Vesicles Exhibit High-Performance Removal of Per- and Polyfluoroalkyl Substances (PFAS) Depending on their Hydrophobic Groups.

The removal of per- and polyfluoroalkyl substances (PFAS) from drinking water is urgently needed. Here, we demonstrated high performance of vesicles on PFAS adsorption. Vesicles used in this study were enclosed amphiphile bilayers keeping their hydrophobic groups inside and their hydrophilic groups outside in water. The distribution coefficient Kd of perfluorooctane sulfonic acid (PFOS) for vesicles was 5.3 × 105 L/kg, which is higher than that for granulated activated carbon (GAC), and Kd of perfluorooctanoic acid (PFOA) for vesicles was 103-104 L/kg. The removal efficiencies of PFOA and PFOS adsorption on DMPC vesicles were 97.1 ± 0.1% and 99.4 ± 0.2%, respectively. The adsorption behaviors of PFOA and PFOS on vesicles were investigated by changing the number of cis-double bonds in the hydrophobic chains of the vesicle constituents. Moreover, vesicles formed by membranes in the different phases were also tested. The results revealed that, when vesicles are formed of a membrane in the liquid-crystalline (liquid-like) phase, the adsorption amounts of both PFOA and PFOS increased as the cis-double bond in the hydrocarbon chains decreased, which is considered due to molecular shape similarity. When vesicles are formed of a membrane in the gel (solid-like) phase, they do not adsorb PFAS as much as in the liquid-crystalline phase, even though the hydrocarbon chains do not have any cis-double bond. Our findings demonstrate that vesicles can be utilized as PFAS adsorbents by optimizing the structure of vesicle constituents and their thermodynamical phase. Indeed, the vesicles (DMPC) were demonstrated that they can adsorb PFOA and PFOS, and be coagulated by a coagulant even in environmental water. The coagulation will enable the removal of PFOA and PFOS from the water after adsorption.

Ammonium salt production in NH3-CO2-H2O system using a highly selective adsorbent, copper hexacyanoferrate.

Ammonia is a beneficial material that is widely used in agriculture, but its emission into the atmosphere causes air pollution. Recently, Prussian blue (PB) and its analogs (PBA) were found to be ammonia adsorbents with high selectivity and capacity. In this study, we utilized a highly potent PBA adsorbent, copper hexacyanoferrate (CuHCF), to desorb ammonia and turn it into a reusable form. Because the reported NH3-CO2-H2O system phase diagram suggests the possibility of the recovery of solid NH4HCO3, we examined whether adsorbed ammonia desorbs into the saturated ammonium hydrogencarbonate solution (sat. NH4HCO3aq). We demonstrated that 40% of adsorbed ammonia desorbed into sat. NH4HCO3aq. After the desorption, CO2 was blown into the washing liquid, and NH4HCO3 precipitated, which was confirmed by Fourier transform infrared spectroscopy. The molar amount of solid NH4HCO3 was almost equal to that of desorbed ammonia. Our findings pave the way for recovery of ammonia as a valuable product from waste gas.

Thermal Decomposition Behavior of Prussian Blue in Various Conditions.

Prussian blue analogs (PBA) are widely studied for radioactive cesium decontamination. However, there are fewer works related to their post use storage. Considering the oxidative stabilization of the material after the selective uptake of Cs, the thermogravimetric properties in powder and bead form, with various Cs and other alkali metal ions adsorbed, and various heating rates were studied. TG-DTA taken in dry air condition shows an exothermic decomposition at ~270 °C. This temperature varied with the heating rate, mass, and the proportion of adsorbed ions. The best condition for complete oxidation of Prussian blue (PB) is found to be a gradual oxidative decomposition by heating in the temperature range of 200-220 °C until the total mass is decreased by >35%. After this, the temperature could be safely increased to >300 °C for the complete oxidative decomposition of PB that formed iron oxide and salt of the adsorbed Cs. A pilot scale test conducted using the radioactive Cs adsorbed Prussian blue microbeads (PB-b) confirmed that no Cs was released in the effluent air during the process.

Trace Ammonia Removal from Air by Selective Adsorbents Reusable with Water.

Ammonia adsorbents effective even in trace concentrations are key to the countermeasure for air pollution of particulate matter caused by ammonia emission from agriculture sectors. We revealed that Prussian blue (PB) and its analogues (PBAs), one of the porous coordination polymers, have higher ammonia adsorption capacity in 10 ppmv of ammonia (parts per million in volume, 10 ppmv = 0.0001 volume percent), ≥8 times that of conventional adsorbents. Moreover, these compounds can be recycled only through water flushing. The adsorption capacity of PBA was restricted to 10 cycles of adsorption/desorption, and the air sample for the experiment was collected from the composting equipment present in a swine farm. Despite the presence of saturated water vapor in the exhaust gas, the adsorbents showed excellent selectivity in the removal of ammonia from the sample.

Pre-enrichment of radioactive cesium in muddy water separated into suspended and dissolved substances for trace analysis.

A new in-situ pre-enrichment system was developed for trace analysis of radioactive Cs in environmental water such as rivers, ponds, and seas, where the radioactive Cs is separated into suspended substances (SS) and dissolved substances (DS). The SS component was collected as the enrichment slurry by cross-flow filtration, thereby compact systems were realized. The DS component was collected in a small cartridge filled with a non-woven fiber with immobilized adsorbent nanoparticles. The recovery rate was estimated at around 95%. The size distribution of the SS and the concentration of radioactive Cs after enrichment were the same as that of the raw water before enrichment. The condensed SS can be used for other evaluations such as ignition loss. From the field test at a pond in the Fukushima-area, the Cs concentration of the SS was found to be 4-5 times higher than that of the sediment in the same pond. The organic content estimated by ignition loss was also three times higher.

Fish oil and fenofibrate inhibit pancreatic islet hypertrophy, and improve glucose and lipid metabolic dysfuntions with different ways in diabetic KK mice.

We examined the effects of fish oil and fenofibrate (FF) on the pancreatic islet hypertrophy, and on the modification of glucose and lipid metabolic dysfunctions in KK mice with insulin resistance. The mice were fed one of four diets [25en% lard/safflower oil (LSO), 25en% fish oil (FO), or each of these diets plus 0.1wt% FF (LSO/FF, FO/FF)] for 9 weeks. FO group and both FF groups had significantly lower final body and adipose tissue weights than LSO group. Pancreatic islet hypertrophy was observed only in LSO group but not in the other groups with fish oil or FF. And, it is likely that fish oil has a stronger therapeutic effect on islet hypertrophy. Plasma adiponectin level was significantly higher in FO group but not in both FF groups. Expression of hepatic lipogenic enzyme genes such as fatty acid synthase (FAS) and stearoyl-CoA desaturase-1 (SCD-1) was lower in FO groups with or without FF, whereas fatty acid oxidation-related mRNAs such as acyl-CoA oxidase (AOX) and uncoupling protein-2 (UCP-2) were more abundant in FF groups with or without fish oil. Our results suggest that both fish oil and FF improve pancreatic islet hypertrophy with the amelioration of insulin resistance. Fish oil enhances insulin sensitivity by increasing plasma adiponectin; however, the beneficial effect of FF on insulin resistance seems to be independent of the plasma adiponectin level. These results mean that improvement of glucose and lipid metabolic dysfuctions in diabetic KK mice are independently approached by fish oil and FF.

High-capacity and selective ammonium removal from water using sodium cobalt hexacyanoferrate.

A new NH4 + adsorbent with high capacity and selectivity, sodium cobalt(ii) hexacyanoferrate(ii) (NaCoHCF, Na y Co(ii) [Fe2+(CN)6] x ·zH2O), was prepared. The adsorption performance was investigated by varying the mixing ratio of [Fe(CN)6]4- to Co2+ during synthesis, R mix. The ammonia capacity was found to be proportional to R mix, indicating that the NH4 + capacity can be increased by increasing the Na+-ion content in NaCoHCF. To conduct a detailed study, we prepared homogeneous nanoparticles by flow synthesis using a micromixer with R mix = 1.00. Even on the addition of a saline solution (NaCl) with an Na+-ion concentration of 9350 mg L-1, the capacity was maintained: q max = 4.28 mol kg-1. Using Markham-Benton analysis, the selectivity factor, defined by the ratio of equilibrium constants for NH4 + to that for Na+, was calculated to be α = 96.2, and 4.36 mol kg-1 was found to be the maximum capacity. The high selectivity of NaCoHCF results in good NH4 +-adsorption performance, even from seawater. In comparison with other adsorbents under the same conditions and even for a NH4Cl solution, NaCoHCF showed the highest capacity. Moreover, the coexisting Na+ caused no interference with the adsorption of ammonium by NaCoHCF, whereas the other adsorbents adsorbed ammonia only slightly from the saline solution. We also found that the pores for NH4 + adsorption changed their sizes and shapes after adsorption.

Protective effects of fish oil and pioglitazone on pancreatic tissue in obese KK mice with type 2 diabetes.

n-3 Polyunsaturated fatty acids, such as eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA), have protective effects against the pancreatic ß-cell dysfunction through several mechanisms. Thiazolidines are insulin sensitizers and are used in treating patients with type 2 diabetes. Our previous study demonstrated that a combination of fish oil, which is rich with EPA and DHA, and pioglitazone exerts beneficial effects on obesity and diabetes through their actions on the liver and adipose tissue. However, it remains largely unknown whether such combination therapy affects the pancreas. To answer this question, KK mice, which serve as a model for obesity and type 2 diabetes, were treated for 8 weeks with fish oil and pioglitazone. The combined regimen suppressed pancreatic islet hypertrophy (mean islet area decreased by an average of 49% vs. control) compared with mice treated with fish oil or pioglitazone alone (decreased by an average of 21% and 32% vs. control, respectively). Compared with the controls, individual or combined treatment significantly increased the percentage of ß-cell area in the pancreatic islets, significantly decreased endoplasmic reticulum stress, and reduced the percentage of apoptotic cell death in the pancreatic islets. These findings suggest that fish oil and/or pioglitazone prevents ß-cell dysfunction by improving the insulin resistance and decreasing the ER stress.

Radiocesium removal system for environmental water and drainage.

With the development of the nuclear power generation, it is expected that severe pollution of environmental water by radiocesium (r-Cs) may occur. We developed a r-Cs removal system with a continuous stirring tank reactor (CSTR) and r-Cs adsorbent of non-woven fiber immobilizing Prussian blue nanoparticles (PBN). Results confirmed that this system can remove r-Cs from environmental water with a removal rate higher than 80% at processing speed of 2 m3/h. In this study, the processing speed and processing capacity of this system were confirmed using kinetic and equilibrium analyses of Cs adsorption behavior on PBN. The equilibrium of Cs adsorption was analyzed using a Langmuir equation. Results show that the maximum adsorption capacity was 160 mg/g (PBN). The kinetic data were well fitted using a pseudo-first order kinetic model. This rate constant was correlated to the PBN/liquid ratio in the system.

Efficient approach to include molecular polarizations using charge and atom dipole response kernels to calculate free energy gradients in the QM/MM scheme.

An efficient approach to evaluate free energy gradients (FEGs) within the quantum mechanical/molecular mechanical (QM/MM) framework has been proposed to clarify reaction processes on the free energy surface (FES) in molecular assemblies. The method is based on response kernel approximations denoted as the charge and the atom dipole response kernel (CDRK) model that include explicitly induced atom dipoles. The CDRK model was able to reproduce polarization effects for both electrostatic interactions between QM and MM regions and internal energies in the QM region obtained by conventional QM/MM methods. In contrast to charge response kernel (CRK) models, CDRK models could be applied to various kinds of molecules, even linear or planer molecules, without using imaginary interaction sites. Use of the CDRK model enabled us to obtain FEGs on QM atoms in significantly reduced computational time. It was also clearly demonstrated that the time development of QM forces of the solvated propylene carbonate radical cation (PC˙(+)) provided reliable results for 1 ns molecular dynamics (MD) simulation, which were quantitatively in good agreement with expensive QM/MM results. Using FEG and nudged elastic band (NEB) methods, we found two optimized reaction paths on the FES for decomposition reactions to generate CO2 molecules from PC˙(+), whose reaction is known as one of the degradation mechanisms in the lithium-ion battery. Two of these reactions proceed through an identical intermediate structure whose molecular dipole moment is larger than that of the reactant to be stabilized in the solvent, which has a high relative dielectric constant. Thus, in order to prevent decomposition reactions, PC˙(+) should be modified to have a smaller dipole moment along two reaction paths.

Uterine tumors resembling ovarian sex cord tumors (UTROSCT) with metastasis: clinicopathological study of two cases.

Uterine tumors with sex cord-like elements are divided in two groups; uterine tumors resembling ovarian sex cord tumors (UTROSCT), and endometrial stromal tumors with sex cord-like elements (ESTSCLE). UTROSCT is currently defined as the neoplasm predominantly or exclusively composed of sex cord-like elements, and generally behaves in a benign fashion. We studied two unusual cases of UTROSCT with metastasis. One case was a 38-year-old multiparous woman presented with hypermenorrhea. The tumor grew as an intramural mass, and metastasized to a pelvic lymph node. Another case was a 57-year-old woman presented with genital bleeding. The tumor grew as a submucosal exophytic mass, and metastasized to the epiploic appendix. Microscopic examination of the 2 cases revealed that they were composed of sex cord-like cells, epithelioid cells and spindle cells. They exhibited solid pattern in predominance. Both solid and sex cord-like elements showed similar immunoreactivities for more than 3 sex cord markers, but simultaneously showed different staining patterns for some other markers. Characteristic features of endometrial stroma such as tongue-like infiltration and spiral arteries-like arterioles were not observed. RT-PCR analysis confirmed the absence of JAZF1-SUZ12 gene fusion, supporting the histopathological diagnosis of UTROSCT rather than ESTSCLE. The current cases warned the potential risk of UTROSCT whose biological behavior is still uncertain. We discuss histopathological, immunohistochemical and molecular findings of UTROSCT with metastasis.

Anti-HIV and immunomodulation activities of cacao mass lignin-carbohydrate complex.

BACKGROUND: Recently, a prominent antiviral and macrophage stimulatory activity of cacao lignin-carbohydrate complex (LCC) has been reported. However, the solubility and sterility of LCC have not been considered yet. In the present study, complete solubilisation and sterilisation was achieved by autoclaving under mild alkaline conditions and the previously reported biological activities were re-examined. MATERIALS AND METHODS: LCCs were obtained by 1% NaOH extraction and acid precipitation, and a repeated extraction-precipitation cycle. Nitric oxide (NO) and cytokine productions were assayed by the Griess method and ELISA, respectively. Inducible NO synthase (iNOS) expression was determined by Western blot analysis. Superoxide anion, hydroxyl radical and nitric oxide radical-scavenging activity was determined by ESR spectroscopy. RESULTS: Cacao mass LCC showed reproducibly higher anti-HIV activity than cacao husk LCC. Cacao mass LCC, up to 62.5 µg/ml, did not stimulate mouse macrophage-like cells (RAW264.7 and J774.1) to produce NO, nor did it induce iNOS protein, in contrast to lipopolysaccharide (LPS). Cacao mass LCC and LPS synergistically stimulated iNOS protein expression, suggesting a different point of action. Cacao mass LCC induced tumour necrosis factor-α production markedly less than LPS, and did not induce interleukin-1ß, interferon-α or interferon-γ. ESR spectroscopy showed that cacao mass LCC, but not LPS, scavenged NO produced from NOC-7. CONCLUSION: This study demonstrated several new biological activities of LCCs distinct from LPS and further confirmed the promising antiviral and immunomodulating activities of LCCs.

Midterm results for endovascular stent grafts via median sternotomy for distal aortic arch aneurysm.

Dislocation or perigraft leakage is a major problem during the follow-up period for endovascular stent graft (EVG) implantation via median sternotomy for distal aortic arch aneurysm. Anchoring sutures have been applied for the prevention of these complications. Here, we evaluate the midterm results and the efficacy of anchoring sutures. There were 21 male and 2 female patients enrolled in the study with an average age of 70 years (59-83). Aneurysm types were 21 true aneurysms (13 fusiform, 8 saccular), 1 chronic dissection, and 1 penetrating aortic ulcer. Total arch replacement was performed in two patients and aortocoronary bypass grafting was combined in four patients. Anchoring sutures to fix the EVG via median sternotomy were applied for 11 recent patients. The average follow-up period was 44 (22-79) months. There were no operative mortalities, but one case of paraplegia, one of stroke, and two of temporary spinal cord dysfunction. Complications related to EVG via median sternotomy occurred in five patients who had not received anchoring sutures, but the 11 patients with anchoring sutures showed no EVG-related complications. A chronic type B dissection revealed impending rupture due to false lumen infection 1 year after operation and repeat surgery was performed. Stent dislocation occurred in four patients, two of whom required repeat surgery via left thoracotomy due to endoleakage 3 and 4 years after surgery. One died from aneurismal rupture 5 years after surgery. One required emergency graft replacement because of graft perforation 5 years after surgery. The proportion of patients free from EVG-related events at 5 years after surgery was 75%. Anchoring sutures (P = 0.0155) and a large aneurysm of more than 80 mm (P = 0.0190) were predictors of late EVG-related complications. There were five late deaths: two were from stroke, one from rupture, one from cancer, and one from multiple organ failure after repeat surgery. EVG shortens postoperative recovery with relatively lower mortality, but spinal cord injury is a complication occurring with a relatively high rate. Patients with large aneurysms are not good candidates for EVG implantation via median sternotomy Anchoring sutures to fix the EVG to the aortic wall should help prevent EVG-related events and improve the durability of EVG.

Intracoronary adenosine triphosphate for refractory coronary artery spasm.

A 62-year-old woman underwent aortic valve replacement for aortic stenosis. Her hemodynamics deteriorated with ST-T depression 6 hours postoperatively. Emergency coronary catheterization showed diffuse right coronary artery spasm. The spasm persisted despite intracoronary infusion of nitrates and calcium antagonists. Intracoronary adenosine triphosphate infusion finally resolved the spasm and stabilized the cardiac function.

[Studies on analysis of terpene resin in imported chewing gums].

We have developed an analytical method for terpene resins in chewing gum. The fraction including terpene resins was prepared by means of hexane extraction and two silica gel column chromatography treatments (hexane and ethyl acetate) from chewing gum. The terpene resin fraction was analyzed with LC/MS and IR. The terpene resins are mixtures of polymeric pinene and/or limonene, which have a monomer molecular weight of 136. The MS spectrum of the terpene resin peak on the LC/MS total ion chromatogram showed protonated molecular ion (M + H)+ peaks at intervals of m/z 136, characteristic of a complex mixture of polyterpenes. IR spectroscopy is a suitable technique to identify the terpene resin type, ie., pinene or limonene. When the method was applied to imported chewing gum sold in Japan, terpene resins were clearly detected.

The amplification of somatic symptoms in upper respiratory tract infections.

To assess the cultural differences in the role of somatosensory amplification in Japan and North America, we re-examined the role of psychological amplification of objective physical symptoms, as measured by the Somatosensory Amplification Scale (SSAS), in 82 Japanese patients with upper-respiratory tract infections. Anxiety and depression were measured with the Hospital Anxiety and Depression Scale (HADS). We determined the association among continuous variables using the Spearman correlation coefficient. Next, we used multiple regression analysis and selected all symptoms as independent variables. The SSAS was significantly associated with all somatic symptoms. It was also closely related to discomfort, but the SSAS was not significantly correlated with either anxiety or depression. All somatic symptoms were not significantly correlated with the objective physical findings. Multiple regression analyses indicated that amplification by SSAS was a statistically significant predictor of the patient's somatic symptoms and discomfort. The objective findings did not significantly predict the patient's symptoms. Our study provides some empirical evidence regarding psychological amplification of objective physical symptoms, as measured by SSAS, in Japanese patients with upper-respiratory tract infections. Our findings suggest that there is no difference in the role of amplification of bodily sensations between Japanese and North Americans.

Treatment of refractory coronary vasospasm during cardiopulmonary bypass with compulsory coronary perfusion.

Coronary vasospasm is still a devastating complication during cardiac surgery. We report on a case of intractable coronary vasospasm in a 45-year-old male during coronary bypass surgery refractory to drugs and intra-aortic balloon pumping (IABP). Under cardiopulmonary bypass (CPB) support, the aorta was again cross-clamped and the aortic root was compulsorily perfused with pump blood using a small pump for infusion of cardioplegia. Vasodilators were administered through the perfusion line. Coronary vasospasm was dramatically resolved. He was then successfully weaned from CPB and recovered without further incidents.