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Raman spectroscopic measurements were carried out for the anhydrous LnCl3·20ROH·XLiCl solutions (Ln3+ = La3+− Lu3+, X = 0–3; ROH = MeOH, EtOH, n-PrOH) in the liquid state. The salt concentration (X) dependence of the wavenumber for the Ln–Cl stretching Raman band (νLn–Cl) is examined in conjunction with the formation of chloro-rare-earth complexes. We have obtained very intriguing results including the fact that the chloro complexations of the middle rare-earth ions (e.g. gadolinium, holmium ions, etc.) in the MeOH and EtOH solutions show peculiar behavior with regard to the salt concentration dependence: the νLn–Cl wavenumber increases with the increasing chloride concentration. However, the νLn–Cl wavenumbers of the light and heavy rare-earth (e.g. lanthanum, lutetium, etc.) salt solutions show normal behavior; i.e. νLn–Cl decreases with the increasing chloride concentration. On the other hand, in the n-PrOH solutions, the νLn–Cl frequency in the solutions of all the rare-earth elements exhibits a normal behavior. We now present a possible mechanism for this anomalous concentration dependence of coordination of Cl− ions to Ln3+ ions in anhydrous LnCl3 alcohol solutions. Copyright © 2007 John Wiley & Sons, Ltd.

Department of Materials Science and Engineering, National Defense Academy, Yokosuka 239-8686, Japan Department of Applied Chemistry, National Defense Academy, Yokosuka 239-8686, Japan Department of Applied Chemistry, Ritsumeikan University, 1-1-1 Nojihigashi, Kusatsu, Shiga 525-8577, Japan Research Center for Neutron Science and Technology, Comprehensive Research Organization for Science and Society (CROSS), IQBRC Bldg, 162-1 Shirakata, Tokai, Ibaraki 319-1106, Japan Japan Atomic Energy Agency, 2-4 Shirane Shirakata, Tokai, Ibaraki 319-1195, Japan

Food contains various compounds that have an impact on our daily lives. Many technologies have been established to analyze these molecules of interest in foods. However, the analysis of the spatial distribution of these compounds in foods using conventional technology, such as high-performance liquid chromatography-mass spectrometry or gas chromatography-mass spectrometry is difficult. Matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI-MSI) is considered an ideal complementary approach. MALDI-MSI is a two-dimensional MALDI-MS technology that can detect compounds in a tissue section without extraction, purification, separation, or labeling. MALDI-MSI can be used to visualize the spatial distribution of chemical compounds or biomolecules in foods. Although the methodology of MALDI-MSI in food science is not yet fully established, the versatility of MALDI-MSI is expected to open a new frontier in food science. Herein, we describe the principles and applications of MALDI-MSI in food science and related fields.

The varying states of water confined in the nano-domain structures of typical room temperature ionic liquids (ILs) were investigated by 1H NMR and by measurements of self-diffusion coefficients while systematically varying the IL cations and anions. The NMR peaks for water in BF4-based ILs were clearly split, indicating the presence of two discrete states of confined water (H2O and HOD). Proton and/or deuterium exchange rate among the water molecules was very slowly in the water-pocket. Notably, no significant changes were observed in the chemical shifts of the ILs. Self-diffusion coefficient results showed that water molecules exhibit a similar degree of mobility, although their diffusion rate is one order of magnitude faster than that of the IL cations and anions. These findings provide information on a completely new type of confinement, that of liquid water in soft matter.

A 43-year-old healthy male traveled to Bali (Indonesia) for 7 days. Ten days after returning home, he experienced high fever, fatigue, and severe headache and was admitted to our hospital 5 days after the onset of symptoms. He had no history indicating the presence of flea bites. On admission, a maculopapular rash on the trunk was recognized, while pulmonary auscultation sounds were normal. A chest X-ray and computerized tomography scan showed a nodular lesion …

To understand the stability of the liquid phase of ionic liquids under high pressure, we investigated the phase behavior of a series of 1-alkyl-3-methylimidazolium tetrafluoroborate ([Cnmim][BF4]) homologues with different alkyl chain lengths for 2 ≤ n ≤ 8 up to ∼7 GPa at room temperature. The ionic liquids exhibited complicated phase behavior, which was likely due to the conformational flexibility in the alkyl chain. The present results reveal that [Cnmim][BF4] falls into superpressed state around 2-3 GPa range upon compression with an implication of multiple phase or structural transitions to ∼7 GPa. Remarkably, a characteristic nanostructural organization in ionic liquids largely diminishes at the superpressed state. The behaviors of imidazolium-based ionic liquids can be classified into, at least, three patterns: (1) pressure-induced crystallization, (2) superpressurization upon compression, and (3) decompression-induced crystallization from the superpressurized glass. Interestingly, the high-pressure phase behavior was relevant to the glass transition behavior at low temperatures and ambient pressure. As n increases, the glass transition pressure (pg) decreases (from 2.8 GPa to ∼2 GPa), and the glass transition temperature increases. The results indicate that the p-T range of the liquid phase is regulated by the alkyl chain length of [Cnmim][BF4] homologues.

To investigate the interaction site between amyloid-like protein aggregates and thiocyanate (SCN(-)) ion, we studied the relationship between protein aggregation (cytochrome c, myoglobin, lysozyme, ribonuclease A, and β-lactoglobulin) and SCN(-) ion in aqueous 1-butyl-3-methylimidazolium thiocyanate ([bmim][SCN]) solutions using optical spectroscopy. The addition of [bmim][SCN] (10 mol % IL) to a protein solution induced protein aggregation owing to the intermolecular β-sheet structures except in the case of cytochrome c. Analysis of the content of 20 amino acid residues for each protein revealed that the degree of intermolecular β-sheet structures (β%) and midpoint concentration from the unfolding to aggregation state ([IL]1/2(U →βA)) is correlated primarily with the content of Lys residue in proteins (correlation coefficient (R(2)) = 0.97). The attractive interaction between the SCN(-) ions and NH3(+) groups of the side chain terminal of Lys residue inhibits protein aggregation owing to the intermolecular β-sheet structure. This finding might be related to the mechanism for the solubilization of amyloid aggregates by strong denaturants containing SCN(-) ions such as guanidine thiocyanate.

Inorganic ions are usually classified as structure makers or structure breakers according to the viscosity B-coefficients of their aqueous solutions at ordinary temperature. Structure-making ions enhance the hydrogen bond strength while structure-breaking ones weaken the hydrogen bonds in aqueous solution. We here show that even structure-making ions (assigned by their viscosity B-coefficients at ordinary temperature) become a structure breaker in the sense that they weaken the hydrogen bonds in aqueous solution at low temperatures when we compare the strength of hydrogen bonds with that for glassy water.

Vibrational spectra reveal that ice VII′ transforms to low-density amorphous ice (LDA) at low temperature on release of pressure to ambient pressure and low temperature. The measurements were obtained using in situ Raman spectroscopy of samples of ice VII′ as a function of pressure at 135 K. The observation of this direct decompression-induced VII′-LDA transition complements the previously observed pressure-induced reversible transition between LDA and high-density amorphous ice (HDA) at 120–140 K and the temperature-induced amorphization of metastable ice VII and ice VIII at 0.1 MPa.

The thermal decomposition of the lanthanoid complexes of trifluoroacetic acid (Ln(CF 3 COO) 3 ·3H 2 O; Ln=La-Lu) was studied by TG and DTA methods. The Ln(CF 3 COO) 3 ·3H 2 O complexes decompose in several stages; first dehydrate to the anhydrous state, then followed by decomposition of the anhydrous salt to a stable product of LnF 3 . From the endothermic and exothermic data of Ln(CF 3 COO) 3 ·3H 2 O complexes, pyrolysis behavior of the complexes is classified into three groups: (1) La-Pr salts; (2) Nd-Gd salts; (3) Tb-Lu salts. It has been shown that all the final decomposition products were found to result in the formation of LnF 3 .

The purpose of this study was to determine whether aged myocardium exhibits decreased responsiveness to adenosine A1 and A(2a) receptor activation. Studies were conducted in adult (4-6 months) and aged (24-26 months) Fischer 344 x Brown Norway hybrid (F344 x BN) rats. Effects of the adenosine A1/A(2a) agonist AMP579 were measured in isolated hearts and in rats submitted to in vivo regional myocardial ischemia. Aged isolated hearts exhibited lower spontaneous heart rates and higher coronary resistance, as well as normal A1- and A(2a)-mediated responses. There was no difference in control infarct size between adult and aged rats; however, AMP579 treatment resulted in a 50% greater infarct size reduction in aged rats (18 +/- 4% of risk area) compared to adult rats (37 +/- 3%). These findings suggest that adenosine A1 and A(2a) receptor-mediated effects are not diminished in normal aged myocardium, and that aged hearts exhibit increased adenosine agonist-induced infarct reduction.

Raman spectroscopic measurements were carried out for the anhydrous LnCl3·20MeOH·XLiCl solutions (Ln3+=Pr3+, Gd3+ and Ho3+, X=0–4) in both liquid and glassy states. Salt concentration dependence of the frequency for the Ln–Cl stretching Raman band (νLn–Cl) is examined in conjunction with the formation of chloro-rare earth complexes. We have obtained the very interesting results that the chloro-complexations of gadolinium and holmium ions in these solutions show very peculiar behavior as to the salt concentration dependence at room temperature: the νLn–Cl frequency increases with increasing concentration. On the other hand, the νLn–Cl frequency of the PrCl3·20MeOH·XLiCl solution shows normal behavior as to the salt concentration dependence: νLn–Cl decreases with increasing chloride concentration. We present a possible mechanism for this anomalous concentration dependence of coordination of Cl− ions to Ln3+ ions in anhydrous methanol LnCl3 solutions.

The protective effects of adenosine receptor acute preconditioning (PC) are well known; however, the signaling mechanism mediating this effect has not been determined in in vivo models. The purpose of this study was to determine the role of the extracellular signal-regulated kinase (ERK) pathway in mediating adenosine PC in in vivo rat myocardium. Open-chest rats were submitted to 25 min of coronary artery occlusion and 2 h of reperfusion. ERK activation was assessed by measuring total and dually phosphorylated p44/42 ERK isoforms in nuclear and/or myofilament, mitochondrial, cytosolic, and membrane fractions. Adenosine receptor PC with the A1/A2a agonist 1 S-[1a,2b,3b,4a( S*)]-4-[7-[[2-(3-chloro-2-thienyl)-1-methylpropyl]amino]-3H-imidazo[4,5-b]pyridyl-3-yl]cyclopentane carboxamide (AMP-579) reduced infarct size from 49 ± 3% to 29 ± 3%, an effect that was blocked by the mitogen-activated protein kinase-ERK inhibitor U-0126. ERK isoforms were present in all fractions, with the greatest expression in the cytosolic fraction and the least in the mitochondrial fraction. AMP-579 treatment increased preischemic p44/42 ERK phosphorylation in all fractions 2.7- to 6.9-fold. Reperfusion increased ERK isoform activation in all fractions, but there were no differences between control and AMP-579 hearts. Preischemic increases in phospo-p44/p42 ERK with AMP-579 were blunted by U-0126, although only in mitochondrial and membrane compartments. The PC effects of AMP-579 on infarct size and ERK were blunted by both the A1 antagonist 8-cyclopentyl-1,3-dipropylxanthine and, surprisingly, the A2a antagonist ZM-241385. These results indicate that the unique adenosine receptor agonist AMP-579 exerts its beneficial effects in vivo via both A1 and A2a receptor modulation of subcellular ERK isoform signaling.

Although acute adenosine preconditioning (PC) is well established, the signaling pathways mediating this cardioprotection remain unclear. Because adenosine receptor agonists activate p38 MAPK and this kinase has been implicated in ischemic and pharmacological PC, the purpose of this study was to determine the role of p38 MAPK in acute adenosine receptor PC. The role of p38 MAPK activation in discrete subcellular compartments during ischemia-reperfusion was also determined. The following groups were used in an in vivo rat ischemia-reperfusion model: 1) control (10% DMSO iv), 2) the A1/A2a adenosine receptor AMP-579 (50 μg/kg iv), 3) AMP-579 + the A1 receptor antagonist 8-cyclopentyl-1,3-dipropylxanthine (DPCPX, 100 μg/kg iv), 4) AMP-579 + the p38 MAPK inhibitor SB-203580 (1 mg/kg iv), and 5) SB-203580 alone. p38 MAPK activation was measured by Western blot analysis in cytosolic, mitochondrial, membrane, and nuclear/myofilament fractions obtained from hearts at preischemic, ischemic, and reperfusion time points. A significant reduction in infarct size was observed with AMP-579 PC, an effect blocked by DPCPX or SB-203580 pretreatment. AMP-579 treatment was associated with a significant increase in p38 MAPK activation in the nuclear/myofilament fraction before ischemia, whereas no activation of this kinase occurred during ischemia or reperfusion. In contrast, p38 MAPK was activated in the mitochondrial fraction by ischemia and in the cytosolic, mitochondrial, and membrane fractions by reperfusion in the control group. SB-203580 blocked the AMP-579-induced increase in phosphorylation of the downstream p38 substrate activating transcription factor-2. These results suggest a role for p38 MAPK activation in discrete subcellular compartments in acute adenosine A1 receptor PC.

The changes in in situ Raman spectra of ice in aqueous KCl solution have been measured as a function of pressure at liquid nitrogen temperature (77 K). The ice that is formed abruptly transforms to a crystalline phase at ∼800 MPa. It has a spectrum close to that of ice VII′ to which high density amorphous (hda) ice transforms at about 4 GPa. This behavior contrasts with that of the ice in aqueous LiCl solution, which transforms to an amorphous phase at ∼500 MPa, as in the case of pressure-induced amorphization of ice Ih to hda.

The intermediary metabolite pyruvate has been shown to exert significant beneficial effects in in vitro models of myocardial oxidative stress and ischemia-reperfusion injury. However, there have been few reports of the ability of pyruvate to attenuate myocardial stunning or reduce infarct size in vivo. This study tested whether supraphysiological levels of pyruvate protect against reversible and irreversible in vivo myocardial ischemia-reperfusion injury. Anesthetized, open-chest pigs ( n = 7/group) underwent 15 min of left anterior descending coronary artery (LAD) occlusion and 3 h of reperfusion to induce stunning. Load-insensitive contractility measurements of regional preload recruitable stroke work (PRSW) and PRSW area (PRSWA) were generated. Vehicle or pyruvate (100 mg/kg iv bolus + 10 mg·kg–1·min–1 intra-atrial infusion) was administered during ischemia and for the first hour of reperfusion. In infarct studies, pigs ( n = 6/group) underwent 1 h of LAD ischemia and 3 h of reperfusion. Group I pigs received vehicle or pyruvate for 30 min before and throughout ischemia. In group II, the infusion was extended through 1 h of reperfusion. In the stunning protocol, pyruvate significantly improved the recovery of PRSWA at 1 h (50 ± 4% vs. 23 ± 3% in controls) and 3 h (69 ± 5% vs. 39 ± 3% in controls) reperfusion. Control pigs exhibited infarct sizes of 66 ± 1% of the area at risk. The pyruvate I protocol was associated with an infarct size of 49 ± 3% ( P < 0.05), whereas the pyruvate II protocol was associated with an infarct size of 30 ± 2% ( P < 0.05 vs. control and pyruvate I). These findings suggest that pyruvate attenuates stunning and decreases myocardial infarction in vivo in part by reduction of reperfusion injury. Metabolic interventions such as pyruvate should be considered when designing the optimal therapeutic strategies for limiting myocardial ischemia-reperfusion injury.

Recent Raman studies on the pressure-induce amorphization of pure ice and ice in aqueous LiCl solution are reviewed. We investigated the change of in situ Raman spectra of ice Ih as functions of pressure and temperature. In this paper, I show the spectral evidence for the formation of strong hydrogen bonds in high-density amorphous ice (HDA) at high pressures and the close similarity in spectral features of relaxed HDA to that of supercooled water at high pressures and low temperatures. It is found that the ice phase in LiCl·12H2O also transforms to an amorphous phase at ∼520 MPa, as in the case of pressure-induced amorphization of pure ice Ih to the HDA. The spectral changes with temperature show the possible existence of a transition from the relaxed amorphous phase to the supercooled liquid at high pressures and low temperatures.

We investigated the effect of six ionic liquids (ILs), and dimethylsulfoxide (DMSO) as a typical molecular liquid (organic solvent), on the hatching of Artemia salina cysts. The effect of an IL on the hatching of Artemia salina strongly depends on the specific combination of cation and anion. Of the ILs tested, choline acetate and choline chloride had a significantly lower toxicity. The level of inhabitation followed the order [chl][dhp] > [bmim][NO3] > [MAN][NO3] > [bmim][Ac] > DMSO > [chl][Ac] ≥ [chl][Cl].

Room-temperature ionic liquid (RTIL)/water mixtures show acidic properties at around 90 mol % H2O. The RTIL is N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetrafluoroborate. The pH of the mixtu...

Here, we have measured the glass transition temperature ( T g ) of the ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate–H 2 O mixed solutions as a function of H 2 O concentration ( x mol% H 2 O). The glass-forming composition region was also determined. Contrary to the results of the quaternary ammonium type of ionic liquid, N , N -diethyl- N -methyl- N -(2-methoxyethyl) ammonium tetrafluoroborate–H 2 O mixed solutions, we did not observed the multiple glass transition behaviour. We also measured the glassy Raman spectra of the solutions at T = 77 K. We find that the “nearly free” hydrogen bonded Raman band of water molecules in the aqueous [bmim][BF 4 ] solution exists up to around x = 60 mol% H 2 O, even at T = 77 K.

Biliary tract infection (BTI) including acalculous cholecystitis is a rare but life-threatening complication after cardiovascular surgery. The objective of our study was to describe epidemiology, clinical characteristics, and risk factors of BTI after cardiovascular surgery. From January 2007 to December 2011, 586 consecutive patients(age68±11;397 men,189 women)were enrolled in this study. BTI was diagnosed according to Centers for Disease Control and Prevention (CDC) surveillance criteria for healthcare associated infection. Data collection included preoperative, intraoperative, and post-operative variables. The overall incidence of BTI was 3.9%. The mortality in BTI group was significantly higher than that in non-BTI group (17.1% vs 5.5%, p0.05). Multi-logistic analysis revealed that operation of the thoracic aorta( p0.05) and massive transfusion(p0.01) were independent risk factors for BTI after cardiovascular surgery.

A 65-year-old female was admitted to our hospital with mitral regurgitation (MR). Transthoracic echocardiography showed severe mitral valve prolapse and subaortic septal hypertrophy with no pressure gradient. Mitral valve plasty consisted of artificial chorda implantation and ring annuloplasty was performed. During intensive care unit( ICU) stay after operation, systolic murmur and low cardiac output syndrome were noted and echocardiography revealed left ventricular outflow tract obstruction (LVOTO) without systolic anterior motion and MR. Cessation of catecholamine, volume administration, beta-blocker and negative inotropic drug like cibenzoline rapidly reduced LVOTO and the hemodynamic condition was improved. Even in a case of subaortic septal hypertrophy with no pressure gradient, emergence of LVOTO should be considered when new systolic murmur and low cardiac output syndrome appeared.

Procalcitonin( PCT) is a new diagnostic marker of severe bacterial infection and sepsis.To evaluate the usefulness of PCT in patients with suspicion of bacterial infection after cardiovascular surgery.From January 2012 to December 2012, 150 consecutive patients after cardiovascular surgery were studied retrospectively. Postoperative infection was diagnosed under Centers for Disease Control and Prevention (CDC) guideline for healthcare associated infection, and biomarker levels and microbiological specimen were evaluated.Only blood stream infection group revealed higher PCT levels( median 5.0 ng/ml) than non blood stream infection group( median 0.1 ng/ml)[p0.01].PCT is the best biomarker available for the clinical diagnosis of blood stream infection after cardiovascular surgery.

A 46-year-old woman was admitted to our hospital because of congestive heart failure and atrial fibrillation. She had undergone atrial septal defect repair at the age of 7 years. Computed tomography( CT)scan revealed right upper pulmonary vein returned to superior vena cave and the left upper pulmonary vein returned to the innominate vein. Cardiac catheterization showed Qp/Qs of 2.6. Pulmonary venous drainage repair and right-sided maze procedure was planned. The right upper pulmonary vein was led to the left atrium using the modified Warden Procedure. The left upper pulmonary vein was divided and anastomosed to the left atrial appendage. Concomitantly right-sided maze procedure was performed. Postoperative course was uneventful and CT scan revealed no stenosis at anastomotic sites. Sinus rhythm was retained and she was discharged on postoperative day 30.

Aortic valve replacement( AVR) is a definitive treatment in patients with severely calcified aortic stenosis (AS). However, elderly patients with multiple comorbidities are considered to be unsuitable for AVR. Percutaneous transcatheter aortic valvuloplasty( PTAV) has been performed as a palliative option to relieve symptoms or to be a bridge use toward definitive therapy. This study aimed to examine the effectiveness and clinical outcome of surgical AVR subsequent to PTAV.Since 2010, 5 symptomatic patients have undergone AVR after PTAV in our institution. PTAV was performed as a bridge to definitive AVR in 2 patients. Other 2 patients developed symptomatic aortic valve restenosis during a follow-up, and required AVR. In the last patient,AVR was carried out after successful noncardiac surgery subsequent to PTAV.AVR improved cardiac hemodynamics in all patients. There was no operative death. Postoperative course was uneventful and all patients were discharged on foot except for 1 patient in whom metastatic liver tumor from advanced gastric cancer was noted.AVR might be performed safely even in high-risk patients with the history of PTAV. PTAV is useful as a palliation or a bridge to definitive therapy for treatment of patients with severe AS unsuitable for surgery.

We have investigated the change of in situ Raman spectra of high-density amorphous ice (HDA) as functions of pressure and temperature. Here we show the spectral evidence for the formation of strong hydrogen bonds in HDA at high pressures and the close similarity in spectral features of relaxed HDA to that of supercooled water at high pressures and low temperatures. It can be also suggested that pressure-induced amorphization is a collapsed transition and HDA is not a glassy state of liquid water.

Homogeneous nucleation temperatures (TH’s) of aqueous alkali chloride and acetate solutions were measured as a function of salt concentration. There is a linear relation between TH and 1/r+ (r+: ionic radius of alkali ion) for aqueous alkali chloride solutions. In the supercooling of aqueous alkali acetate solutions, the ionization constant also plays an important role in their supercooling behavior. The TH results were discussed in relation to nucleation theory.

An attempt has been made to interpret the anomalous properties of supercooled water in a unified way by using Stillinger's postulate that the formation of bulky clathrate-like local structures is the main cause of the anomalous thermodynamic and transport properties exhibited by liquid water at low temperatures. Comparison of the thermodynamic properties of liquid water, tellurium, and sulfur suggests the existence of a λ-like Cp transition in supercooled water below TH (but above TK). It is inferred that the diverging trends of various anomalous properties with lowering temperature are preserved up to high pressures (

Raman spectroscopic measurements were carried out for anhydrous alcoholic rare earth chloride solutions (LnCl3 · 20ROH; ROH = MeOH, EtOH, and n-PrOH) in the glassy state at liquid nitrogen temperature. Series behavior of the Ln–Cl stretching Raman band is examined in conjunction with the formation of chloro complexes. The results are summarized as follows: (1) Comparing the results with those in the liquid state at room temperature, more Cl- ions tend to coordinate to heavy rare earth ions in the three alcohol solutions upon going from a liquid to a glassy state, while the coordination number of the Cl- ions of the light rare earth ions remains almost unchanged on vitrification. (2) In the former half region of the rare earth series, the coordination number of the Cl- ions of the rare earth ions in the methanol LnCl3 solution is apparently the same as that in the ethanol LnCl3 solution. (3) In the latter half region, the higher chloro complexes, such as [LnClx+1(ROH)y-2](z-1) (x + y = 8; x = 1, z = 2 or x = 2, z = 1) are more abundant in the methanol LnCl3 solution than in the ethanol and n-propanol LnCl3 solutions.

For a room temperature ionic liquid, N,N -diethyl- N -methyl- N -(2-methoxyethyl) ammonium tetrafluoroborate, [DEME][BF 4 ]–H 2 O system, we have observed two glass transitions in the region of 16.5–30.0 mol% H 2 O. The nano-phase separations in [DEME][BF 4 ] enhanced by a small amount of H 2 O may be the cause for this.

Experimental results are reported on the application of a new type of activated carbon having very high specific surface area, 3000 m2/g, formed in granular or supported on a honeycomb board, to the recovery of chlorinated hydrocarbon solvent vapors. The activated carbon showed an excellent adsorption capacity and the type of its adsorption was found to be volume-filling. Intraparticle diffusion was found to be the same as that for conventional activated carbons, i.e. the intraparticle diffusion proceeds mostly by surface migration.

Sake is made from fermented rice and has been drunk in Japan for more than 1000 years. The rice must be polished prior to fermentation to obtain high-quality sake. It is traditionally recognized that the quality of sake is improved as the rice polishing ratio (percentage removed in the polishing process) increases. However, the underlying chemistry of the rice polishing process is incompletely understood. Herein, we analyzed the distribution of lysophosphatidylcholine (LPC) molecular species with unsaturated fatty acids in rice, as their presence is thought to exert a negative effect on the flavor of sake.The distribution of LPC molecular species in rice was visualized via matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI-MSI).LPC (16:0) is ubiquitously present in the endosperm of rice while LPC (18:0) is localized in the core of the endosperm. In contrast, LPC (18:2) and LPC (18:1) are present in the outer region of the endosperm.The enhancement of the quality of sake as the polishing ratio of the rice increases might be explained in terms of the distribution of LPC with unsaturated fatty acids in the rice.

We have found that the room-temperature ionic liquid (RTIL) reveals outstanding pressure-induced phase changes from a liquid state to a crystal polymorph and finally to a glass form upon compression by up to 8 GPa. The RTIL is 1-butyl-3-methylimidazolium hexafluorophosphate, [C4mim][PF6], which offers the opportunity to investigate a variety of fluctuations in one system and can be completely recovered without dissociation or polymerization, even after decompression. Similar to charge frustration, spin ice-like frustration, and geometric frustration in high potential spintronics/multiferroic materials, the RTIL frustrations are classified into charge (scalar), orientation (vector), and coordination number (topology). Degrees of freedom at each state of [C4mim][PF6] are described by charge balancing, molecular orientational order/disorder, molecular conformations of the C4mim(+) cation, and the coordination number. Here, we show a novel "conformation glass" induced by high pressure.

Cardiac resynchronization therapy (CRT)has been accepted broadly as an alternative to medical treatment in managing severe heart failure patients. Despite advance in CRT, the presence of a significant valvular heart disease was currently specific exclusion criteria and a response to this therapy remains unclear. The purpose of this study was to determine the effectiveness of CRT in heart failure patients undergoing valvular operation simultaneously.Between July 2010 and May 2012, 8 heart failure patients who underwent CRT in conjunction with valvular surgery were experienced. Right and left ventricular and atrial epicardial leads were implanted after completion of valvular procedures. In patients with chronic atrial fibrillation(Af),maze procedure was performed in order to eliminate Af. To evaluate the improvement of ventricular mechanical dyssynchrony, the echocardiographic assessment was repeated on admission and 1 month after the CRT implantation.There was no operative death. One patient of ischemic cardiomyopathy died of sustained ventricular tachycardia 2 months after the operation. Postoperative course of severe heart failure patients was uneventful and all patients except 1 discharged on foot with improved New York Heart Association (NYHA) class. Echocardiographic parameters of dyssynchrony did not reach to statistical significance, but several parameters, left ventricular( LV)-pre-ejectionperiod( PEP) and interventricular mechanical delay (IVMD) showing time delay of cardiac contraction, tended to be improve, suggesting contribution to satisfactory postoperative course.The acceptable outcome was demonstrated with our concept to recover the intraventricular and atrioventricular synchrony. Although it might be difficult to establish the patient selection criteria for concomitant CRT and valvular surgery, our strategy is considered to be a feasible procedure to improve the morbidity and mortality in patients with severe heart failure due to valvular disease.

Structural modification of bovine milk β-lactoglobulin (β-LG) in aqueous 1-butyl-3-methylimidazolium nitrate ([bmim][NO3]) and ethylammonium nitrate ([EAN][NO3]) solutions has been investigated by Fourier transform infrared and circular dichroism spectroscopy. Remarkably, high ionic liquid (IL) concentrations (15 mol %IL) caused formation of a non-native α-helical structure of β-LG and disruption of its tertiary structure. Furthermore, while [bmim][NO3] promoted protein aggregation, [EAN][NO3] inhibited it probably owing to differences in the unique solution structure (nanoheterogeneity) of the ILs by the different cationic species. The IL-induced α-helical formation of β-LG shows a behavior similar to the alcohol denaturation, but a disordered structure-rich state was observed in the β-α transition process by adding IL, in contrast to the case of an aqueous alcohol solution of protein. We propose that the molten salt-like property of aqueous IL solutions strongly support α-helical formation of proteins.

We described a case of a neonate of 13 trisomy with hypoplastic aortic arch and multiple ventricular septal defect (VSD). The patient presented symptoms of congestive heart failure due to pulmonary high flow. Because of ductal patency without prostaglandin infusion, bilateral pulmonary artery banding was performed for regulation of pulmonary high flow. Surgical intervention improved the clinical symptoms of the patient and permitted the patient to be discharged. We concluded that palliative surgery for the patient contributes to improve the quality of life both the patient and the family. This is the 1st report of bilateral pulmonary artery banding for a patient with 13 trisomy.

A 40-year-old man had undergone total arch replacement using the elephant trunk technique. Three years after the initial operation, stenosis of the elephant trunk due to enlargement of a false lumen was detected. Replacement of the descending thoracic aorta was performed. A narrow segment of the elephant trunk was compressed by old hematoma and lapped around the connective tissue. A new graft was anastomosed to the narrow segment of the elephant trunk in an end-to-side fashion. Postoperative course was uneventful, and he was discharged 18 days after the operation.

We experienced a rare case of congenital pericardial defect incidentally found during off-pump coronary artery bypass grafting (CABG)[OPCAB]. We performed off-pump for a 61-year-old man. He was asymptomatic but was noted to have an abnormal chest X-ray showing the enlarged heart. He had right ventricule lifting upward and apex shifting far to left side. Partial absence of the left pericardium was found. The surgery was technically more demanding than usual, because of heart rotation and inadequate pericardial stitch.

We explore the phase behavior of room-temperature ionic liquids (RTILs) compressed under high pressure to determine whether they crystallize or hold a liquid state. RTILs have attractive supercooling properties compared with ordinary molecular liquids, which easily become a glassy state without crystallizing at ambient pressure. Thus, phase behavior under extreme stress, such as pressure, might yield interesting results. Here, we show that N,N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium tetrafluoroborate ([DEME][BF4]) could be crystallized upon compression, but it usually formed a superpressed liquid. Alternatively, unusual crystallization could be induced by releasing the pressure on the superpressed liquid. Notably, crystal polymorphism was observed in the decompression process. These facts along with visual observations indicate the possibility of [DEME][BF4] serving as a superpressurized glass. Our findings may facilitate the development of a new range of applications for RTILs that have undergone high-pressure recrystallization.

A 46-year-old woman with homozygous familial hypercholesterolemia was referred due to aortic regurgitation. The patient was introduced selective low density lipoprotein cholesterol(LDL)apheresis 20 years ago. Echocardiogram revealed severe aortic regurgitation, and computed tomography revealed thoracoabdominal aortic aneurysm. We considered 2 staged operations were necessitated. Firstly, aortic valve replacement was performed. Emergent coronary artery bypass grafting was also done because intraoperative myocardial ischemia was strongly suspected from left ventricular hypokinesis. One year later, replacement of thoracoabdominal aorta was performed. Post-operative course was uneventful and the patient was discharged at post-operative day 21. The patients with homozygous familial hypercholesterolemia must be strictly followed up because systemic atherosclerosis frequently exacerbates despite selective LDL apheresis.

Port-access minimally invasive cardiac surgery (MICS) is complicated by limited skin incision and surgical field. In order to optimize the set-up and port placement in this surgery, we have employed image overlay technique prior to operation consisted of three-dimentional computed tomography (3DCT)image projection on the patient surface. With the aid of this technique, we successfully performed port-access MICS in 12 patients and mitral valve replacement in 1 patient with severe mediastinal displacement after previous pneumonectomy. Image overlay projection could allow surgeons to view underlying anatomical structures virtually and obtain a good operative field. Our proposed technique would be expected to make port-access MICS easier and probably safer in this particular circumstance.

A survey of HIV-1 strains circulating in the Tokyo-Kanagawa metropolitan area of Japan during 2004 to 2011 ( n = 477) identified six Japanese males (patients 1 to 6), who harbored viruses with genome segments derived from a distinct CRF01_AE variant uniquely found among men who have sex with men (MSM) in China (designated CN.MSM.01-1). These six HIV infections were diagnosed in 2010 and 2011 among MSM (3 of 75) and men with unknown risk factors (3 of 63) and differed from the vast majority of HIV infections among MSM in Japan, which are overwhelmingly characterized by subtype B (239 of 246 [97.2%]). Approximately one-third (91 of 239 [38.1%]) of subtype B strains from MSM in Japan belong to a large monophyletic cluster (designated JP.MSM.B-1). In addition, we identified a smaller subtype B cluster ( n = 8) (designated JP.MSM.B-2) that also contains strains from two Chinese MSM living in Japan. Interestingly, patients 5 and 6 were found to be coinfected with CRF01_AE (CN.MSM.01-1) and subtype B (JP.MSM.B-2 or JP.MSM.B-1) variants that are unique to the HIV-1 epidemics among MSM in China and Japan, respectively. Our study demonstrates for the first time the effect of the expanding HIV epidemic among MSM in China on transmission in neighboring countries and shows the ongoing mixing of CRF01_AE and subtype B lineages unique to HIV-1 that cocirculate in MSM populations in East Asia. This finding highlights the importance of strengthening epidemiological surveillance in the region and the need for effective measures to limit transmission among MSM in East Asia.

The viscosity of aqueous ammonium bromide solutions is measured at 0.1-1.0 mol kg-1, 278.2-323.2 K, and 0.1-375 MPa, using a high-pressure rolling-ball viscometer. The activation energy (Ev) for viscous flow and Jones-Dole's B coefficient are estimated. Ev against pressure yields a concave curve with a minimum and B yields a convex one with a maximum. These phenomena are attributed to pressure, temperature, and concentration effects on the water-structure.

To minimize the risk of malperfusion, axillary arterial cannulation which avoids retrograde flow, has been widely used in patients undergoing operations for various types of aortic pathologies. Despite several advantages of this technique, cerebral malperfusion is getting known and might be due to newly developed arterial damage or dissection. Eighty-four patients underwent cannulation of the axillary artery in recent 5 years. Malperfusion occurred in 3 patients with significant regional cerebral oxygen desaturation during operation. Axillary arterial perfusion was stopped and oxygen saturation was elevated immediately. The perfusion was switched to the femoral artery and following procedure was completed. Although axillary arterial cannulation is an attractive alternative, neither axillary nor femoral arterial perfusion is perfect to avoid the cerebral malperfusion. Whichever perfusion site is used, special care should be taken for intraoperative finding and appropriate use of each techniques.

We describe a case of replacement with a cryopreserved homograft for graft infection. A 48-year-old man had been performed ascending aorta replacement using woven dacron graft for type A aortic dissection. Two months ago, methicillin-resistant Staphylococcus aureus infection was suspected because of high-grade fever. Computed tomography (CT) scan revealed abscess formation around the prosthetic graft and redo operation using cryopreserved homograft was scheduled to avoid re-infection into mediastinum at Tohoku University Hospital, an institute cooperating with University of Tokyo tissue bank. However, Catastrophic Great East Japan Earthquake occurred the day before the scheduled date, and the patient could not have an operation at the institution. He was transferred to our hospital by helicopter. Then homograft was successfully implanted in ascending aorta after complete excision of infectious graft.

The structural change of chicken egg white lysozyme in aqueous 1-butyl-3-methylimidazolium nitrate ([bmim][NO(3)]) solutions (0-24 M) has been investigated by optical spectroscopy and small-angle X-ray scattering (SAXS) methods. Fourier-transform infrared (FTIR) and circular dichroism (CD) spectra and SAXS profiles indicated that the addition of up to 6 M of [bmim][NO(3)] induces unfolding of lysozyme resulting from disruption of the α-helix by the NO(3)(-) ion. On the other hand, even with the addition of more than 10 M of [bmim][NO(3)], lysozyme aggregation is inhibited and the protein adopts a partially globular state (the secondary structure is partially refolded while the tertiary structure is disrupted). Observation of the structural features of the aqueous [bmim][NO(3)] solution by Raman OD stretching spectra indicated that bulk-like water still remains at concentrations above 10 M and form an "aggregated water" (water pool) in the nanoheterogeneous structure consisting of a polar domain (the high charge-density region) and nonpolar areas (the alkyl-chain region) in the IL. At these concentrations (above 10 M), lysozyme is not sufficiently hydrated because of the reduced number of water molecules. Consequently lysozyme above 10 M assumes the partially globular state. We propose that the changes of the unique IL solution structure (nanoheterogeneous) between the lower and higher [bmim][NO(3)] concentrations strongly correlated to the differences in the protein stability of the present results.