RESUMEN
Aeroacoustic fields of a supersonic free jet at the Mach and Reynolds numbers of 2.1 and 70 000, respectively, of the transitional conditions are computationally investigated by large-eddy simulations. The supersonic transitional jets of different shear layer thicknesses without disturbances and those of the fixed shear layer thickness with disturbances are computationally investigated, and the effects of the shear layer thickness and the disturbance are discussed. The position of the transition and the turbulence intensity in the vicinity of the transition are clearly affected by those parameters. The turbulent fluctuation along the shear layer and the resulting intensity of the generated Mach waves are substantially attenuated by decreasing the shear layer thickness or adding the disturbance. A 5 dB increase in the sound pressure level is observed. This relatively lower increment in the sound pressure level compared with the 10-20 dB increase in the subsonic jet case is discussed as being due to the transition process promoted by the spiral mode in the supersonic jet case, unlike the axisymmetric case in the subsonic jet case. This point is confirmed by the linear stability analysis, the proper orthogonal decomposition analysis, and the visualization of vortex structures in the transition region.
RESUMEN
The phase behavior of a representative ammonium-based ionic liquid, trimethylpropylammonium bis(fluorosulfonyl)amide ([N1113][FSA]), was investigated using a laboratory-made differential scanning calorimeter (DSC). The apparatus possesses extremely high sensitivities with stability of ±2 nW in thermal flux and ±1 mK in temperature and a very slow scanning rate of 0.001 mK s-1 in the slowest scanning speed. Besides two ordinary signals from crystallization and melting, a very weak exothermic peak, 1/1000 times that of the main crystallization peak, was observed during the cooling process. The peak was assigned to the crystallization of the surface-melting layer. Both the normal and novel crystallizations occurred during the structural relaxation process. The thickness of the surface-melting layer was estimated to be roughly 70-200 nm. To study the details of the melting processes, DSC experiments were performed with very slow scanning rates (0.02 and 0.03 mK s-1). Two novel endothermic peaks were found in the usual melting trace for the sample with the surface crystallization, and no unusual peaks were observed in the sample without the surface crystallization. We believe that the structure of the surface crystallization phase is different from that of the bulk crystalline phase.
RESUMEN
A nitroxyl-radical-catalyzed oxidative coupling reaction between amines with an N-protecting electron-withdrawing group (EWG) and silylated nucleophiles was developed to furnish coupling products in high yields, thus opening up new frontiers in organocatalyzed reactions. This reaction proceeded through the activation of N-halogenated amides by a nitroxyl-radical catalyst, followed by carbon-carbon coupling with silylated nucleophiles. Studies of the reaction mechanism indicated that the nitroxyl radical activates N-halogenated amides, which are generated from N-EWG-protected amides and a halogenation reagent, to give the corresponding imines.
RESUMEN
Some of the important factors that characterise room-temperature ionic liquids (RTILs) are the variety of conformations adopted by the constituent ions and their flexibility. Using 1,3-dimethylimidazolium bis(fluorosulfonyl)amide ([C1mim][FSA]) and 1,3-dimethylimidazolium bis(trifluoromethylsulfonyl)amide ([C1mim][NTf2]) as samples, the longitudinal and transverse relaxation times (T1 and T2) for (19)F and (1)H were determined as a function of temperature and were correlated with the dynamics of the phase behaviours of the two RTILs. Because the anions and cations in the two compounds have (19)F and (1)H nuclei, respectively, their dynamics can be independently investigated and the relationships between them can be discussed. For [C1mim][FSA], the only observed phase changes included melting and crystallisation. The temperature dependences of T1 and T2 for (19)F were similar to those of T1 and T2 for (1)H, indicating similar dynamics due to the formation of strong anion-cation interactions. For [C1mim][NTf2], the T1 and T2 values for both (19)F and (1)H discontinuously changed at same temperatures, which were assigned to the crystallisation and melting points. However, the T1 curves for (19)F and (1)H were different in the crystalline region, suggesting independent dynamics for the anions and cations in [C1mim][NTf2]. In the crystalline state for each salt, the cation dynamics was distinctly separated into the framework movement of the imidazolium ring and the movement of the methyl groups, while the anion dynamics was characterised by the movement of the entire anion. The influence of the crystal structure on the dynamics of each salt was also considered.
Asunto(s)
Aniones/química , Cationes/química , Imidazoles/química , Líquidos Iónicos/química , Transición de Fase , Conformación Molecular , Temperatura , Factores de TiempoRESUMEN
Abdominal aortic aneurysm (AAA) is a common disease among elderly people that, when surgical treatment is inapplicable, results in progressive expansion and rupture of the aorta with high mortality. Although nonsurgical treatment for AAA is much awaited, few options are available because its molecular pathogenesis remains elusive. Here, we identify JNK as a proximal signaling molecule in the pathogenesis of AAA. Human AAA tissue showed a high level of phosphorylated JNK. We show that JNK programs a gene expression pattern in different cell types that cooperatively enhances the degradation of the extracellular matrix while suppressing biosynthetic enzymes of the extracellular matrix. Selective inhibition of JNK in vivo not only prevented the development of AAA but also caused regression of established AAA in two mouse models. Thus, JNK promotes abnormal extracellular matrix metabolism in the tissue of AAA and may represent a therapeutic target.
Asunto(s)
Antracenos/farmacología , Aneurisma de la Aorta Abdominal/tratamiento farmacológico , Aneurisma de la Aorta Abdominal/prevención & control , Matriz Extracelular/metabolismo , Regulación de la Expresión Génica/genética , Proteínas Quinasas JNK Activadas por Mitógenos/antagonistas & inhibidores , Adenoviridae , Animales , Aorta/química , Western Blotting , Células Cultivadas , Ensayo de Inmunoadsorción Enzimática , Proteínas de la Matriz Extracelular/biosíntesis , Vectores Genéticos , Humanos , Metaloproteinasa 9 de la Matriz/metabolismo , Ratones , Análisis por Micromatrices , Extractos de Tejidos/metabolismoRESUMEN
Background: The myocardial perfusion stress conducted by physicians and nurses requires two imaging sessions, one during stress and the other during rest. Echocardiography is sometimes performed before delayed imaging, and medical laboratory technicians (MLTs) have similar exposure in such cases. This study was designed to investigate the radiation exposure of physicians, nurses, radiologists, and MLTs involved in thallium-201 chloride (201TlCl) stress myocardial perfusion imaging and echocardiography, the details of which have not been reported to date. Methods: The dose rate at thallium-201 (201Tl) was examined using a cylindrical phantom. The exposure of physicians, nurses, and radiologists involved in the 201TlCl stress myocardial perfusion imaging was measured using pocket dosimeters, and that of the MLTs in charge of echocardiography were measured using glass-batch dosimeters. Results: The attenuation of radiation exposure from the phantom with distance was 95% at 50 cm from the center of the phantom, demonstrated that the attenuation of the exposure dose increased with distance. The exposure dose for physicians, nurses, and radiological technologists that participated in 201TlCl stress myocardial perfusion imaging was 0.20-0.23 µSv per exam, whereas it was 6.67-10.00 µSv per exam for MLTs. Conclusion: This study measured the dose received by physicians, nurses, and radiological technologists during stress MPI and the dose received by MLTs during echocardiography. The results provided advanced knowledge for the management of dose received by medical personnel.
RESUMEN
We developed a nitroxyl-catalyzed bromoesterification of alkenes with bromo reagents, which includes a six-membered ring bromolactonization of alkenyl carboxylic acids catalyzed by AZADO as the nitroxyl radical catalyst, and an intermolecular bromoesterification of alkenes with carboxylic acids using NMO as the N-oxide catalyst. We also accomplished a remote diastereoselective bromohydroxylation via an AZADO-catalyzed six-membered ring bromolactonization and a subsequent ring cleavage reaction with alkylamines to furnish ε-bromo-δ-hydroxy amides with high diastereoselectivity.
RESUMEN
Detail of control technique of bit-wise phase correlation in 160 (4 x 40) Gbit/s optical time division multiplexing (OTDM) signal using a phase-correlation monitor based on 1-bit delay asymmetric interferometers (AIFs) is described. The 1-bit delay AIF transforms a bit-by-bit optical phase discontinuity to an optical power variation, so that it enables to quantify the phase-jump between adjacent bits. By use of this unique technique, we experimentally demonstrated stable generation of bitwisely phase-controlled 160 Gbit/s periodical alternate-phase return-to-Zero (APRZ) signal in addition to other different modulation formats such as conventional RZ, carrier suppressed RZ (CS-RZ), pair-wise alternate-phase CSRZ (PAP-CSRZ) and pi/2-APRZ. And long term stability was observed with CS-RZ signal. Also, we show some experimental results of 120 km un-repeatered transmission using standard single mode fiber (SSMF) and then discuss the impact of bit-wise phase change on 160 Gbit/s OTDM transmission performance.
Asunto(s)
Interferometría/instrumentación , Interferometría/métodos , Óptica y Fotónica , Diseño de Equipo , Análisis de Fourier , Modelos Estadísticos , Modelos Teóricos , Distribución Normal , Temperatura , TransductoresRESUMEN
The flexibility and conformational variety of the butyl group in cations of ionic liquids (ILs) play an important role in dictating the macroscopic and microscopic properties of ILs. Here we calculate potential energy surfaces for the dihedral angles of the butyl group in four different types of cyclic cations, imidazolium, pyridinium, pyrrolidinium, and piperidinium, using the density functional theory method. The calculation results highlight the role of the butyl group in these cations by comparison of five-membered and six-membered rings, and of aromatic and alicyclic rings, in terms of stable conformations and rotational barriers. A striking result is that the butyl group rotation in pyrrolidinium induces pseudorotation of the ring whereas such a phenomenon does not occur in piperidinium. This difference is thought to be because of the relationship in rotational activation energy between the butyl group (10-40 kJ mol-1) and the ring (<6 kJ mol-1 for pyrrolidinium and 40-50 kJ mol-1 for piperidinium). The calculated stable conformers are compared with the ones observed in crystals recorded in the Cambridge Structural Database. Although conformers with lower calculated energy generally have higher chances to be experimentally observed, roughly independent of the cation structure, some calculated conformers deviate from this trend and show very low population. It is found that not only low energy but also high rotational activation energy (i.e., long lifetime) is required to observe conformers in crystalline states. In the last part of this article, to identify conformers in real systems, the applicability of the calculated Raman bands of cations with different butyl group conformations is discussed.
RESUMEN
By use of pulse NMR methods, the temperature dependences of the longitudinal and transverse relaxation times for (1)H and (19)F were measured for the three phases of 1-butyl-1-methylpiperidinium bis(fluorosulfonyl)amide ([Pip1,4][FSA]), i.e., liquid or supercooled liquid, Cryst-α, and Cryst-ß, to investigate the ion dynamics and phase behavior related to the dynamics. Since the cations and anions in the room-temperature ionic liquid have (1)H and (19)F nuclei, respectively, the dynamics of the [Pip1,4] cation and [FSA] anion can be independently observed and the relation between them can be evaluated. The relevant local motions of the ions are fluctuational motion around the chair form of the piperidinium ring, libration or rotation of the alkyl groups, and libration or rotation of the SO2F groups around the N-S axes. Each phase preferentially exhibits these motions. In the Cryst-ß phase, it is thought that O atoms in the SO2F groups form strong hydrogen bonds with the H atoms in the piperidinium ring. As a result, the motions of the SO2F groups and the piperidinium ring are restricted. In the liquid or supercooled liquid states and Cryst-α phase, the motion of the anion is more significant than that of the cation and the former works as a trigger for phase changes. Particularly, the motion of the SO2F groups in the Cryst-α phase becomes very significant with rising temperature and is directly related to the melting phase transition.
RESUMEN
The structural flexibility and conformational variety of the ions in room-temperature ionic liquids (RTILs) have significant effects on their physicochemical properties. To begin a systematic study of the thermodynamic properties of nonaromatic RTILs, 1-methyl-1-butylpiperidinium bis(fluorosulfonyl)amide ([Pip1,4][FSA]) was selected as the first sample. In addition to the rotational flexibility of the alkyl group, the [Pip1,4](+) cation has characteristic ring-flipping flexibility, which is very different from the behavior of the well-studied imidazolium-based cations. Calorimetry investigations using laboratory-made high-sensitivity calorimeters and Raman spectroscopy revealed that [Pip1,4][FSA] has two crystalline phases, Cryst-α and Cryst-ß, and that every phase change is linked to conformational changes of both the cation and anion. Each phase change is also governed by very slow dynamics. The phase changes from supercooled liquid to Cryst-α and from Cryst-α to Cryst-ß, which were observed only during heating, are not in fact phase transitions but structural relaxations. Notably, the temperatures of these structural relaxations exhibited heating rate dependences, from which the activation energy of the ring-flipping was estimated to be 38.8 kJ/mol. It is thought that this phenomenon is due to the associated conformational changes of the constituent ions in viscous surroundings.
RESUMEN
Akt is activated by growth factors to regulate various aspects of vascular smooth muscle cell function. Platelet-derived growth factor (PDGF) and insulin-like growth factor-1 activated Akt in vascular smooth muscle cells with a rapid reduction of total Akt protein that lasted for several hours. The downregulation of Akt required phosphatidylinositol 3-kinase activity, but not intrinsic Akt activity. The downregulation of Akt was abrogated by MG-132, a proteasome inhibitor, but not by inhibitors of calpain or cathepsins. Akt was found in ubiquitin immune complex after PDGF treatment. Proteasome-dependent degradation of Akt may provide a counter-regulatory mechanism against overactivation of Akt.
Asunto(s)
Cisteína Endopeptidasas/metabolismo , Sustancias de Crecimiento/farmacología , Complejos Multienzimáticos/metabolismo , Músculo Liso Vascular/citología , Proteínas Serina-Treonina Quinasas , Proteínas Proto-Oncogénicas/metabolismo , Animales , Regulación hacia Abajo/efectos de los fármacos , Inhibidores Enzimáticos/farmacología , Factor I del Crecimiento Similar a la Insulina/farmacología , Cinética , Masculino , Músculo Liso Vascular/metabolismo , Fosfatidilinositol 3-Quinasas/metabolismo , Factor de Crecimiento Derivado de Plaquetas/farmacología , Complejo de la Endopetidasa Proteasomal , Proteínas Proto-Oncogénicas c-akt , Ratas , Ratas WistarRESUMEN
Flow fields created by underexpanded sonic jets impinging on an inclined flat plate were studied experimentally using the pressure sensitive paint (PSP) measurement technique. The measurement system and some representative results are presented here. Two binders, thin-layer chromatography (TLC) plates and anodized aluminum (A-A) plates were tested with bathophen ruthenium chloride as a luminophore. The results show that both the binders can be used. TLC plates are preferable because their luminescent intensity is almost twice that of the A-A plates. Quantitative measurements require accurate temperature calibration. A preliminary effort to elucidate the flow structure by combining the PSP results with a computer simulation of the same flow field is presented. Although good agreement is obtained between the experimental and numerical results, future quantitative comparisons are necessary to yield a useful tool in the analysis of the jet-plate interaction flows.
Asunto(s)
Aluminio/química , Pintura , Calibración , Cromatografía en Capa Delgada/métodos , Cinética , Luz , Presión , Sonido , TermodinámicaRESUMEN
To clarify the precise mechanisms involved in the reduced coronary flow reserve in hypertension, we compared the effects of the angiotensin II type 1 (AT1) receptor antagonist FK-739 with those of the angiotensin-converting enzyme (ACE) inhibitor enalapril for 6 weeks on the smooth muscle (SM) cell phenotype in intramyocardial arteries from male Wistar-Kyoto rats (WKY) and spontaneously hypertensive rats (SHR). Compared with WKY, SHR showed a significant increase in left ventricular (LV) hypertrophy and fibrosis, blood pressure (BP), and vascular remodeling of the intramyocardial arteries, and a significant decrease in endothelial NO synthase and the contractile-type myosin heavy chain isoform SM2 of the intramyocardial arteries as well as calponin 1 and GATA-6. In the hearts of SHR, both drugs equivalently and significantly reduced BP, which was still significantly higher than that in the WKY groups, and also reduced LV hypertrophy and fibrosis, whereas endothelial NO synthase was significantly restored. Although both drugs showed little effect on the vascular remodeling of the intramyocardial arteries in the SHR hearts, FK-739, but not enalapril, significantly restored SM2 and GATA-6 in the SHR hearts to the same levels as those of the vehicle WKY group. The effects of the two drugs on these indices were not observed in the three WKY hearts. Thus, the AT1 receptor antagonist may modulate the SM cell phenotype toward the contractile-type more effectively than the ACE inhibitor before the morphological changes occur in the intramyocardial arteries of the SHR hearts.
Asunto(s)
Bloqueadores del Receptor Tipo 1 de Angiotensina II/farmacología , Vasos Coronarios/efectos de los fármacos , Hipertensión/tratamiento farmacológico , Imidazoles/farmacología , Músculo Liso Vascular/efectos de los fármacos , Piridinas/farmacología , Actinas/metabolismo , Inhibidores de la Enzima Convertidora de Angiotensina/farmacología , Animales , Peso Corporal , Proteínas de Unión al Calcio/metabolismo , Vasos Coronarios/fisiología , Proteínas de Unión al ADN/metabolismo , Enalapril/farmacología , Factor de Transcripción GATA6 , Frecuencia Cardíaca , Hipertensión/fisiopatología , Immunoblotting , Masculino , Proteínas de Microfilamentos , Músculo Liso Vascular/metabolismo , Cadenas Pesadas de Miosina/metabolismo , Óxido Nítrico Sintasa/metabolismo , Óxido Nítrico Sintasa de Tipo III , Ratas , Ratas Endogámicas SHR , Ratas Endogámicas WKY , Factores de Transcripción/metabolismo , CalponinasRESUMEN
We report a case of microscopic polyangitis presenting with acute pericarditis. A 75-year-old man, who had recurrent acute pericarditis, was referred by a cardiologist because of bilateral infiltrates in the chest radiograph, microhematuria and progressive renal failure. The test for MPO-ANCA was positive. Transbronchial and renal biopsies were compatible with microscopic polyangitis, showing alveolar hemorrhage and crescentic glomerulonephritis. After 3 days, intravenous methylpredonisolone was given, followed by oral prednisolone 40 mg/day, and the patient's radiographic infiltrates cleared and renal dysfunction improved. However, he died from opportunistic infection 109 days after the onset of treatment.
Asunto(s)
Pericarditis/etiología , Vasculitis/complicaciones , Enfermedad Aguda , Anciano , Anticuerpos Anticitoplasma de Neutrófilos/análisis , Glomerulonefritis/complicaciones , Glomerulonefritis/patología , Humanos , Masculino , Infecciones Oportunistas/etiología , Peroxidasa/inmunología , Recurrencia , Vasculitis/patologíaRESUMEN
The dielectric barrier discharge (DBD) plasma actuator that controls flow separation is one of the promising technologies to realize energy savings and noise reduction of fluid dynamic systems. However, the mechanism for controlling flow separation is not clearly defined, and this lack of knowledge prevents practical use of this technology. Therefore, large-scale computations for the study of the DBD plasma actuator have been conducted using the Japanese Petaflops supercomputer 'K' for three different Reynolds numbers. Numbers of new findings on the control of flow separation by the DBD plasma actuator have been obtained from the simulations, and some of them are presented in this study. Knowledge of suitable device parameters is also obtained. The DBD plasma actuator is clearly shown to be very effective for controlling flow separation at a Reynolds number of around 10(5), and several times larger lift-to-drag ratio can be achieved at higher angles of attack after stall. For higher Reynolds numbers, separated flow is partially controlled. Flow analysis shows key features towards better control. DBD plasma actuators are a promising technology, which could reduce fuel consumption and contribute to a green environment by achieving high aerodynamic performance. The knowledge described above can be obtained only with high-end computers such as the supercomputer 'K'.
RESUMEN
We studied the crystallization process of 1-butyl-3-methylimidazolium bromide ([C(4)mim]Br) using measurements of supersensitive scanning calorimetry, free induction decay (FID) signals of (1)H NMR, and direct observation. These three methods provided consistent, complementary results, which showed extremely slow dynamics at crystallization. This sample does not crystallize during the cooling process, loses mobility, and changes to a coagulated state, which is not the thermodynamic glass state. The FID signals and direct observation in the heating process indicate that the coagulated sample liquefies just before crystallization. The crystallization of [C(4)mim]Br does not occur from specialized locations such as the surface or wall of the sample tube but randomly in the liquid. The calorimetric measurements show that it takes 150 min for approximately 3 mg of this sample to crystallize perfectly. Conformational changes of the butyl group continue for approximately 330 min after crystallization. Such slow dynamics are thought to be due to the cooperative linking of crystallization and complex conformational changes in dense fields with high viscosity.