Microstructural investigation of morphology and kinetics of methane hydrate in the presence of tetrabutylammonium bromide: Insights for preservation and inhibition.

Developing highly efficient methane (CH4) hydrate storage methods and understanding the hydrate dissociation kinetics can contribute to advancing CH4 gas storage and transport. The effects of tetrabutylammonium bromide (TBAB) (a thermodynamic promoter) addition on the kinetics of CH4 hydrate were evaluated on the microscopic scale using synchrotron x-ray computed tomography (CT) and powder x-ray diffraction. Microscopic observations showed that a 5 wt. % TBAB solution facilitated the nucleation of CH4 hydrate owing to the initial growth of TBAB semi-clathrate hydrate particles. The CH4 hydrate crystals in the CH4 + TBAB hydrate sample were sponge-like with many internal pores and exhibited slightly enhanced self-preservation compared to the pure CH4 hydrate, both in the bulk and after pulverization to a fine powder. This study demonstrates the feasibility of controlling the rate of CH4 hydrate formation and preservation by using aqueous TBAB solutions in CH4 hydrate formation.

Multi-phase retrieval of methane hydrate in natural sediments by cryogenic x-ray computed tomography.

In this study, we observed natural methane (CH4) hydrate sediments, which are a type of unconventional natural gas resources, using x-ray computed tomography (CT). Because CH4 hydrates are formed by hydrogen bonding of water molecules with CH4, material decomposition becomes challenging when CH4 hydrates coexist with liquid or solid water in natural sediments. Tri-contrast (absorption, refraction, and scattering) imaging was performed via diffraction enhanced x-ray CT optics using monochromatic synchrotron x rays. The quantitative characterization of the contrast changes successfully enabled the decomposition of CH4 hydrates coexisting with frozen seawater (ice) in natural sediments obtained from the Okhotsk Sea. This study reveals complementary structural information about the microtexture and spatial relation among CH4 hydrates, ice, and pores by utilizing the distinct physical properties of x rays when passing through the materials. These results highlight the exceptional capabilities of high-resolution multicontrast x-ray tomography in materials science and geoscience applications.

Evaluation of high intensity synchrotron radiation x-ray imaging using Si crystals with lapped surface at 33.3 keV.

In x-ray imaging methods, such as synchrotron radiation microangiography, the x-ray intensity has become more important in recent years for real-time dynamic observations to evaluate temporal changes in samples. Many synchrotron radiation facilities use x-rays monochromated by diffraction from perfect Si crystals to improve the spatial resolution of x-ray images and obtain detailed information about a sample. In this paper, monochromatic synchrotron x-ray images were acquired using Si crystals lapped with abrasives to enhance the x-ray intensity using white synchrotron radiation x-rays for observing dynamic changes in samples. The x-ray intensity, spatial resolution, and contrast noise ratio (CNR) in the acquired x-ray images were quantitatively evaluated using a state-of-the-art high-spatial-resolution detector. The x-ray intensity was substantially increased by a factor of ∼8 when a lapped Si crystal was used. When the lapped Si crystal was used, the spatial resolution of x-ray images in the diffraction-plane direction was ∼70% lower than when an etched Si crystal was used at a spatial resolution of 10 lp/mm. By contrast, the CNR in x-ray images, which is important for observing the interior of a sample, increased threefold when a contrast agent containing iodine at a concentration of 38 wt. % was used. It was confirmed that the combination of white synchrotron radiation x-rays and a lapped crystal produces an intense monochromatic x-ray, providing an important evaluation for the use of optics for each research purpose.

Large-view x-ray imaging for medical applications using the world's only vertically polarized synchrotron radiation beam and a single asymmetric Si crystal.

Objective.X-ray microangiography provides detailed information on the internal structure and function of a biological subject. Its ability to evaluate the microvasculature of small animals is useful for acquiring basic and clinical medical knowledge. The following three conditions are necessary to attain detailed knowledge of biological functions: (1) high temporal resolution with sufficient x-ray intensity, (2) high spatial resolution, and (3) a wide field of view. Because synchrotron radiation microangiography systems provide high sapatial resolution and high temporal resolution as a result of their high x-ray intensity, such systems have been developed at various synchrotron radiation facilities, starting with the photon factory, leading to numerous medical discoveries. However, the three aforementioned functions are incompatible with the use of synchrotron radiation because the x-ray intensity decreases when a wide field of view is obtained. To overcome these problems, we developed a new x-ray optical system for microangiography in rats using synchrotron radiation x-rays.Approach.Instead of using monochromatic synchrotron radiation x-rays with a conventional double-crystal monochromator, we used white synchrotron radiation x-rays and an asymmetric Si crystal to simultaneously monochromatize the beam and widen the field of view.Main results.The intensity profile and spatial resolution of the x-ray images were then evaluated. The proposed x-ray optics increased the x-ray intensity and beam width by factors of 1.3 and 2.7, respectively, compared with those of conventional monochromatic x-rays. In addition,in vivostudies on microangiography in rats were performed to confirm that the images had sufficient intensity, spatial resolution, and field of view. One of a series of images taken at 50 ms frame-1was shown as an example.Significance.This x-ray optics provides sufficient x-ray intensity, high spatial resolution, and a wide field of view. This technique is expected providing new insights into the evaluation of the vascular system.

X-ray zooming microscopy with two Fresnel zone plates.

We propose a variable-magnification full-field x-ray microscope using two Fresnel zone plates (FZPs). By moving the positions of the two FZPs, the magnification can be continuously changed even if the sample and camera positions are fixed. It was demonstrated that the magnification can be changed in the range of 25-150× using a hard x-ray beam at 14.4 keV. Using the first FZP as a convex lens and the second FZP as a concave lens, high magnification can be achieved at a short camera length. Even under the condition of a camera length of about 7 m, a magnification higher than 300× was achieved, and a line and space pattern with a pitch of 40 nm was observed at 10 keV. By inserting a knife edge at an appropriate position in the optical system, a phase-contrast image can be easily obtained, which is useful for soft-tissue observation of biological samples.

Superheating of Structure I Gas Hydrates within the Structure II Cyclopentane Hydrate Shell.

The superheated state of methane (CH4) hydrate that exists under the surface ice layer can persist for considerable lengths of time, which showed promise as a method for storing and transporting natural gas. This study extends this further by coating sI CH4 hydrate with one of several sII hydrates, thus eliminating the need for a defect-free continuous interface between the sI and sII hydrates. Gas hydrate crystals were kept intact above their dissociation temperature by immersing them in liquid cyclopentane (CP), as observed with powder X-ray diffraction and X-ray CT methods. It was observed that placing the CH4 hydrate in CP converted the outer layer of CH4 hydrate to a thin layer of CP hydrate at around 270 K under atmospheric pressure, which is ∼80 K higher than the usual dissociation temperature. It was also observed that sI CO2 hydrate and C2H6 hydrate could be preserved by CP hydrate.

White matter imaging of ethanol-fixed rat brain by phase-contrast X-ray computed tomography.

BACKGROUND: Phase-contrast X-ray computed tomography imaging (PCI) based on crystal X-ray interferometry can detect minute density differences within biological soft tissues without contrast agents. Ethanol fixation yields increased tissue-background density differences due to the dehydrating and delipidifying effects of ethanol. PURPOSE: To obtain high image contrast of cerebral white matter structures in PCI, tissue fixation using ethanol and routinely used formalin have been examined. MATERIAL AND METHODS: Ethanol-fixed (EF) (n = 4) and formalin-fixed (FF) (n = 4) rat brains were imaged by crystal X-ray interferometry-based PCI. Tissue staining/microscopy was also performed for histological comparison and myelin density evaluation. Three-dimensional white matter tract images were reconstructed. RESULTS: Superior image contrast was obtained in the images of EF brains (EF images) compared to those of formalin-fixed brains (FF images), particularly for white matter structures. Significant density differences between the white matter structures and hippocampus (P < 0.01)/thalamus (P < 0.001) were observed in the EF, but not FF, images. Ethanol fixation enhanced the image contrast of white matter tracts by approximately sixfold compared to formalin fixation, and close agreement (r2 = 0.97; P < 0.05) between the density values on the CT images and the myelin density values in histological images was observed for the EF brains. Three-dimensional reconstruction of the white matter tracts was possible from the EF images, but not FF images. CONCLUSION: Ethanol fixation resulted in marked contrast enhancement of cerebral white matter structures in PCI. Thus, high-resolution PCI using ethanol for tissue fixation could be valuable for experimental neurological studies and postmortem neuropathology evaluation.

Dynamic X-ray elastography using a pulsed photocathode source.

X-ray absorption of breast cancers and surrounding healthy tissue can be very similar, a situation that sometimes leads to missed cancers or false-positive diagnoses. To increase the accuracy of mammography and breast tomosynthesis, we describe dynamic X-ray elastography using a novel pulsed X-ray source. This new imaging modality provides both absorption and mechanical properties of the imaged material. We use a small acoustic speaker to vibrate the sample while a synchronously pulsed cold cathode X-ray source images the mechanical deformation. Using these stroboscopic images, we derive two-dimensional stiffness maps of the sample in addition to the conventional X-ray image. In a breast phantom composed of ZrO2 powder embedded in gel, dynamic elastography derived stiffness maps were able to discriminate a hard inclusion from surrounding material with a contrast-to-noise ratio (CNR) of 4.5. The CNR on the corresponding absorption image was 1.1. This demonstrates the feasibility of dynamic X-ray elastography with a synchronously pulsed X-ray source.

X-Ray attenuation and image contrast in the X-ray computed tomography of clathrate hydrates depending on guest species.

In this study, X-ray imaging of inclusion compounds encapsulating various guest species was investigated based on the calculation of X-ray attenuation coefficients. The optimal photon energies of clathrate hydrates were simulated for high-contrast X-ray imaging based on the type of guest species. The proof of concept was provided by observations of Kr hydrate and tetra-n-butylammonium bromide (TBAB) semi-clathrate hydrate using absorption-contrast X-ray computed tomography (CT) and radiography with monochromated synchrotron X-rays. The radiographic image of the Kr hydrate also revealed a sudden change in its attenuation coefficient owing to the K-absorption edge of Kr as the guest element. With a photon energy of 35 keV, X-ray CT provided sufficient segmentation for the TBAB semi-clathrate hydrate coexisting with ice. In contrast, the simulation did not achieve the sufficient segmentation of the CH4 and CO2 hydrates coexisting with water or ice, but it revealed the capability of absorption-contrast X-ray CT to model the physical properties of clathrate hydrates, such as Ar and Cl2 hydrates. These results demonstrate that the proposed method can be used to investigate the spatial distribution of specific elements within inclusion compounds or porous materials.

Correction: X-ray CT observation and characterization of water transformation in heavy objects.

Correction for 'X-ray CT observation and characterization of water transformation in heavy objects' by Satoshi Takeya et al., Phys. Chem. Chem. Phys., 2020, 22, 3446-3454, DOI: 10.1039/c9cp05983k.

X-ray CT observation and characterization of water transformation in heavy objects.

Nondestructive observations and characterization of low-density materials composed of low-Z elements, such as water or its related substances, are essential for materials and life sciences. However, visualizing these compounds and their phase changes is still challenging. In this study, an approach to X-ray imaging of water-related substances in heavy objects without the use of contrast agents is proposed. The implementation of the approach is based upon X-ray phase shift, in which the optimal photon energy is simulated for high-contrast X-ray imaging. Proof of concept is provided by observations of resins, water, and clathrate hydrates such as CO2 hydrate and tetrahydrofuran (THF) hydrate in an aluminum container by diffraction-enhanced X-ray imaging with synchrotron X-rays of 35 keV. These results suggest that the proposed approach is a unique method for visualizing the transformation of these clathrate hydrates and is also applicable to in situ observations of other objects composed of multiphase materials with small density differences.

Feasibility study of phase-contrast X-ray laminography using X-ray interferometry.

For fine observation of laminar samples, phase-contrast X-ray laminography using X-ray interferometry was developed. An imaging system fitted with a two-crystal X-ray interferometer was used to perform the observations, and the sectional images were calculated by a three-dimensional iterative reconstruction method. Obtained images of an old flat slab of limestone from the Carnic Alps depicted fusulinids in the Carboniferous period with 3 mg cm-3 density resolution, and those of carbon paper used for a fuel-cell battery displayed the inner fibrous structures clearly.

Testicular seminoma in the aged rat visualized by phase-contrast X-ray computed tomography.

Spontaneously growing testicular seminoma in the aged rat was imaged by one of the most sensitive imaging modalities, namely, phase-contrast X-ray computed tomography (CT) with crystal X-ray interferometry. Phase-contrast X-ray CT clearly depicted the detailed inner structures of the tumor and provided 20× magnified images compared to light-microscopic images. Phase-contrast X-ray CT images are generated based on density variations in the object, whereas pathological images are based on differentiation of cellular structures, such as the cellular nuclei and cytoplasm. The mechanism of image generation differs between the two techniques: phase-contrast X-ray CT detects even minute differences in the density among pathological structures, depending, for example, on the number and sizes of the nuclei, variations of the cytoplasmic components, and presence/absence of fibrous septa, cystic changes, and hemorrhage. Thus, phase-contrast X-ray CT with a spatial resolution of 26 µm might allow prediction of the morphological characteristics of a tumor even before histopathological processing.

Three-dimensional X-ray thermography using phase-contrast imaging.

Thermal management is a key technology to desterilize unused energy sources for building sustainable societies. However, conventional temperature measurement methods such as infrared thermography can detect only the surface temperature of objects because they use infrared light. We thus present a novel three-dimensional X-ray thermography using a phase-contrast X-ray imaging technique, which enables non-destructive observations of the inner thermal distribution of samples. The sensitivity of phase-contrast X-ray imaging is about 1000 times higher than that of conventional X-ray imaging. Therefore, temperature changes can be detected by using density changes caused by thermal expansion. We applied X-ray interferometric imaging (XI) that detects phase-shift by using a crystal X-ray interferometer. The highest sensitivity of XI was utilized to successfully obtain the first three-dimensional image that visualizes the thermal distribution in heated water nondestructively. Additionally, projection images visualizing the dynamic thermal flow in heated water were also obtained, and their distribution and diffusion velocity agreed well with those of the calculated images obtained by computational fluid dynamics analysis. These results show that the novel thermography enables nondestructive observations of inner temperature and thermal flow and can provide solutions for optimum thermal design of electrical devices, motors, and engines.

A new method for visualizing pulmonary artery microvasculature using synchrotron radiation pulmonary microangiography: the measurement of pulmonary arterial blood flow velocity in the high pulmonary blood flow rat model.

BACKGROUND: Increased pulmonary blood flow (PBF) and shear stress may provoke irreversible vascular remodeling, yet invasive visualization of the microvasculature complicates monitoring. A non-invasive imaging methodology would therefore safely provide mechanistic insights into the progression of high PBF-induced vascular remodeling. PURPOSE: To establish a novel microvasculature visualization method using synchrotron radiation pulmonary microangiography (SRPA) that can also calculate PBF velocity in vivo. MATERIAL AND METHODS: A high PBF rat model was established by making a fistula between the abdominal aorta and inferior vena cava. After eight weeks, SRPA was performed and the dynamic density changes in the right lower pulmonary artery (PA) were calculated by software. SRPA was performed with a HARP (High-Gain Avalanche Rushing amorphous Photoconductor) receiver. PBF velocity was calculated by contrast medium transit time within the PA. All data were presented as mean ± standard error (SE). Student's t-test was used for comparison between the two groups. RESULTS: High dynamic spatial and contrast resolution from SRPA in the PA allowed for clear pulmonary microangiography and accurate detection of higher PBF in the rat model (82.3 ± 8.5 mm/s high-PBF group vs. 46.1 ± 4.3 mm/s control group, P < 0.01). CONCLUSIONS: These novel results demonstrate that SRPA was useful in both visualizing the dynamic flow distribution within the microvasculature and calculating PBF velocity. This newly developed, non-invasive technology may become a powerful tool in clarifying the mechanism of vascular remodeling associated with high PBF-induced shear stress.

Multi-pinhole fluorescent x-ray computed tomography for molecular imaging.

We propose a multi-pinhole fluorescent x-ray computed tomography (mp-FXCT) technique for preclinical molecular imaging that can provide the complete data necessary to produce 3-D tomographic images during anaesthesia. In this method, multiple projections are simultaneously acquired through a multi-pinhole collimator with a 2-D detector and full-field volumetric beam to accelerate the data acquisition process and enhance the signal-to-noise ratios of the projections. We constructed a 15-pinhole mp-FXCT imaging system at beamline ARNE-7A at KEK and performed preliminary experiments to investigate its imaging properties using physical phantoms and a non-radioactive I imaging agent. The mp-FXCT system could detect an I concentration of 0.038 mg/ml, the minimum required for in-vivo imaging, at a spatial resolution of about 0.3 mm during a data acquisition time of 90 min, which is less than the time for which anaesthesia is effective and suggests that preclinical molecular imaging is feasible with mp-FXCT.

Dual-energy fluorescent x-ray computed tomography system with a pinhole design: Use of K-edge discontinuity for scatter correction.

We propose a pinhole-based fluorescent x-ray computed tomography (p-FXCT) system with a 2-D detector and volumetric beam that can suppress the quality deterioration caused by scatter components. In the corresponding p-FXCT technique, projections are acquired at individual incident energies just above and below the K-edge of the imaged trace element; then, reconstruction is performed based on the two sets of projections using a maximum likelihood expectation maximization algorithm that incorporates the scatter components. We constructed a p-FXCT imaging system and performed a preliminary experiment using a physical phantom and an I imaging agent. The proposed dual-energy p-FXCT improved the contrast-to-noise ratio by a factor of more than 2.5 compared to that attainable using mono-energetic p-FXCT for a 0.3 mg/ml I solution. We also imaged an excised rat's liver infused with a Ba contrast agent to demonstrate the feasibility of imaging a biological sample.

Renal contrast microangiography with synchrotron radiation: a novel method for visualizing structures within nephrons in vivo.

Background No non-invasive method of observing renal microcirculation in vivo has been established as yet. Although angiography is considered to be ideally suited for the purpose, conventional X-rays cannot be used to image structures smaller than 100 µm. Purpose To develop a method for visualizing the renal arterioles, glomeruli, and proximal tubules of rats in vivo making use of synchrotron radiation. Material and Methods Male Wistar rats were anesthetized, and a catheter was inserted via laparotomy into the abdominal aorta with its tip placed above the renal arteries. The rats were paralyzed with a neuromuscular blocking agent and mechanically ventilated. An inorganic iodine contrast medium was injected via the catheter. The SR derived X-rays transmitted through the subjects were recorded with a CCD camera. Two-dimensional images with a pixel size of 9 µm were obtained. The exposure time was fixed at 50 ms, with a maximum acquisition rate of three images/s. Results Renal arterioles as small as 18 µm in diameter, glomeruli with an average diameter of 173 ± 21 µm, as well as proximal tubules, were clearly visualized. In addition, glomerular density at the peripheral renal cortex was measurable. Conclusion Rat renal microcirculation could be successfully observed in real-time, without exteriorization of the kidney in this study.

X-ray analyzer-based phase-contrast computed laminography.

X-ray analyzer-based phase-contrast imaging is combined with computed laminography for imaging regions of interest in laterally extended flat specimens of weak absorption contrast. The optics discussed here consist of an asymmetrically cut collimator crystal and a symmetrically cut analyzer crystal arranged in a nondispersive (+, -) diffraction geometry. A generalized algorithm is given for calculating multi-contrast (absorption, refraction and phase contrast) images of a sample. Basic formulae are also presented for laminographic reconstruction. The feasibility of the method discussed was verified at the vertical wiggler beamline BL-14B of the Photon Factory. At a wavelength of 0.0733 nm, phase-contrast sectional images of plastic beads were successfully obtained. Owing to strong circular artifacts caused by a sample holder, the field of view was limited to about 6 mm in diameter.

Association between endothelial function and micro-vascular remodeling measured by synchrotron radiation pulmonary micro-angiography in pulmonary arterial hypertension.

OBJECTIVES: Pulmonary arterial hypertension (PAH) is a progressive disease which causes increased vascular resistance. In this study, our purpose was to quantify the micro-vascular remodeling in monocrotaline-induced PAH rats using synchrotron radiation pulmonary micro-angiography (SRPA), a method we have previously established in an in vivo rat model. To determine the relationship between endothelial function and vascular remodeling, the local expression of endothelin-1 (ET-1), endothelial nitric oxide synthase (eNOS) and vascular endothelial growth factor (VEGF) was evaluated using immunohistochemical staining. METHODS: Monocrotaline-induced PAH rats were created by subcutaneous injection of monocrotaline. After 2 weeks, SRPA was performed at the Photon Factory of the High Energy Accelerator Research Organization. The internal diameters of pulmonary arterioles were measured using SRPA images. Semi-quantified analyses of ET-1, eNOS and VEGF expression in pulmonary arterioles were performed by immunohistochemical staining. RESULTS: Micro-vascular density and the internal diameters of pulmonary arterioles were significantly decreased in PAH. ET-1 expression was significantly increased in PAH compared with the control (1.53 ± 0.45 vs. 0.80 ± 0.14) and eNOS expression was significantly decreased in PAH compared with the control (1.12 ± 0.59 vs. 1.91 ± 0.66), although VEGF expression did not differ between the groups. CONCLUSIONS: SRPA can be effectively used for visualizing the decreased pulmonary micro-vasculature associated with PAH. Increased ET-1 expression and decreased eNOS expression may contribute to the proliferation and vasospasm of pulmonary arterioles induced by endothelial dysfunction due to PAH. This SRPA technology may help to identify a correlation between endothelial function and micro-vasculature remodeling in PAH.