The mechanism for negative photochromism of spiropyran in silica

The mechanism for negative photochromism of spiropyran in silica was investigated. Prior to our study, the chemical origin of the high thermal stability of the photomerocyanine form (PMC‐form) dispersed in perhydropolysilazane (PHPS), which is converted to silica at ambient temperature, had been investigated. The high thermal stability of the PMC‐form is attributed to the protonated PMC‐form (H???PMC‐form), which is produced by intermolecular hydrogen bonding between oxide anions generated by the cleavage of the C ? O bonds and the partially uncondensed Si ? OH and O ? H bonds of silica. Furthermore, the H???PMC‐form could be thermally isomerized from the SP‐form without UV light irradiation. This specific phenomenon is caused by the so‐called negative photochromism. In this study, we proposed a mechanism for negative photochromism according to the relationship of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). The relationship between the HOMOs was determined using cyclic voltammetry (CV) and ultraviolet photoelectron spectroscopy (UPS). On the other hand, the relationship between the LUMOs was determined from the respective optical bandgap. As a result, the HOMO level of H???PMC‐form was ?6.1 eV and that of SP‐form was ?5.3 eV. Accordingly, the thermodynamic stabilization of H???PMC‐form was attributed to the thermal isomerization through negative photochromism from the SP‐form. Copyright © 2011 John Wiley & Sons, Ltd.     

Response of HD-V2 radiochromic film to argon ions

A two-dimensional dose detector for ion beam is required in many high energy density physics experiments. As a solid detector, the GAFChromic film offers a good spatial resolution and dosimetric accuracy. For an absolute dose measurement, the relative effectiveness, which represents the darkening efficiency of the film to a radiation source, needs to be taken into consideration. In this contribution, the dose-response of HD-V2 to argon ions is presented for the first time. The calibration was taken over the dose range of 65 Gy-660 Gy with 8-keV argon ions. The response of net optical density is from 0.01 to 0.05. Triple-color dose-response functions are derived. The relative effectiveness for the argon ion beams is about 5%, much lower than that of protons and carbon ions. To explain this effect, the inactivation probability based on track theory of ion bombardment is proposed. Furthermore, a theoretical prediction of the relative effectiveness for single ion is presented, showing the dependence of the darkening efficiency on the atomic number and the incident energy of ions.     

30‐Lens interferometer for high‐energy X‐rays

A novel high‐energy multi‐lens interferometer consisting of 30 arrays of planar compound refractive lenses is reported. Under coherent illumination each lens array creates a diffraction‐limited secondary source. Overlapping such coherent beams produces an interference pattern demonstrating strong longitudinal functional dependence. The proposed multi‐lens interferometer was tested experimentally at the 100 m‐long ID11 ESRF beamline in the X‐ray energy range from 30 to 65 keV. The interference pattern generated by the interferometer was recorded at fundamental and fractional Talbot distances. An effective source size (FWHM) of the order of 15 µm was determined from the first Talbot image, proving the concept that the multi‐lens interferometer can be used as a high‐resolution tool for beam diagnostics.     

Ultrafast switching of hard X‐rays

A new concept for shortening hard X‐ray pulses emitted from a third‐generation synchrotron source down to few picoseconds is presented. The device, called the PicoSwitch, exploits the dynamics of coherent acoustic phonons in a photo‐excited thin film. A characterization of the structure demonstrates switching times of ≤ 5 ps and a peak reflectivity of ～10^?3. The device is tested in a real synchrotron‐based pump–probe experiment and reveals features of coherent phonon propagation in a second thin film sample, thus demonstrating the potential to significantly improve the temporal resolution at existing synchrotron facilities.     

Synchrotron X‐ray microbeam dosimetry with a 20 micrometre resolution scintillator fibre‐optic dosimeter

Cancer is one of the leading causes of death worldwide. External beam radiation therapy is one of the most important modalities for the treatment of cancers. Synchrotron microbeam radiation therapy (MRT) is a novel pre‐clinical therapy that uses highly spatially fractionated X‐ray beams to target tumours, allowing doses much higher than conventional radiotherapies to be delivered. A dosimeter with a high spatial resolution is required to provide the appropriate quality assurance for MRT. This work presents a plastic scintillator fibre optic dosimeter with a one‐dimensional spatial resolution of 20 µm, an improvement on the dosimeter with a resolution of 50 µm that was demonstrated in previous work. The ability of this probe to resolve microbeams of width 50 µm has been demonstrated. The major limitations of this method were identified, most notably the low‐light signal resulting from the small sensitive volume, which made valley dose measurements very challenging. A titanium‐based reflective paint was used as a coating on the probe to improve the light collection, but a possible effect of the high‐Z material on the probes water‐equivalence has been identified. The effect of the reflective paint was a 28.5 ± 4.6% increase in the total light collected; it did not affect the shape of the depth‐dose profile, nor did it explain an over‐response observed when used to probe at low depths, when compared with an ionization chamber. With improvements to the data acquisition, this probe design has the potential to provide a water‐equivalent, inexpensive dosimetry tool for MRT.     

U and Th thin film neutron dosimetry for fission-track dating: application to the age standard Moldavite

Neutron dosimetry based on U and Th thin films was used for fission-track dating of the age standard Moldavite, the central European tektite, from the Middle Miocene deposit of Jankov (southern Bohemia, Czech Republic). Our fission-track age () agrees with a recent ⁴⁰Ar/³⁹Ar age, , based on several determinations on Moldavites from different sediments, including the Jankov deposit. This result indicates that the U and Th thin film neutron dosimetry represents a reliable alternative for an absolute approach in fission-track dating.     

Simple dose rate measurements for a very high synchrotron X‐ray flux

Dose measurements based on methylene blue (MB) bleaching, widely used for ultraviolet light, can also be applied to X‐rays including very high flux levels. This method has been tested by using both MB bleaching and Fricke dosimetry for a conventional monochromatic X‐ray source and then for `white‐beam' synchrotron radiation. The results show that MB bleaching dosimetry can easily measure X‐ray doses up to at least 10⁵ Gy s^?1, as long as the MB concentration is sufficiently high. This condition can be verified from the deviations from linearity of the bleaching versus exposure time.     

Transient spectroscopic characterization of the ring‐opening reaction of tetrahydrochromeno[2,3‐dimethyl]indole

Tetrahydrochromeno is a structural variant of spiropyran that undergoes a reversible ring‐opening to generate a colored nitrophenolate intermediate. Earlier work confirmed this intermediate through trimethylsilyl cyanide trapping under continuous irradiation. We have performed transient absorption spectroscopy to further characterize the mechanism of the ring‐opening reaction. Excitation at 355 nm produced a transient species with an absorption maximum at 445 nm, which we assign to the nitrophenolate unit of the ring‐opened product. The transient absorption decays after ~970 ns with small optical density changes corresponding to a 0.15 quantum yield. Exposure to oxygen did not exhibit a significant deleterious effect on the photoisomerization of the chromeno dye. Time‐dependent density functional theory corroborated spectroscopic assignments of the starting chromeno and the putative ring‐opened intermediate. The excited state behavior of this system parallels the structurally similar oxazine system reported by Raymo and coworkers. The one significant difference is the longer lifetime of the photochemically generated intermediate from chromeno. Copyright © 2015 John Wiley & Sons, Ltd.     

Combined measurement of X‐ray photon correlation spectroscopy and diffracted X‐ray tracking using pink beam X‐rays

Combined X‐ray photon correlation spectroscopy (XPCS) and diffracted X‐ray tracking (DXT) measurements of carbon‐black nanocrystals embedded in styrene–butadiene rubber were performed. From the intensity fluctuation of speckle patterns in a small‐angle scattering region (XPCS), dynamical information relating to the translational motion can be obtained, and the rotational motion is observed through the changes in the positions of DXT diffraction spots. Graphitized carbon‐black nanocrystals in unvulcanized styrene–butadiene rubber showed an apparent discrepancy between their translational and rotational motions; this result seems to support a stress‐relaxation model for the origin of super‐diffusive particle motion that is widely observed in nanocolloidal systems. Combined measurements using these two techniques will give new insights into nanoscopic dynamics, and will be useful as a microrheology technique.     

Radiobiological features of the anti‐cancer strategies involving synchrotron X‐rays

Synchrotrons are opening new paths in innovative anti‐cancer radiotherapy strategies. Indeed, the fluence of X‐rays induced by synchrotrons is so high (10⁶ times higher than standard medical irradiators) that it enables the production of X‐ray beams tunable in energy (monochromatic beams) and in size (micrometric beams). Monochromatic synchrotron X‐ray beams theoretically permit photoactivate high‐Z elements to be introduced in or close to tumours in order to increase the yield of damage by enhanced energy photoabsorption. This is notably the case of attempts with iodinated contrast agents used in tumour imaging (the computed tomography therapy approach) and with platinated agents used in chemotherapy (the PAT‐Plat approach). Micrometric synchrotron X‐ray beams theoretically permit very high radiation doses to accumulate in tumours by using arrays of parallel microplanar beams that spare the surrounding tissues (the microbeam radiation therapy approach). These anti‐cancer applications of synchrotron radiation have been developed at the European Synchrotron Radiation Facility to be applied to glioma, one of the tumour tissues most refractory to standard treatments. In the present paper the molecular and cellular mechanisms involved in these three approaches are reviewed, in the context of recent advances in radiobiology. Furthermore, by considering the unavoidable biases, an attempt to propose a comparison of the different results obtained in preclinical trials dealing with rats bearing tumours is given.     

Fluorescence imaging of reactive oxygen species by confocal laser scanning microscopy for track analysis of synchrotron X‐ray photoelectric nanoradiator dose: X‐ray pump–optical probe

Bursts of emissions of low‐energy electrons, including interatomic Coulomb decay electrons and Auger electrons (0–1000 eV), as well as X‐ray fluorescence produced by irradiation of large‐Z element nanoparticles by either X‐ray photons or high‐energy ion beams, is referred to as the nanoradiator effect. In therapeutic applications, this effect can damage pathological tissues that selectively take up the nanoparticles. Herein, a new nanoradiator dosimetry method is presented that uses probes for reactive oxygen species (ROS) incorporated into three‐dimensional gels, on which macrophages containing iron oxide nanoparticles (IONs) are attached. This method, together with site‐specific irradiation of the intracellular nanoparticles from a microbeam of polychromatic synchrotron X‐rays (5–14 keV), measures the range and distribution of OH radicals produced by X‐ray emission or superoxide anions () produced by low‐energy electrons. The measurements are based on confocal laser scanning of the fluorescence of the hydroxyl radical probe 2‐[6‐(4′‐amino)phenoxy‐3H‐xanthen‐3‐on‐9‐yl] benzoic acid (APF) or the superoxide probe hydroethidine‐dihydroethidium (DHE) that was oxidized by each ROS, enabling tracking of the radiation dose emitted by the nanoradiator. In the range 70 µm below the irradiated cell, radicals derived mostly from either incident X‐ray or X‐ray fluorescence of ION nanoradiators are distributed along the line of depth direction in ROS gel. In contrast, derived from secondary electron or low‐energy electron emission by ION nanoradiators are scattered over the ROS gel. ROS fluorescence due to the ION nanoradiators was observed continuously to a depth of 1.5 mm for both oxidized APF and oxidized DHE with relatively large intensity compared with the fluorescence caused by the ROS produced solely by incident primary X‐rays, which was limited to a depth of 600 µm, suggesting dose enhancement as well as more penetration by nanoradiators. In conclusion, the combined use of a synchrotron X‐ray microbeam‐irradiated three‐dimensional ROS gel and confocal laser scanning fluorescence microscopy provides a simple dosimetry method for track analysis of X‐ray photoelectric nanoradiator radiation, suggesting extensive cellular damage with dose‐enhancement beyond a single cell containing IONs.     

Diffraction of partially coherent X‐rays in clessidra prism arrays

When small triangular prisms are arranged in arrays which have an overall appearance like an hourglass (in Italian: clessidra) they can focus X‐rays owing to a combined action of diffraction and refraction. From the optical point of view these objects can be regarded as a Fresnel variant of concave transmission lenses. Consequently they can provide larger apertures than purely refractive lenses. However, one has to recognize that clessidra lenses will strongly diffract as the lens structure is periodic in the direction perpendicular to the incident beam. In experiments the diffraction is reduced because it is difficult to illuminate the large apertures with a full spatially coherent wavefront. So the illumination is at best partially coherent. In order to interpret available experimental data for this condition, diffraction theory has been applied appropriately to the clessidra structure, taking into account the limited spatial coherence. The agreement between the theoretical simulations and experimental data is very good, keeping the lens properties at their projected values and allowing for only two free model parameters. The first is the lateral spatial coherence; the second is a lens defect, a rounding of all edges and tips in the structure. Both values obtained from the simulations have been found to be in agreement with expectations.     

Nanofabrication and characterization of a grating‐based condenser for uniform illumination with hard X‐rays

In the development of full‐field transmission X‐ray microscopy for basic study in science and technology, a condenser capable of providing intense illumination with high uniformity and stability on tested specimens in order to achieve high‐quality images is essential. The latest design of a square‐shaped condenser based on diffractive gratings has demonstrated promising uniformity in illumination. This paper describes in more detail the development of such a beam shaper for hard X‐rays at 10 keV with regard to its design, manufacture and optical characterization. The effect of the grating profile on the diffracted intensity has been theoretically predicted by numerical simulation using the finite‐difference time‐domain method. Based on this, the limitations of the grating‐based condenser are discussed.     

An X‐ray Raman spectrometer for EXAFS studies on minerals: bent Laue spectrometer with 20 keV X‐rays

An X‐ray Raman spectrometer for studies of local structures in minerals is discussed. Contrary to widely adopted back‐scattering spectrometers using ≤10 keV X‐rays, a spectrometer utilizing ～20 keV X‐rays and a bent Laue analyzer is proposed. The 20 keV photons penetrate mineral samples much more deeply than 10 keV photons, so that high intensity is obtained owing to an enhancement of the scattering volume. Furthermore, a bent Laue analyzer provides a wide band‐pass and a high reflectivity, leading to a much enhanced integrated intensity. A prototype spectrometer has been constructed and performance tests carried out. The oxygen K‐edge in SiO₂ glass and crystal (α‐quartz) has been measured with energy resolutions of 4 eV (EXAFS mode) and 1.3 eV (XANES mode). Unlike methods previously adopted, it is proposed to determine the pre‐edge curve based on a theoretical Compton profile and a Monte Carlo multiple‐scattering simulation before extracting EXAFS features. It is shown that the obtained EXAFS features are reproduced fairly well by a cluster model with a minimal set of fitting parameters. The spectrometer and the data processing proposed here are readily applicable to high‐pressure studies.     

A monolithic Fresnel bimirror for hard X‐rays and its application for coherence measurements

Experiments using a simple X‐ray interferometer to measure the degree of spatial coherence of hard X‐rays are reported. A monolithic Fresnel bimirror is used at small incidence angles to investigate synchrotron radiation in the energy interval 5–50 keV with monochromatic and white beam. The experimental set‐up was equivalent to a Young's double‐slit experiment for hard X‐rays with slit dimensions in the micrometre range. From the high‐contrast interference pattern the degree of coherence was determined.     

Holographic grating recorded by He–Ne laser operating at 632.8 nm in polymer film containing push–pull azo dye

Holographic gratings were optically recorded by two beams from a He–Ne laser operating at 632.8 nm in poly (methyl methacrylate) (PMMA) film containing push–pull azo dye. The holographic characteristics of the recorded gratings were dependent on the polarization direction of the recording beams and the relationship between the diffractive signals and the power density of recording beams was investigated. The formation of holographic gratings accompanied by 532 nm (double-frequency of Nd:YAG laser) irradiation was studied in detail. It was found that the effect of 532 nm laser to the holographic grating lay in two aspects. The acceleration effect of 532 nm laser to the formation of holographic grating is predominant when the power density of 532 nm laser is low. While at relatively high power density of 532 nm laser, the erasure is the main factor to the holographic grating. Moreover, the holographic grating was probed by 532 nm laser at low power density and the dependence of the first order diffractive signal on the recording beam power density was also presented.     

Large‐aperture prism‐array lens for high‐energy X‐ray focusing

A new prism‐array lens for high‐energy X‐ray focusing has been constructed using an array of different prisms obtained from different parabolic structures by removal of passive parts of material leading to a multiple of 2π phase variation. Under the thin‐lens approximation the phase changes caused by this lens for a plane wave are exactly the same as those caused by a parabolic lens without any additional corrections when they have the same focal length, which will provide good focusing; at the same time, the total transmission and effective aperture of this lens are both larger than those of a compound kinoform lens with the same focal length, geometrical aperture and feature size. This geometry can have a large aperture that is not limited by the feature size of the lens. Prototype nickel lenses with an aperture of 1.77 mm and focal length of 3 m were fabricated by LIGA technology, and were tested using CCD camera and knife‐edge scan method at the X‐ray Imaging and Biomedical Application Beamline BL13W1 at Shanghai Synchrotron Radiation Facility, and provided a focal width of 7.7 µm and a photon flux gain of 14 at an X‐ray energy of 50 keV.     

Third‐order nonlinear and linear time‐dependent dynamical diffraction of X‐rays in crystals

For the first time the third‐order nonlinear time‐dependent Takagi's equations of X‐rays in crystals are obtained and investigated. The third‐order nonlinear and linear time‐dependent dynamical diffraction of X‐rays spatially restricted in the diffraction plane pulses in crystals is investigated theoretically. A method of solving the linear and the third‐order nonlinear time‐dependent Takagi's equations is proposed. Based on this method, results of analytical and numerical calculations for both linear and nonlinear diffraction cases are presented and compared.     

Visualization of microvessels by angiography using inverse‐Compton scattering X‐rays in animal models

The fundamental performance of microangiography has been evaluated using the S‐band linac‐based inverse‐Compton scattering X‐ray (iCSX) method to determine how many photons would be required to apply iCSX to human microangiography. ICSX is characterized by its quasi‐monochromatic nature and small focus size which are fundamental requirements for microangiography. However, the current iCSX source does not have sufficient flux for microangiography in clinical settings. It was determined whether S‐band compact linac‐based iCSX can visualize small vessels of excised animal organs, and the amount of X‐ray photons required for real time microangiography in clinical settings was estimated. The iCSX coupled with a high‐gain avalanche rushing amorphous photoconductor camera could visualize a resolution chart with only a single iCSX pulse of ～3 ps duration; the resolution was estimated to be ～500 µm. The iCSX coupled with an X‐ray cooled charge‐coupled device image sensor camera visualized seventh‐order vascular branches (80 µm in diameter) of a rabbit ear by accumulating the images for 5 and 30 min, corresponding to irradiation of 3000 and 18000 iCSX pulses, respectively. The S‐band linac‐based iCSX visualized microvessels by accumulating the images. An iCSX source with a photon number of 3.6 × 10³–5.4 × 10⁴ times greater than that used in this study may enable visualizing microvessels of human fingertips even in clinical settings.     

Quick X‐ray reflectivity using monochromatic synchrotron radiation for time‐resolved applications

A new technique for the parallel collection of X‐ray reflectivity (XRR) data, compatible with monochromatic synchrotron radiation and flat substrates, is described and applied to the in situ observation of thin‐film growth. The method employs a polycapillary X‐ray optic to produce a converging fan of radiation, incident onto a sample surface, and an area detector to simultaneously collect the XRR signal over an angular range matching that of the incident fan. Factors determining the range and instrumental resolution of the technique in reciprocal space, in addition to the signal‐to‐background ratio, are described in detail. This particular implementation records ～5° in 2gθ and resolves Kiessig fringes from samples with layer thicknesses ranging from 3 to 76 nm. The value of this approach is illustrated by showing in situ XRR data obtained with 100 ms time resolution during the growth of epitaxial La_0.7Sr_0.3MnO₃ on SrTiO₃ by pulsed laser deposition at the Cornell High Energy Synchrotron Source (CHESS). Compared with prior methods for parallel XRR data collection, this is the first method that is both sample‐independent and compatible with the highly collimated, monochromatic radiation typical of third‐generation synchrotron sources. Further, this technique can be readily adapted for use with laboratory‐based sources.