Colossal barocaloric effects in plastic crystals.

Refrigeration is of vital importance for modern society-for example, for food storage and air conditioning-and 25 to 30 per cent of the world's electricity is consumed for refrigeration1. Current refrigeration technology mostly involves the conventional vapour compression cycle, but the materials used in this technology are of growing environmental concern because of their large global warming potential2. As a promising alternative, refrigeration technologies based on solid-state caloric effects have been attracting attention in recent decades3-5. However, their application is restricted by the limited performance of current caloric materials, owing to small isothermal entropy changes and large driving magnetic fields. Here we report colossal barocaloric effects (CBCEs) (barocaloric effects are cooling effects of pressure-induced phase transitions) in a class of disordered solids called plastic crystals. The obtained entropy changes in a representative plastic crystal, neopentylglycol, are about 389 joules per kilogram per kelvin near room temperature. Pressure-dependent neutron scattering measurements reveal that CBCEs in plastic crystals can be attributed to the combination of extensive molecular orientational disorder, giant compressibility and highly anharmonic lattice dynamics of these materials. Our study establishes the microscopic mechanism of CBCEs in plastic crystals and paves the way to next-generation solid-state refrigeration technologies.

Second Percutaneous Transluminal Angioplasty Versus Surgical Reconstruction for Hemodialysis Access Failure Within a Short Time Period.

BACKGROUND: The purpose of this study was to compare patency and nonabandonment rates for second percutaneous transluminal angioplasty (PTA) and surgical reconstruction for the treatment of failing vascular access due to restenosis or reocclusion in a short time after initial PTA. METHODS: Seventy two consecutive patients who underwent second treatment within 90 days after the initial PTA were evaluated retrospectively. The patency (time to corrective procedure) and access abandonment were compared among patients who underwent a second PTA (n = 35) and those who underwent surgical reconstruction (n = 37). Univariate and multivariate analyses were performed to determine independent predictors of patency and access abandonment at 1 year after the treatment. RESULTS: At 1 year after the treatment, the patency rates were 35.1% and 11.4% (P = 0.02) and nonabandonment rates were 64.9% and 77.1% (P = 0.25) for surgical reconstruction and second PTA, respectively. The Kaplan-Meier survival analysis showed that the surgical reconstruction group had better patency probability (P = 0.02), but there was no difference in the nonabandonment probability between the groups (P = 0.29). Shorter time to retreatment was associated with good patency. The female gender was likely to be associated with access abandonment. CONCLUSIONS: The access abandonment between the 2 procedures had no difference, although surgical reconstruction provided better patency than second PTA.

Pressure-induced evolution in the durability of nickel-metal hydride batteries under high-current charge.

We found that an AAA-type battery (min. 750 mAh) pressurized with Ar or N2 at pressures of up to 5 MPa exhibited a significant durability enhancement even under high-current conditions. As an example of a charge-discharge cycle test at 3 amperes, the residual ratio of capacity at atmospheric pressure decreased to approximately 90% of the standard capacity before 50 cycles. However, at a pressure of 3 MPa of N2, the capacity remained at more than 90% until 180 cycles. With an increase in the pressure, the residual ratio of capacity was further improved. It has been considered that, at the positive electrode of the Ni-MH battery, the chemical reaction from nickel(II) hydroxide (Ni(OH)2) crystals to nickel oxide hydroxide (NiOOH) crystals occurs during the charging process. However, X-ray diffraction (XRD) results in the present study do not support this solid-solid reaction between these two types of crystal. To address this contradiction, we propose a different reaction mechanism by introducing the concept of non-crystalline fine particles of compounds, which are undetected by XRD. This mechanism clearly explains how the pressure affects the durability improvement. Pressurized batteries, which are capable of fast charge-discharge operation under high-current conditions, can provide a new route for application fields of unconventional energy storage.

Reactions of HOCO radicals through hydrogen-atom hopping utilizing clathrate hydrates as an observational matrix.

The carboxyl (HOCO) radical, which is an important species in atmospheric chemistry and combustion, is an intermediate in the reaction: CO + OH → CO2 + H and serves as a hydrogen donor to the reaction partners. The cis-HOCO radical, one of the ground-state HOCO radicals, is supposed to be decomposed into CO2 and the hydrogen atom by a tunneling effect. In order to prove the hypothesis, we performed electron spin resonance (ESR) measurements to investigate the decay mechanisms of the ground-state HOCO and DOCO radicals in gamma-ray-irradiated CO2 hydrates, which may hold the radicals stably. The ground-state HOCO and DOCO radicals decayed according to a second-order decay model and transformed into formic acid and CO2. The ratio of the decay rate constants of HOCO and DOCO radicals shows a good agreement with that in the kinetic isotope effect for the hydrogen and deuterium abstraction reactions. These results indicate that they react with another HOCO radical in the adjacent hydrate cage without the tunneling effect. This implies that the ground-state HOCO radicals are not decomposed by the tunneling effect but are decayed through reactions with some atoms, molecules, and/or radicals even in the gas phase. In addition, the hydrogen-atom hopping through the temporary hydrogen bonds between the HOCO radical and CO2 results in a seeming diffusion of the HOCO radicals in the CO2 hydrate; this would be an important concept for the studies of the radical diffusions and the supply of hydrogen atoms in gas, liquid, and solid phases.

Structure-H methane + 1,1,2,2,3,3,4-heptafluorocyclopentane mixed hydrate at pressures up to 373 MPa.

Thermodynamic stability boundary of structure-H hydrates with large guest species and methane (CH4) at extremely high pressures has been almost unclear. In the present study, the four-phase equilibrium relations in the structure-H CH4 + 1,1,2,2,3,3,4-heptafluorocyclopentane (1,1,2,2,3,3,4-HFCP) mixed hydrate system were investigated in a temperature range of (281.05 to 330.12) K and a pressure range up to 373 MPa. The difference between equilibrium pressures in the structure-H CH4 + 1,1,2,2,3,3,4-HFCP mixed hydrate system and the structure-I simple CH4 hydrate system gets larger with increase in temperature. The structure-H CH4 + 1,1,2,2,3,3,4-HFCP mixed hydrate survives even at 330 K and 373 MPa without any structural phase transition. The maximum temperature where the structure-H CH4 + 1,1,2,2,3,3,4-HFCP mixed hydrate is thermodynamically stable is likely to be beyond that of the structure-H simple CH4 hydrate.

Giant adiabatic temperature change and its direct measurement of a barocaloric effect in a charge-transfer solid.

Solid refrigerants exhibiting a caloric effect upon applying external stimuli are receiving attention as one of the next-generation refrigeration technologies. Herein, we report a new inorganic refrigerant, rubidium cyano-bridged manganese-iron-cobalt ternary metal assembly (cyano-RbMnFeCo). Cyano-RbMnFeCo shows a reversible barocaloric effect with large reversible adiabatic temperature changes of 74 K (from 57 °C to -17 °C) at 340 MPa, and 85 K (from 88 °C to 3 °C) at 560 MPa. Such large reversible adiabatic temperature changes have yet to be reported among caloric effects in solid-solid phase transition refrigerants. The reversible refrigerant capacity is 26000 J kg-1 and the temperature window is 142 K. Additionally, cyano-RbMnFeCo shows barocaloric effects even at low pressures, e.g., reversible adiabatic temperature change is 21 K at 90 MPa. Furthermore, direct measurement of the temperature change using a thermocouple shows +44 K by applying pressure. The temperature increase and decrease upon pressure application and release are repeated over 100 cycles without any degradation of the performance. This material series also possesses a high thermal conductivity value of 20.4 W m-1 K-1. The present barocaloric material may realize a high-efficiency solid refrigerant.

Intermolecular hydrogen transfer between guest species in small and large cages of methane + propane mixed gas hydrates.

To investigate the molecular interaction between guest species inside of the small and large cages of methane + propane mixed gas hydrates, thermal stabilities of the methyl radical (possibly induced in small cages) and the normal propyl and isopropyl radicals (induced in large cages) were investigated by means of electron spin resonance measurements. The increase of the total amount of the normal propyl and isopropyl radicals reveals that the methyl radical in the small cage withdraws one hydrogen atom from the propane molecule enclathrated in the adjacent large cage of the structure-II hydrate. A guest species in a hydrate cage has the ability to interact closely with the other one in the adjacent cages. The clathrate hydrate may be utilized as a possible nanoscale reaction field.

Long-term prognostic value of the combined assessment of clinical and computed tomography findings in type: An acute aortic dissection.

Type A acute aortic dissection (TAAAD) carries a high mortality rate in the absence of surgical treatment. This study sought to determine whether combining the assessment of clinical and computed tomography (CT) findings can be used to predict the long-term all-cause mortality rate of patients with TAAAD.Eighty-five consecutive patients with TAAAD who had undergone CT imaging and surgery were retrospectively reviewed. For the clinical and CT findings, univariate testing followed by multivariate logistic regression analysis was conducted to identify independent predictors of death. Then, the area under the receiver operating characteristic curve of the combined prediction model was calculated.The long-term mortality rate was 34.1% in our cohort (a median follow-up period of 60 months). Multivariate logistic regression analysis identified the following presenting variables as predictors of death: male sex (odds ratio [OR]: 6.67; 95% confidence interval [CI]: 1.67-25.0; P = .007), kidney malperfusion (OR: 2.18; 95% CI: 1.16-4.1; P = .02), and descending aorta size (OR: 1.12; 95% CI: 1.00-1.25; P = .05). Receiver operating characteristic curve analysis revealed an area under the receiver operating characteristic curve of 0.84 when using the combined model for prediction of long-term all-cause mortality (P ≤ .01).The combined assessment of clinical and CT findings can reasonably predict the long-term prognosis of TAAAD with surgery.

Perfusion abnormality on three-dimensional arterial spin labeling in patients with acute encephalopathy with biphasic seizures and late reduced diffusion.

PURPOSE: Acute encephalopathy with biphasic seizures and late reduced diffusion (AESD) is the most common encephalopathy subtype in Japanese children. Few case reports have shown perfusion abnormality on arterial spin labeling (ASL) in patients with AESD. The present study aimed to review the chronological change of cerebral perfusion on three-dimensional (3D) ASL in patients with AESD. METHODS: Twenty consecutive patients with AESD were enrolled; the patients underwent MRI including 3D ASL. The clinical course of AESD was divided into four phases according to the time from occurrence of seizures to MRI. Two neuroradiologists independently assessed presence or absence, distribution, and severity of perfusion abnormality using ASL and qualitatively scored perfusion abnormality using a five-point grading system. The level of interobserver agreement in the evaluation was analyzed using weighted κ statistics. Additionally, the signal ratio of abnormal perfusion region and peri-central sulcus region on ASL was semi-quantitatively evaluated. Moreover, we qualitatively compared the distribution between perfusion abnormality on ASL and bright tree appearance (BTA) on diffusion-weighted image (DWI). RESULTS: ASL showed hypoperfusion from 8.5 to 22 h after early seizures (ESs) and hyperperfusion within 24 h after late seizures (LSs). Various perfusions were found >3 days after LSs. Interobserver agreement for qualitative scored perfusion abnormality was good (κ = 0.77). The distribution of abnormal perfusion was relatively consistent with BTA. CONCLUSION: In AESD, cerebral perfusion changes with time. ASL showed hypoperfusion from 8.5 to 22 h after ESs, hyperperfusion within 24 h after LSs in patients with AESD.

Increasing hydrogen storage capacity using tetrahydrofuran.

Hydrogen hydrates with tetrahydrofuran (THF) as a promoter molecule are investigated to probe critical unresolved observations regarding cage occupancy and storage capacity. We adopted a new preparation method, mixing solid powdered THF with ice and pressurizing with hydrogen at 70 MPa and 255 +/- 2 K (these formation conditions are insufficient to form pure hydrogen hydrates). All results from Raman microprobe spectroscopy, powder X-ray diffraction, and gas volumetric analysis show a strong dependence of hydrogen storage capacity on THF composition. Contrary to numerous recent reports that claim it is impossible to store H(2) in large cages with promoters, this work shows that, below a THF mole fraction of 0.01, H(2) molecules can occupy the large cages of the THF+H(2) structure II hydrate. As a result, by manipulating the promoter THF content, the hydrogen storage capacity was increased to approximately 3.4 wt % in the THF+H(2) hydrate system. This study shows the tuning effect may be used and developed for future science and practical applications.

Grading astrocytic tumors by using apparent diffusion coefficient parameters: superiority of a one- versus two-parameter pilot method.

PURPOSE: To assess the utility of both minimum apparent diffusion coefficients (ADCs) and ADC difference values for grading astrocytic tumors at magnetic resonance imaging. MATERIALS AND METHODS: The hospital's institutional review board approved this retrospective study and waived informed consent. Fifty patients (23 male patients, 27 female patients; median age, 53 years) with newly diagnosed astrocytic tumors were evaluated. Two observers blinded to clinical information independently measured the ADCs by manually placing three to five regions of interest (40-60 mm(2)) within the solid tumor either with or without contrast material-enhanced components and calculated the average ADC. Minimum and maximum ADCs were selected, and the difference between them was recorded as the ADC difference value. These ADC values were used as the parameters for tumor grading and were compared by using the Kruskal-Wallis test and receiver operating characteristic (ROC) curve analysis. RESULTS: According to ROC analyses for distinguishing tumor grade, minimum ADCs showed the largest areas under the ROC curve. Minimum ADCs optimally helped distinguish grade 1 from higher-grade tumors at a cutoff value of 1.47 x 10(-3) mm(2)/sec and grade 4 from lower-grade tumors at a cutoff value of 1.01 x 10(-3) mm(2)/sec (P < .001 for both). ADC difference values helped distinguish grade 2 from grade 3 tumors at a cutoff value of 0.31 x 10(-3) mm(2)/sec (P < .001). When tumors were graded by using the combined minimum ADC and ADC difference cutoff values mentioned above (the two-parameter method), the following positive predictive values were obtained: grade 1 tumors, 73% (eight of 11); grade 2 tumors, 100% (five of five); grade 3 tumors, 67% (eight of 12); and grade 4 tumors, 91% (20 of 22). CONCLUSION: Using a combination of minimum ADCs and ADC difference values (the two-parameter method) facilitates the accurate grading of astrocytic tumors.

Hydrogen storage in double clathrates with tert-butylamine.

The first proof-of-concept of the formation of a double tert-butylamine (t-BuNH(2)) + hydrogen (H(2)) clathrate hydrate has been demonstrated. Binary clathrate hydrates with different molar concentrations of the large guest t-BuNH(2) (0.98-9.31 mol %) were synthesized at 13.8 MPa and 250 K, and characterized by powder X-ray diffraction and Raman microscopy. A structural transformation from sVI to sII of t-BuNH(2) hydrate was clearly observed under hydrogen pressures. Raman spectroscopic data suggested that the hydrogen molecules occupied the small cages and had similar occupancy to hydrogen in the double tetrahydrofuran (THF) + H(2) clathrate hydrate. The hydrogen storage capacity in this system was approximately 0.7 H(2) wt % at the molar concentration of t-BuNH(2) close to the sII stoichiometry.

Structural transformations of sVI tert-butylamine hydrates to sII binary hydrates with methane.

Binary clathrate hydrates with methane (CH(4), 4.36 A) and tert-butylamine (t-BuNH(2), 6.72 A) as guest molecules were synthesized at different molar concentrations of t-BuNH(2) (1.00-9.31 mol %) with methane at 7.0 MPa and 250 K, and were characterized by powder X-ray diffraction (PXRD) and Raman microscopy. A structural transformation from sVI to sII of t-BuNH(2) hydrate was clearly observed on pressurizing with methane. The PXRD showed sII signatures and the remnant sVI signatures were insignificant, implying the metastable nature of sVI binary hydrates. Raman spectroscopic data on these binary hydrates suggest that the methane molecules occupy the small cages and vacant large cages. The methane storage capacity in this system was nearly doubled to approximately 6.86 wt % for 5.56 mol % > t-BuNH(2) > 1.0 mol %.

Tetra-n-butylammonium borohydride semiclathrate: a hybrid material for hydrogen storage.

In this study, we demonstrate that tetra-n-butylammonium borohydride [(n-C(4)H(9))(4)NBH(4)] can be used to form a hybrid hydrogen storage material. Powder X-ray diffraction measurements verify the formation of tetra-n-butylammonium borohydride semiclathrate, while Raman spectroscopic and direct gas release measurements confirm the storage of molecular hydrogen within the vacant cavities. Subsequent to clathrate decomposition and the release of physically bound H(2), additional hydrogen was produced from the hybrid system via a hydrolysis reaction between the water host molecules and the incorporated BH(4)(-) anions. The additional hydrogen produced from the hydrolysis reaction resulted in a 170% increase in the gravimetric hydrogen storage capacity, or 27% greater storage than fully occupied THF + H(2) hydrate. The decomposition temperature of tetra-n-butylammonium borohydride semiclathrate was measured at 5.7 degrees C, which is higher than that for pure THF hydrate (4.4 degrees C). The present results reveal that the BH(4)(-) anion is capable of stabilizing tetraalkylammonium hydrates.

Synchronous spontaneous arteriovenous fistula and aneurysm of the deep femoral artery incidentally found in a patient with aortic aneurysmal dissection.

The patient was a 77-year-old man with sudden-onset chest and back pain. Computed tomography angiography (CTA) from the abdomen to the proximal thigh showed an aortic aneurysmal dissection (AAD) and a left deep femoral artery (DFA) aneurysm. The AAD was conservatively managed as there was no sign of increase. The left DFA aneurysm was surgically resected to avoid complications such as rupture, thromboembolism, and limb ischemia. On follow-up CTA obtained 3 weeks later, a spontaneous AVF in a varicose vein of the right DFA was noted. There were no symptoms associated with the AVF, and he was conservatively managed. However, the varicose vein gradually increased, and he underwent successful transarterial catheter embolization (TAE) with metal coils without any complications. After vascular repair of the aneurysm and the AVF of the right DFA, there was no sign of recurrence.

Enclathration of Ethane, Propane, and Propylene into Urea Clathrates and Roles of Methanol on Urea Clathrate Formation.

As a guest molecule of urea clathrate, a long-chain normal alkane and its derivative with low substituents in methanol solutions have been reported. To investigate the role of methanol in the urea clathrate formation, in the present study, we used propane (C3H8), propylene (C3H6), ethane (C2H6), and methane (CH4) as guest molecules. Raman spectra and powder X-ray diffraction profiles revealed that, regardless of the existence of methanol, the C3H8, C3H6, and C2H6 molecules are enclathrated into urea clathrates with a hexagonal structure, whereas there is no urea clathrate formation enclathrating CH4. The pressurization of the urea clathrates including C2H6 and C3H8 reveals that no pressure-induced structural phase transition occurs at pressures up to 200 MPa. In spite of the guest molecule much shorter than the lattice constant of the c-axis of the hexagonal channel structure, the urea clathrates have a fairly rigid structure against the compression. Methanol as an auxiliary solution is not always necessary for the urea clathrate formation. Methanol plays a role in decreasing the activation energy of the urea clathrate formation, although it makes urea clathrate thermodynamically unstable due to the high solubility of urea in methanol.

Emergency radiology after a massive earthquake: clinical perspective.

Earthquakes are unpredictable and inevitable disasters, causing various earthquake-related disorders. Medical imaging, including digital radiography, computed tomography, and magnetic resonance imaging, plays a key role in the evaluation of earthquake-related disorders. We here demonstrate the concept of diagnostic imaging after a massive earthquake and review the common imaging features of various disorders in casualties and evacuees. This summary of imaging features can facilitate the diagnosis of various earthquake-related disorders and promote judicious therapy planning.

Perfusion abnormality on three-dimensional arterial spin labeling with a 3T MR system in pediatric and adolescent patients with migraine.

PURPOSE: Few studies have assessed the prevalence of perfusion abnormality with migraine. This study aimed to determine the prevalence and topography of perfusion abnormality on three-dimensional (3D) arterial spin labeling (ASL) and assess the correlation between perfusion abnormality and clinical data in pediatric and adolescent patients with migraine. METHODS: Forty-nine consecutive pediatric and adolescent patients with migraine were enrolled, and they underwent 3 T MRI, including 3D ASL. Perfusion abnormality on 3D ASL was qualitatively evaluated using a five-point grading system and was compared with non-ASL MR findings. In patients with perfusion abnormality, relative cerebral perfusion signal intensity (rCPS) was measured. Moreover, we compared clinical data and 3D ASL findings between patients with and those without perfusion abnormality. RESULTS: Of the 49 patients, 11 (22%) exhibited perfusion abnormality, and the occipital lobe was the most frequently involved (73%). One patient showed mild hyperperfusion (rCPS =2.474), and 10 showed hypoperfusion (mean rCPS = 0.405 ±â€¯0.134). There was no abnormality on non-ASL MRI, except in one case. We found statistically significant differences in the presence of aura (P < .001), motor disabilities (P = .019), confusion (P = .004), hospitalization (P = .004), between patients with and those without perfusion abnormality. CONCLUSION: In pediatric and adolescent patients with migraine, 3D ASL shows a high prevalence of perfusion abnormality, especially in the occipital lobe. Patients with perfusion abnormality tend to show the specific clinical symptoms at disease onset and need hospitalization.