximately 1 h to less than 10 min that is sufficient to observe the storage-ring current dependence of the calibration factors. This method can be applied to the calibration of vuv-CD spectra measured using a conventional photoelastic modulator and for performing an accurate analysis of protein secondary structures.

Compact optical cell system for vacuum ultraviolet absorption and circular dichroism spectroscopy and its application to aqueous solution sample.

We have designed a compact optical cell for studying the absorption and circular dichroism (CD) of a solution sample in the vacuum ultraviolet (VUV) region using a temperature control unit. The cell size was 34 mm in diameter and 14 mm in length. Such compactness was obtained by coating the VUV scintillator onto the outside of the back window. Because this scintillator converts the transmitted VUV light to visible light, the outside of this cell is operated under atmospheric pressure. The temperature of the sample solution was maintained in the range of 5 degrees C to 80 degrees C using a temperature control unit with a Peltier thermoelectric element. Changes in the sample temperature were observed by monitoring the absorption intensity of water. Through the study of VUV-CD spectra of ammonium camphor-10-sulfonate aqueous solutions and the transmitted spectrum of an empty cell, it was concluded that this cell unit has sufficient performance for use in VUV spectroscopy.

Recent progress in vacuum-ultraviolet polarization modulation spectroscopy using polarizing undulator at the TERAS BL5 beamline.

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.

Development of vacuum-ultraviolet circular dichroism measurement system using a polarizing undulator.

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.