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High-temperature superconductor (HTS) Josephson junctions (JJs) are primarily based on artificial grain boundaries. Bi-crystal JJs are typically utilized in HTS superconducting quantum interference devices (SQUIDs). However, the performances of bi-crystal JJs depend significantly on the quality of the interface at the junction. In this study, we investigate a method for forming nanobridge JJs via gallium focused ion beam (FIB) irradiation. A 100-nm-thick YBa2Cu3O7- δ was deposited on an MgO (100) substrate via pulsed laser deposition. An additional 20-nm-thick Au layer, which serves as a protection layer preventing ion damage during alignment, was deposited in situ. HTS microchannels with a width of 4 μm were defined via photolithography and argon ion milling. The HTS microchannel widths are decreased via FIB line scans to create nanobridges. The JJs are fabricated using two types of HTS thin films, in which one has a higher critical current density ( J C) that the other. The fabrication process using the gallium FIB was optimized and nanobridges with a junction width of 80 nm were prepared. As a result, a better with higher J C (5 MA/cm2) HTS films allowed for making junctions exhibiting up to five Shapiro steps at 77 K.

Metal-organic polyhedra (MOPs) can act as elementary structural units for the design of modular porous materials; however, their association with biological systems remains greatly restricted by their typically low stabilities and solubilities in water. Hereby, we describe the preparation of novel MOPs bearing either anionic or cationic groups and exhibiting a high affinity for proteins. Simple mixing of protein (BSA) and ionic MOPs aqueous solutions resulted in the spontaneous formation of MOP-protein assemblies, in a colloidal state or as solid precipitates depending on the initial mixing ratio. The versatility of the method was further illustrated using two enzymes, catalase and cytochrome c, with different sizes and isoelectric points (pI) below and above 7. This mode of assembly led to the high retention of catalytic activity and enabled recyclability. Furthermore, the co-immobilization of cytochrome c with highly charged MOPs resulted in a substantial 44-fold increase of its catalytic activity.

The ortho-isomer of molecular hydrogen (o-H2) was converted to the para-isomer (p-H2) within 600 s by using Prussian blue analogs, {MII3[CrIII(CN)6]2} (MCr; M = Mn and Ni), as nuclear-spin conversi...

Prussian blue analogues (PBAs), a class of microporous crystalline coordination frameworks, are long known for their diverse properties in porosity, magnetic, charge transport, catalysis, optics, and more. Versatile structural composition and the ability to control defect ordering through synthetic conditions offer opportunities to manipulate the functionality in the crystalline state. However, developments in Prussian blue analogues (PBAs) have primarily revolved around the ordered crystalline state, and the glassy state of PBAs has not yet been explored. Here we report the discovery of a disordered glassy state of the PBA via mechanically induced crystal–glass transformation. We found the preservation of metal–ligand–metal connectivity, confirming the short-range order and semiconductor behaviour, exhibiting an electronic conductivity value of 0.31 mS cm−1 at 50 ˚C. Mechanical-induced glass transformation also triggers changes in electronic states, where electroneutrality is compensated by introducing unconventional CN− vacancies. Partial disorders and ligand vacancies in recrystallized PBA give rise to an enhanced porosity, inaccessible in the crystalline parent. The present work also established a correlation between the mechanical stress required to initiate crystal–glass transformation and intrinsic mechanical properties, which are controlled by the vacancy/defect content, the presence of interstitial water, and the overall composition of PBAs.

Background: This study aimed to investigate the association between serum apolipoprotein A1 (ApoA1) levels, ischemic stroke subtypes and plaque properties. Methods: We enrolled 92 patients with ischemic stroke and 21 age-matched controls (CONT). The stroke patients were divided into three subtypes: cardioembolic (CE, n = 15), atherothrombotic infraction (ATBI, n = 52), and lacunar infarction (LI, n = 25). Carotid plaques were classified as low, intermediate, or high intensity, and either simple or mixed type. Serum lipids (total cholesterol (TC), low-density lipoprotein cholesterol (LDL-C), high-density lipoprotein cholesterol (HDL-C), triglyceride (TG)), ApoA1, and ApoB were analyzed using commercially available kits. Results: There was no difference in TC, LDL-C, HDL-C, and ApoB levels among the four groups. Serum ApoA1 levels in the ATBI group were significantly lower compared with the CONT group. Among the ATBI group, the serum ApoA1 levels in the low-intensity plaque-type were significantly lower than those in the intermediate or hard-intensity plaque-type. Furthermore, serum ApoA1 levels in the mixed plaque-type were significantly lower than those in the simple type. Conclusions: These findings suggest that serum ApoA1 levels might be associated with the development of ATBI and plaque properties of the carotid artery. J Clin Med Res. 2020;12(9):598-603 doi: https://doi.org/10.14740/jocmr4284

International audience; BACKGROUND: Patients who have had a stroke with unknown time of onset have been previously excluded from thrombolysis. We aimed to establish whether intravenous alteplase is safe and effective in such patients when salvageable tissue has been identified with imaging biomarkers. METHODS: We did a systematic review and meta-analysis of individual patient data for trials published before Sept 21, 2020. Randomised trials of intravenous alteplase versus standard of care or placebo in adults with stroke with unknown time of onset with perfusion-diffusion MRI, perfusion CT, or MRI with diffusion weighted imaging-fluid attenuated inversion recovery (DWI-FLAIR) mismatch were eligible. The primary outcome was favourable functional outcome (score of 0-1 on the modified Rankin Scale [mRS]) at 90 days indicating no disability using an unconditional mixed-effect logistic-regression model fitted to estimate the treatment effect. Secondary outcomes were mRS shift towards a better functional outcome and independent outcome (mRS 0-2) at 90 days. Safety outcomes included death, severe disability or death (mRS score 4-6), and symptomatic intracranial haemorrhage. This study is registered with PROSPERO, CRD42020166903. FINDINGS: Of 249 identified abstracts, four trials met our eligibility criteria for inclusion: WAKE-UP, EXTEND, THAWS, and ECASS-4. The four trials provided individual patient data for 843 individuals, of whom 429 (51%) were assigned to alteplase and 414 (49%) to placebo or standard care. A favourable outcome occurred in 199 (47%) of 420 patients with alteplase and in 160 (39%) of 409 patients among controls (adjusted odds ratio [OR] 1·49 [95% CI 1·10-2·03]; p=0·011), with low heterogeneity across studies (I(2)=27%). Alteplase was associated with a significant shift towards better functional outcome (adjusted common OR 1·38 [95% CI 1·05-1·80]; p=0·019), and a higher odds of independent outcome (adjusted OR 1·50 [1·06-2·12]; p=0·022). In the alteplase group, 90 (21%) patients were severely disabled or died (mRS score 4-6), compared with 102 (25%) patients in the control group (adjusted OR 0·76 [0·52-1·11]; p=0·15). 27 (6%) patients died in the alteplase group and 14 (3%) patients died among controls (adjusted OR 2·06 [1·03-4·09]; p=0·040). The prevalence of symptomatic intracranial haemorrhage was higher in the alteplase group than among controls (11 [3%] vs two [\textless1%], adjusted OR 5·58 [1·22-25·50]; p=0·024). INTERPRETATION: In patients who have had a stroke with unknown time of onset with a DWI-FLAIR or perfusion mismatch, intravenous alteplase resulted in better functional outcome at 90 days than placebo or standard care. A net benefit was observed for all functional outcomes despite an increased risk of symptomatic intracranial haemorrhage. Although there were more deaths with alteplase than placebo, there were fewer cases of severe disability or death. FUNDING: None.

We report an 86-year-old woman who suffered sudden onset of diplopia while cooking. The patient presented with binocular diplopia, bilateral adduction weakness, convergence disorder and bilateral abduction nystagmus. Although brain MRI on admission detected no abnormality, a repeat MRI examination on the following day demonstrated a focal hyperintense lesion in the tegmentum of the midbrain on diffusion-weighted images. At 36 hours after admission, lower abdominal distension became apparent, and about 1 liter of urine was drained via a urethral catheter. Bladder filling sensation was not present, and we considered that the midbrain lesion had been responsible for the oculomotor disorder and urinary retention. As cerebral infarction was the most likely pathology of this lesion, an antiplatelet agent was administered. At two months after onset, the eye movement disorder was resolved and there was no diplopia. Bladder voiding also resumed at normal intervals. We considered that the bilateral medial longitudinal fasciculi and subgroups of the oculomotor nucleus, which contain motor neurons supplying the medial rectus muscle, had been responsible for the oculomotor disorder. The urinary retention was thought to have been caused by a lesion in the periaqueductal gray, which is one structure controlling micturition. This was a rare case of urinary retention due to a small midbrain infarction.

A 73-year-old women visited emergency department because of sudden right hemiplegia. She had a history of duodenum papilla cancer terminal stage and multiple liver metastasis. On admission, diffusion weighted images revealed high intensity area at left middle cerebral artery territory. In addition, 3D-TOF MRA depicted proximal part of the left internal carotid artery. We performed endovascular thrombectomy because low platelet count met contraindication of intravenous recombinant tissue plasminogen activator therapy. Although we could get partial recanalization of middle cerebral artery occlusion after thrombectomy, the patient eventually died due to multiple organ failure. Autopsy findings showed white thrombus on mitral valve and also left middle cerebral artery occluded by similar white thrombus without infective findings. The patient was finally diagnosed with nonbacterial thrombotic endocarditis due to white thrombus on the mitral valve. We should select appropriate mechanical thrombectomy devices with a case of cerebral infarction due to nonbacterial thrombotic endocarditis because its thrombus is often white thrombus and would be hard.

High dielectric constants (er) were observed in two-dimensional composites obtained from stacking of reduced graphene oxide (RGO) with Ca2Nb3O10 and with TiO2 nanosheets. The relative dielectric permittivity values of the composites were found to be higher than 105, an amazingly high value compared to that of similar GO composites and other common dielectric materials. As a consequence, we considered application of the hybrids as super dielectric materials in high capacitance supercapacitors. The route to high capacitance involves the variation of oxygen vacancies within the surface and in the closest bulk interior of the hybrids. The effective charges generated throughout the metal oxide and carbon–oxygen polar bonding systems within the graphene skeleton appear to highly influence dielectric polarization. Moreover, the replenishment of oxygen vacancies at the RGO and metal oxide interface also contributes to polarizability.

A 40-year-old man visited our department because of chest and back pain. He had a history of diagnosis of chronic inflammatory demyelinating polyneuropathy (CIDP) 20 years ago. He received immunosuppressive therapy and had no relapses after that. On Admission, MRI showed tuberous hypertrophy of the spinal roots, intercostal nerves, and brachial and lumbar plexuses. The genetic analysis showed no mutations in any of Charcot-Marie-Tooth related genes. He was finally diagnosed with CIDP and administration of high dose intravenous methylprednisolone relieved his chest and back pain within a few days. We present a rare case of CIDP in which showed marked enlarged spinal roots in long clinical course and have a relapse with radicular pain without sensorimotor symptoms.

Hybrid materials that are obtained from intercalation of different polar and hydrophilic acid guest molecules within graphene oxide (GO) have been found to exhibit high proton conductivity. The accommodation of these guest precursors within the GO interlayer takes place through weak physical forces. PXRD patterns with enhanced interlayer distance confirmed successful intercalation processes. Raman and IR spectral data reveal the absence of any covalent bond between the functional groups of the guest and the GO host. TGA data confirms improved water adsorbing capacity of the hybrids. At ambient conditions and 90% relative humidity (RH), a RH dependent impedance study shows that intercalation of formic acid (FA) and phosphoric acid (PA) within GO results in ∼7 times higher proton conductivity compared with that for the pristine GO sample. The low activation energy values suggest that proton conduction in the samples is aided by the Grotthuss mechanism. Improvement in the water adsorbing capacity is primarily responsible for such high proton conductivity. The current study suggests that cheap and environmentally friendly GO-based intercalated hybrid materials, such as GO/PA and GO/FA with enhanced proton conductivity, can be appropriate replacements for the expensive Nafion-based solid electrolytes.

Fe[((py)im-C16) 3 ](BF 4 ) 2 ( 1 ) and Fe[((py)imH) 3 ](BF 4 ) 2 ( 2 ), the Iron(II) compounds with C16 long alkyl chain appended (py)imH and unmodified (py)imH [(py)imH = 2-(2-pyridyl)imidazole] have been synthesized and characterized by NMR, IR spectra and elemental analysis. For containing C16 long alkyl chain, complex 1 exhibits the liquid crystalline property around room temperature. The magnetic study suggests that 1 exists only in low spin state but 2 exhibits gradual spin crossover behavior. These observation suggests the possibility for synchronizing liquid crystallinity and spin crossover behavior of (py)imH complex in near future.

The metal atom of the title compound is four coordinated. The asymmetrically appended Cl atom and a widely spread π-conjugated system of the complex mol­ecule construct the supra­molecular structures of a hydrogen-bonded chain and a π–π inter­acted column., The title complex, [Ni(C20H14ClN3O)], with an asymmetrically chloride-appended Schiff base ligand has been synthesized and structurally characterized at 100 K. In the compound, the central nickel(II) ion has a square-planar coordination geometry with N3O donors of the π-conjugated tetra­dentate Schiff base ligand. In the crystal, the complexes are connected into an inversion dimer via an Ni⋯Ni inter­action [3.1753 (5) Å] and a pair of π–π inter­actions [centroid–centroid distance = 3.8416 (16) Å]. The dimers are linked via a C—H⋯Cl hydrogen bond, forming a chain along the c-axis direction. The dimer chains inter­act with each other through π–π inter­actions [centroid–centroid distance = 3.8736 (16) Å], forming a layer expanding parallel to the ac plane.

High Temperature Superconductor Josephson Junctions (HTS-JJs) are based on artificial grain boundaries. However, the layout of HTS Superconducting QUantum Interference Devices (SQUIDs) on a bi-crystal substrate was restricted. Therefore, we considered to form low noise nano-bridge JJs by Ga Focused Ion Beam (Ga-FIB) irradiation. An 100 nm thick and 4 μm wide YBa2Cu3O7-δ (YBCO) micro-channels protected by a 20 nm thick Au protection layer were irradiated by line scans of Ga-FIB (Acceleration voltage: 40 kV, Beam diameter: ∼30 nm) and they were became normal conductivity except for the restricted region. In those nano-bridges, W N = 500 nm and fluence Φ = 2.0×1015 ions/cm2 of the nano-bridge was I C = 170 μA and we confirmed Shapiro steps by microwave irradiation of f RF = 2 GHz.

A 61-year-old woman developed hearing difficulties and became thirsty after experiencing cold symptoms. A neurological examination revealed a loss of odor sensation, facial palsy, dysphasia, and dysarthria. Vocal cord palsy was observed during pharyngoscopy. Brain magnetic resonance imaging (MRI) showed a thickened pituitary stalk and swelling of the pituitary gland, but no high signal intensity regions were seen in the posterior portion of the pituitary gland. Gadolinium-enhanced MRI demonstrated a thickened dura mater over the anterior cranial fossa. A biopsy specimen of the thickened dura mater showed fibrosis, granulomatous inflammation, and necrotic foci. Blood tests detected myeloperoxidase anti-neutrophil cytoplasmic antibody (MPO-ANCA). The patient's urine osmolarity was low even though she exhibited hypernatremia. We diagnosed her with hypertrophic pachymeningitis associated with MPO-ANCA and diabetes insipidus. The patient received two courses of 5-day high-dose intravenous methylprednisolone (1.0 g/day), and was subsequently administered oral prednisolone, which gradually relieved her symptoms. However, the patient's symptoms recurred despite the high-dose prednisolone treatment. It was difficult to control the patient's symptoms in this case with oral prednisolone monotherapy, but combined treatment with cyclosporine resulted in sustained remission. It is considered that patients with MPO-ANCA-positive hypertrophic pachymeningitis require combination therapy with prednisolone and immunosuppressive agents at an early stage.

An antimalarial drug artesunate (ATS) was encapsulated in both functionalized MCM-41 and ordinary MCM-41 with an excellent loading capacity and sustained release behavior for possible biomedical applications.

To determine whether output from the forebrain (termed central command) may descend early enough to increase cardiac and renal sympathetic outflows at the onset of voluntary exercise, we examined the changes in regional tissue blood flows of bilateral prefrontal cortices with near-infrared spectroscopy, precisely identifying the onset of voluntary ergometer 30-s exercise at 41 ± 2% of the maximal exercise intensity in humans. Prefrontal oxygenated-hemoglobin (Oxy-Hb) concentration was measured as index of regional blood flow unless deoxygenated-hemoglobin concentration remained unchanged. Prefrontal Oxy-Hb concentration increased significantly ( P < 0.05) 5 s prior to the onset of exercise with arbitrary start, whereas such increase in prefrontal Oxy-Hb was absent before exercise abruptly started by a verbal cue. Furthermore, the increase in prefrontal Oxy-Hb observed at the initial 15-s period of exercise was greater with arbitrary start than cued start. The prefrontal Oxy-Hb, thereafter, decreased during the later period of exercise, irrespective of either arbitrary or cued start. The reduction in prefrontal Oxy-Hb had the same time course and response magnitude as that during motor-driven passive exercise. Cardiac output increased at the initial period of exercise, whereas arterial blood pressure and total peripheral resistance decreased. The depressor response was more pronounced ( P < 0.05) with arbitrary start than cued start. Taken together, it is suggested that the increase in prefrontal Oxy-Hb observed prior to the onset of voluntary exercise may be in association with central command, while the later decrease in the Oxy-Hb during exercise may be in association with feedback stimulated by mechanical limb motion.

Heart failure (HF) increases the risk of ischemic stroke. Data regarding the incidence and predictors of ischemic stroke during hospitalization for HF are limited. The study population of this retrospective cohort study consisted of patients with congestive HF, consecutively admitted to our center from October 2010 to April 2014. We excluded patients complicated with acute myocardial infarction, infective endocarditis, and takotsubo cardiomyopathy. We also excluded those with dialysis or mechanical circulatory support. We investigated the incidence of ischemic stroke during hospitalization for HF. Thereafter, we divided the patients without oral anticoagulants at admission into two groups: patients with ischemic stroke and those without it, and explored the predictors of ischemic stroke. A total of 558 patients (287 without atrial fibrillation (AF), 271 with AF) were enrolled. The mean age was 76.8 ± 12.3 years, and 244 patients (44 %) were female. The mean left-ventricular ejection fraction was 47.4 %. Oral anticoagulants were prescribed in 147 patients (8 without AF, 139 with AF). During hospitalization (median length 18 days), symptomatic ischemic stroke (excluding catheter-related) occurred in 15 patients (2.7 % of the total, 8 without AF, 7 with AF). Predictors significantly associated with increased risk of ischemic stroke in patients without oral anticoagulants were as follows; short-term increases in blood urea nitrogen after admission (at day 3; odds ratio (per 1 md/dl): 1.06, 95 % confidence interval (CI) 1.01-1.11, p = 0.02, and at day 7; odds ratio: 1.03, 95 % CI 1.00-1.07, p = 0.03, respectively), and previous stroke (odds ratio; 3.33, 95 % CI 1.01-11.00, p = 0.04). The incidence of ischemic stroke during hospitalization for HF was high, even in patients without AF. Previous stroke and short-term increases in blood urea nitrogen was significantly associated with the incidence of ischemic stroke.

Two solvated cobalt(II) terpyridine complexes, [Co(MeO-terpy)2](BF4)2·H2O (1·H2O) and [Co(MeO-terpy)2](BF4)2·acetone (1·acetone) were prepared. Annealing each of these complexes resulted in the formation of two desolvated species, 1 and 1′, respectively. 1·H2O and 1 exhibited two-step and gradual SCO. The compound 1·acetone has high-spin at all temperatures and 1′ undergoes a reverse spin transition due to a phase change.

The cover picture shows the solid state battery where graphene oxide (GO) is used as proton conducting solid electrolyte. Respective discharge capacity and power density of the cell is found to be 360 μA h and 19.5 mW kg−1 at a constant current drain of 3 μA under experimental condition. GO based proton conductors as solid electrolyte are cleaner, cheaper and fascicle alternative for applications with low energy feedback. More information can be found in article number 1700054 by Yuta Shudo, Md. Saidul Islam, Mohammad Razaul Karim, Nurun Nahar Rabin, Kosuke Wakata, Ryo Ohtani, Masaaki Nakamura, Leonard F. Lindoy, and Shinya Hayami*.

Tuneable pressure effects associated with changing interlayer distances in two-dimensional graphene oxide (GO)/reduced GO (rGO) layers are demonstrated through monitoring the changes in the spin-crossover (SCO) temperature (T1/2) of [Fe(Htrz)2(trz)](BF4) nanoparticles (NPs) incorporated in the interlayer spaces of the GO/rGO layers. The interlayer separation along the GO to GO/rGO-NP composites to rGO series decreases smoothly from 9.00 Å (for GO) to 3.50 Å (for rGO) as the temperature employed for the thermal reduction treatments of the GO-NP composites is increased. At the same time, T1/2 increases from 351 K to 362 K along the series. This T1/2 increment of 11 K corresponds to that observed for pristine [Fe(Htrz)2(trz)](BF4) NPs under a hydrostatic pressure of 38 MPa. The influence of the stacked layer structures on the pseudo-pressure effects has been further probed by investigating the differences in T1/2 for [Fe(Htrz)2(trz)](BF4) that is present in the composite as larger bulk particles rather than as NPs.

Background: Large-scale clinical trials have analyzed risk factors for any ischemic stroke in patients with atrial fibrillation (AF). However, the risk factors for cardioembolic stroke (CES), specifically, have not been reported. To clarify the risk factors for CES and clinically significant cardioembolic infarction, we examined the incidence of CES and larger infarct volume (IV) (> 30 mL) CES, employing the Fushimi AF Registry, a community-based prospective cohort of AF patients in the Fushimi ward, Kyoto, Japan. Methods: A total of 4,182 Fushimi AF patients were enrolled from March 2011 to December 2014. The risk factors for CES were evaluated using multivariate analysis. Results: Of 4,182 patients enrolled, 3,749 patients were observed for ≥1 year. During the follow-up period (mean duration, 979 ± 7.7 days), 91/3,749 patients experienced a CES (2.43%). Significant risk factors associated with CES were older age (odds ratio [OR], 1.31; 95% confidence interval [CI], 1.01–1.72; p = 0.046), low body weight (OR, 1.30; 95% CI, 1.03–1.65; p = 0.033), sustained AF (OR, 1.67; 95% CI, 1.05–2.71; p = 0.034), and previous stroke or transient ischemic attack (TIA) (OR, 1.94; 95% CI, 1.22–3.06; p = 0.004). Predictors of a large IV were chronic kidney disease (CKD) (OR, 2.08; 95% CI, 1.09–4.05; p = 0.027) and previous stroke/TIA (OR, 2.27; 95% CI, 1.19–4.24; p = 0.011). Conclusions: In this population-based cohort of Japanese patients with AF, in addition to previous stroke/TIA and older age, sustained AF and low body weight emerged as risk factors for CES, as opposed to any stroke, which may have a different risk profile. Patients with CKD or previous stroke/TIA who developed cardioembolic infarction exhibited more advanced severity. There is a need for direct oral anticoagulants that can be used safely in patients with comorbid AF and CKD.

The title compound, bis­[4′-(1,4,7,10-tetra­oxa-13-aza­cyclo­penta­decan-13-yl)-2,2′:6′,2"-terpyridine]­cobalt(III) tris­(perchlorate) methanol monosolvate monohydrate, is a novel complex in which the metal centre is hexa­coordinated., In the title compound, [Co(C25H30N4O4)2](ClO4)3·CH3OH·H2O, the metal atom is coordinated by two tridentate crown ether terpyridine ligands, forming a distorted CoN6 octa­hedron. The three pyridine rings in each crown–terpyridine ligand are approximately coplanar [maximum deviations = 0.088 (12) and 0.102 (15) Å] and the mean planes through the three pyridine rings are perpendicular to each other, making a dihedral angle of 89.95 (17)°. An intra­molecular C—H⋯π inter­action is observed between the two terpyridine ligands. In the crystal, O—H⋯O and C—H⋯O hydrogen bonds, a π–π stacking inter­action [centroid–centroid distance = 3.923 (7) Å] and a C—H⋯π inter­action connect the complex cation, the perchlorate anions and the two types of solvent molecules, forming a three-dimensional network.

Two 2D Hofmann-type spin-crossover coordination polymers, [Fe(stpy)2Pt(CN)4]·0.5MeOH (stpy = 4-styrylpyridine; 1) and [Fe(pep)2Pt(CN)4] {pep = 4-(2-phenylethyl)pyridine; 2}, have been prepared by using long co-ligands with different flexibilities. These compounds form 3D interdigitate structures based on 2D layers extended by Pt–CN–Fe linkages with different interlayer structures depending on the nature of the axial co-ligand. The stpy co-ligand forms one-directional π–π networks between the layers, whereas pep forms two-directional π–π networks as a result of its perpendicularly twisted structure. Coordination polymer 1 exhibits a half-spin transition with Tc = 106 K and Tc = 110 K. In contrast, coordination polymer 2 shows a sharp, two-step spin transition in the temperature range 184–236 K. The difference in spin-transition behavior is discussed in terms of the interlayer packing structure.

Neuroblasts in the subventricular zone (SVZ) proliferate markedly after brain ischemia, and migrate to the site of injury along with blood vessels. However, a large fraction of stroke-generated neuroblasts die shortly after being born, in part, because of local inflammation. In spontaneously hypertensive rats (SHRs) subjected to permanent middle cerebral artery occlusion, we primed E-selectin-specific regulatory T cells (Tregs) by repetitive intranasal administration of recombinant E-selectin to target local secretion of immunomodulating, antiinflammatory cytokines to activating blood vessel segments. E-selectin-tolerized SHRs had decreased infarction volumes, and increased numbers of Tregs in the cervical lymph nodes and ischemic brain. The brain Tregs were distributed primarily in periinfarct regions. E-selectin tolerization did not alter cellular proliferation in the ipsilateral SVZ after stroke, but the expression of tumor necrosis factor on vascular niche blood vessels was suppressed and both doublecortin protein levels and the number of newly generated neuroblasts or neurons were increased in the brain. This enhanced survival of neural progenitor cells and neurons was paralleled by improved functional performance. These studies suggest that E-selectin-specific Tregs can modulate the efficacy of neurogenesis after ischemia and promote repair after brain injury.

The racemic oxovanadium(IV) salmmen complexes, [VO((rac)-(4-X-salmmen))] (X = C12C10C5 (1), C16 (2) and C18 (3); salmmen = N,N′-monomethylenebis-salicylideneimine) with “banana shaped” molecular structures were synthesized and their ferroelectric properties were investigated. These complexes exhibit well-defined hysteresis loops in their viscous phases, moreover, 1 also displays liquid crystal behaviour. We observed a synergetic effect influenced by three structural aspects; the methyl substituents on the ethylene backbone, the banana shaped structure and the square pyramidal metal cores all play an important role in generating the observed ferroelectricity, pointing the way to a useful strategy for the creation of advanced ferroelectric soft materials.

Graphene oxide (GO) shows high proton conductivity (≈10−4 Scm−1), excellent mechanical stability, and electrical insulation property, which makes it an ideal candidate for use as a proton conducting solid state electrolyte. The prospects of using GO as single phase solid electrolyte in an all solid battery is presented herein. A battery with the cell configuration: Zn + ZnSO4•7H2O + graphite (anode) || GO (electrolyte) || MnO2 + graphite (cathode) is fabricated. Cyclic voltammetry confirms its rechargeable nature. The respective discharge capacity and power density of the cell are 360 μAh and 19.5 mW kg−1 at a constant current drain of 3 μA under the experimental conditions employed. GO based proton conductors are cleaner and cheaper than other solid electrolytes. The current study strongly suggests that GO can be used as a practical and beneficial component in solid state battery applications with low energy feedback.

The synthesis, structure, and magnetic properties of three clathrate derivatives of the spin-crossover porous coordination polymer {Fe(pyrazine)[Pt(CN)(4)]} (1) with five-membered aromatic molecules furan, pyrrole, and thiophene is reported. The three derivatives have a cooperative spin-crossover transition with hysteresis loops 14-29 K wide and average critical temperatures T-c=201 K (1.fur), 167 K (1.pyr), and 114.6 K (1.thio) well below that of the parent compound 1 (T-c=295 K), confirming stabilization of the HS state. The transition is complete and takes place in two steps for 1.fur, while 1.pyr and 1.thio show 50% spin transition. For 1.fur the transformation between the HS and IS (middle of the plateau) phases occurs concomitantly with a crystallographic phase transition between the tetragonal space groups P4/mmm and I4/mmm, respectively. The latter space group is retained in the subsequent transformation involving the IS and the LS phases. 1.pyr and 1.thio display the tetragonal P4/mmm and orthorhombic Fmmm space groups, respectively, in both HS and IM phases. Periodic calculations using density functional methods for 1.fur, 1.pyr, 1.thio, and previously reported derivatives 1.CS2, 1.I, 1.bz(benzene), and 1.pz(pyrazine) have been carried out to investigate the electronic structure and nature of the host-guest interactions as well as their relationship with the changes in the LS-HS transition temperatures of 1.Guest. Geometry-optimized lattice parameters and bond distances in the empty host 1 and 1.Guest clathrates are in general agreement with the X-ray diffraction data. The concordance between the theoretical results and the experimental data also comprises the guest molecule orientation inside the host and intermolecular distances. Furthermore, a general correlation between experimental T-c and calculated LS-HS electronic energy gap was observed. Finally, specific host-guest interactions were studied through interaction energy calculations and crystal orbital displacement (COD) curve analysis., The research reported herein was supported by the Spanish Ministerio de Ciencia e Innovacion (MICINN) and FEDER funds (CTQ2013-46275-P and CTQ2011-23862-C02-01), Generalitat de Catalunya (2009SGR-1459) and Generalitat Valenciana through PROMETEO/2012/049. D. A. thanks Conicyt-Chile for a predoctoral fellowship. Z.A.C. thanks the Spanish M.E.C.D. for a predoctoral FPU fellowship. M.O. thanks a Grant-In-Aid for Science Research for Innovative Areas "Coordination Programming (Area 2107, No. 22108512)" and for Scientific Research Program (A) (No. 23245014) from MEXT, Japan. The authors thankfully acknowledge the computer resources, technical expertise, and assistance provided by the Barcelona Supercomputer Center.

椎骨・脳底動脈系の切迫卒中に対し血管内手術が著効した1例を, 文献的考察を加え報告した.症例は61歳, 男性で構音障害, 下肢の脱力で発症した.来院時, 意識障害, 四肢麻痺を認めた.脳血管写で左椎骨動脈V4部での閉塞, 右椎骨動脈でのPICA endの所見を認め, 選択的血栓溶解療法 (PTR) を施行した.発症7時間後に左椎骨動脈・脳底動脈双方に糸状開通を認めた.残存する狭窄部に対しバルーンを用いて血管形成術 (PTA) を行ない, 発症7.5時間後に病変部の十分な拡張を得た.頭蓋内, 特に脳底動脈のPTAには, 穿通枝梗塞の危険性があるが, 本例のように進行性の急性脳卒中に対しては, 保存的治療や外科手術では得られない効果をPTR, PTAで得ることができ, 症例を慎重に選んだ場合, 有効な治療法と考えられた.

頸動脈内膜剥離術 (CEA) 後の頸部超音波所見に関する報告は少ない.CEA24±29カ月後に頸部超音波検査をした62例の総頸動脈断端部, 分岐部, 内頸動脈近位部におけるプラーク陽性率, プラーク性状, プラーク形成影響因子を検討した.いずれの部位でも術後早期よりプラークがみられることが多く, 術後期間とプラーク陽性率は無関係であった.プラーク性状は部位によって異なり, 特に総頸動脈断端部において動脈硬化性ではない隆起性のものがみられるのが特徴的であった.いずれの部位でもプラーク指数 (プラークの高さの総和) は動脈硬化危険因子の有無と無関係であった.CEA後にみられるプラークは早期よりみられてその後変化しないこと等から, 主として術後修復機転の結果を反映するものではないかと考えられる.

A quasielastic neutron scattering and solid-state 2H NMR spectroscopy study of the polymeric spin-crossover compound {Fe(pyrazine)[Pt(CN) 4]} shows that the switching of the rotation of a molecular fragment-the pyrazine ligand-occurs in association with the change of spin state. The rotation switching was examined on a wide time scale (10 -13-10 -3 s) by both techniques, which clearly demonstrated the combination between molecular rotation and spin-crossover transition under external stimuli (temperature and chemical). The pyrazine rings are seen to perform a 4-fold jump motion about the coordinating nitrogen axis in the high-spin state. In the low-spin state, however, the motion is suppressed, while when the system incorporates benzene guest molecules, the movements of the system are even more restricted. © 2012 American Chemical Society., This work was supported by the Spanish MICINN and FEDER, projects MAT2007-61621, CSD2007-00010, MAT2011-27233-C02-02, and CTQ2010-18414, and by a CREST JST program and Grant-In-Aid for Scientific Research (No. 23245014 and 22108512) from the Ministry of Education, Culture, Sports, Science and Technology of Japan.

Background and Purpose— We recently designed a mouse model of chronic cerebral hypoperfusion, in which the cerebral white matter is damaged without significant gray matter lesions. The behavioral characteristics of these mice were studied using a test battery for neurological and cognitive functions. Methods— Adult C57Bl/6 male mice were subjected to either sham-operation or bilateral common carotid artery stenosis (BCAS) using microcoils with an internal diameter of 0.18 mm. At 30 days after BCAS, 70 animals were divided into 3 groups and subjected to behavioral test batteries. The first group underwent comprehensive behavioral test, including the neurological screen, prepulse inhibition, hot plate, open field, light/dark transition, Porsolt forced swim and contextual and cued fear conditioning (BCAS n=13; sham-operated n=11). The second group was for the working memory task of the 8-arm radial maze test (BCAS n=12; sham-operated n=10), and the third for the reference memory task of the 8-arm radial maze test (BCAS n=13; sham-operated n=11). Another batch of animals were examined for histological changes (BCAS n=11; sham-operated n=12). Results— The white matter including the corpus callosum was consistently found to be rarefied without clear ischemic lesions in the hippocampus. No apparent differences were observed in the comprehensive test batteries between the control and BCAS mice. However, in the working memory tasks tested with the 8-arm radial maze, the BCAS mice made significantly more errors than the control mice ( P Conclusions— At 30 days after BCAS, working memory deficits as well as white matter changes were apparent in the mice. Working memory deficit was attributable to damage of the frontal-subcortical circuits, suggesting the BCAS model is useful to evaluate the substrates of subcortical vascular dementia.

Background and Purpose— Cerebrovascular white matter (WM) lesions are closely associated with cognitive impairment and gait disorders in the elderly. We have successfully established a mouse model of chronic cerebral hypoperfusion that may provide new strategies for the molecular analysis of cerebrovascular WM lesions. Methods— Adult C57Bl/6 male mice were subjected to bilateral common carotid artery stenosis (BCAS) using external microcoils with varying inner diameters from 0.16 to 0.22 mm. Cerebral blood flow (CBF) in the frontal cortices was measured by laser-Doppler flowmetry at 2 hours and at 1, 3, 7, 14, and 30 days after BCAS. The brains were then removed and examined at 30 days with histological stains and immunohistochemistry for markers of microglia and astroglia. Results— At 2 hours, the CBF values (ratio to the preoperative value) did not change in the 0.22 mm group but decreased significantly to 77.3±13.4% in the 0.20 mm group, 67.3±18.5% in the 0.18 mm group, and 51.4±11.5% in the 0.16 mm group. At day 1, the CBF began to recover in all groups but remained significantly lower until 14 days in comparison to the control group. In the 0.20 mm and 0.18 mm groups, WM lesions occurred after 14 days without any gray matter involvement. These lesions were the most intense in the corpus callosum adjacent to the lateral ventricle but were mild in the anterior commissure and optic tract. In contrast, 4 of 5 mice developed some gray matter changes in the 0.16 mm group. The proliferation of activated microglia and astroglia was observed in the WM beyond 3 days after BCAS. Conclusions— WM lesions were successfully induced after chronic cerebral hypoperfusion with relative preservation of the visual pathway. These features in this mouse model are appropriate for cognitive assessment and genetic analysis, and it may provide a powerful tool to understand the pathophysiology of WM lesions.

Accumulating evidences indicate that ceramide is closely involved in apoptotic cell death in neurodegenerative disorders and aging. We examined ceramide levels in the cerebrospinal fluid (CSF) or brain tissues from patients with neurodegenerative disorders and the mechanism of how intra- and extracellular ceramide was regulated during neuronal apoptosis. We screened the ceramide levels in the CSF of patients with neurodegenerative disorders, and found that ceramide was significantly increased in patients with Alzheimer's disease (AD) than in patients with age-matched amyotrophic lateral sclerosis (ALS) and other neurological controls. With immunohistochemistry in AD brains, ceramide was aberrantly expressed in astroglia in the frontal cortices, but not detected in ALS and control brains. To explore for the regulation of ceramide in astroglia in Alzheimer's disease brains, we examined the metabolism of ceramide during neuronal apoptosis. In retinoic acid (RA)-induced neuronal apoptosis, RA slightly increased de novo synthesis of ceramide, but interestingly, RA dramatically inhibited conversion of [14C] ceramide to glucosylceramide (GlcCer), suggesting that the increase of ceramide mass is mainly due to inhibition of the ceramide-metabolizing enzyme GlcCer synthase. In addition, a significant increase of the [14C] ceramide level in the culture medium was detected by chasing and turnover experiments without alteration of extracellular [14C] sphingomyelin levels. A 2.5-fold increase of ceramide mass in the supernatant was also detected after 48 h of treatment with RA. These results suggest a regulatory mechanism of intracellular ceramide through inhibition of GlcCer synthase and a possible role of ceramide as an extracellular/intercellular mediator for neuronal apoptosis. The increased ceramide level in the CSF from AD patients, which may be derived from astroglia, raises a possibility of neuronal apoptosis by the response to intercellular ceramide in AD.