Asymmetric synthesis of (-)-dehydro-exo-brevicomin with a photoisomerisation-intramolecular acetalisation sequence.

We herein report a novel, short asymmetric synthesis of (-)-dehydro-exo-brevicomin (DHB, 1), a sex pheromone isolated from house mice, in 44% overall yield, the highest yield reported so far, over eight steps from trans-3-hexen-1-ol (7). We successfully prepared the target molecule (-)-1 from spontaneous intramolecular acetalisation after the photoisomerisation of trans-enone 6, which generated the corresponding cis-enone 5in situ, the possible biosynthetic precursor of DHB.

Biokinetics of 13C in the human body after oral administration of 13C-labeled glucose as an index for the biokinetics of 14C.

The retention of 13C in the human body after oral administration of 13C-labeled glucose was studied in three healthy volunteer subjects to estimate the 50 year cumulative body burden for 13C as an index of the committed dose of the radioisotope 14C. After administration of 13C-labeled glucose, the volunteers ingested controlled diets with a fixed number of calories for 112 d. Samples of breath and urine were collected up to 112 d after administration. Samples of feces were collected up to 14 d after administration. Hair samples were obtained at 119 d after administration and analyzed as a representative index of the rate of excretion of organic 13C via pathways such as skin cell exfoliation and mucus secretion. All samples were analyzed for 13C/12C atomic ratio to determine the rate of excretion via each pathway. We then constructed a metabolic model with a total of four pathways (breath, urine, feces, and other) comprising seven compartments. We determined the values of the biokinetic parameters in the model by using the obtained excretion data. From 74% to 94% of the 13C administered was excreted in breath, whereas <2% was excreted in urine and feces. In the other pathway, the excretion rate constant in the compartment with the longest residence time stretched to hundreds of days but the rate constant for each subject was not statistically significant (P value > 0.1). In addition, the dataset for one of the three subjects was markedly different from those of the other two. When we estimated the 50 year cumulative body burden for 13C by using our model and we included non-statistically significant parameters, a considerable cumulative body burden was found in the compartments excreting to the other pathway. Although our results on the cumulative body burden of 13C from orally administered carbon as glucose were inconclusive, we found that the compartments excreting to the other pathway had a markedly long residence time and therefore should be studied further to clarify the fate of carbon in the human body. In addition to excreta, data for serum and blood cell samples were also collected from the subjects to examine the metabolism of 13C in human body.

[An autopsy case report of adenosquamous cell carcinoma of the duodenal papilla with multiple liver and lung metastases].

A 63-year-old man was admitted to Saitama-Kyodo Hospital for the management of obstructive jaundice. Gastrointestinal endoscopy revealed a tumor of the duodenal papilla, and tumor biopsy suggested adenosquamous cell carcinoma. Computed tomography revealed multiple tumors in both the liver and lung, and these were diagnosed as metastases using bronchoscopy-guided lung biopsy and ultrasound-guided liver biopsy, respectively. The patient was treated with gemcitabine therapy after successful management of the jaundice by percutaneous transhepatic cholangiodrainage. However, he died three months after hospitalization. Autopsy confirmed a tumor of the duodenal papilla that had invaded both the pancreas and bile duct; moreover, multiple liver and lung metastases were observed. The pathological diagnoses were adenosquamous cell carcinoma. Histopathological findings revealed a mixture of adenocarcinoma and squamous cell carcinoma and promotion of multiplication of the adenocarcinoma. Adenosquamous cell carcinoma of the duodenal papilla is rare and preoperative diagnosis is challenging. Our case is unique because biopsy suggested the diagnosis before treatment.

High-Efficiency Near-Infrared-to-Visible Photon Upconversion in Poly(vinyl alcohol) Porous Film.

Triplet-triplet annihilation photon upconversion (TTA-UC) has received significant attention in energy harvesting applications such as solar cells. The realization of high upconversion (UC) performance in the form of films is a crucial factor for the incorporation of this technology into large-area devices. Herein, we propose a porous UC film prepared by an emulsification method with a poly(vinyl alcohol) (PVA) aqueous solution and a toluene solution of chromophores (rubrene/Pd-tetraphenyltetraanthraporphyrin pair) that achieved considerable UC performance in the near-infrared (NIR) (810 nm) to visible (560 nm) range with a maximum quantum yield of 3.7% (out of 50%). Notably, the films displayed a UC emission when using an NIR light-emitting diode as a low-power-density noncoherent light source, which was confirmed by the naked eye. Excitation-power-dependent time-resolved photoluminescence measurements showed almost identical triplet lifetimes of emitter species for the films and toluene solutions; however, lower threshold intensities (Ith = 1-2 W/cm2) were observed for the films than those of the solutions (Ith = ∼10 W/cm2). An evaluation of the remaining toluene in the film and UC emission behavior in liquid nitrogen suggested that the chromophores exist as an amorphous solid in the pores, thus enabling hybrid triplet energy transfer (chromophore mobility based and exciton migration) in this unique film. The presented methodology can be generalized to other wavelengths and can enable diverse applications of the TTA-UC technology.

METABOLISMS OF 13C IN CATTLE SEMITENDINOSUS MUSCLE AFTER ADMINISTRATION OF 13C LABELED ORCHARD GRASS.

14C released from nuclear facilities is transferred to cattle through their consumption of 14C contaminated grasses. To estimate the concentrations of 14C in their meat, we conducted two sets of experiments. In the first experiment, 230 mg of 13C per day was administered to cattle aged 10 months for 28 days in the form of 13C-labeled grass. The 13C concentration in the semitendinosus muscle decreased exponentially after reaching its peak value. The mean half-life was 76 ± 13 days. In the second experiment, 550 mg of 13C per day was administered to 24-month-old cattle. The change in the semitendinosus muscle was smaller than that recorded in the first experiment, even though the amount of 13C administered per body weight was slightly higher than that in the first experiment. Consequently, the half-life was not determined. Therefore, further studies are required to clarify the metabolism of carbon in 2-year-old cattle.

Estimation of radiation dose from ingested tritium in humans by administration of deuterium-labelled compounds and food.

Radiation doses from organically bound tritium (OBT) in foods have been a major concern near nuclear facilities. The current dose coefficient for OBT is calculated using a standard model from the International Commission on Radiological Protection, in which some biokinetic values are not based on human metabolic data. Here, the biokinetics of ingested OBT, and radiation doses from them, were estimated by administering labelled compounds and foods to volunteers, using a deuterium (D) tracer as a substitute for tritium. After the administration of D-labelled glucose, alanine, palmitic acid, or soybean, the D/H ratios in urine were measured for up to 119 days, and the biokinetic parameter values were determined for OBT metabolism. The slow degradation rates of OBT could not be obtained, in many volunteers administered glucose and alanine. The estimated committed effective dose for 1 Bq of tritium in palmitic acid varied from 3.2 × 10-11 to 3.5 × 10-10 Sv Bq-1 among volunteers and, for those administered soybean, it varied from 1.9 × 10-11 to 1.8 × 10-10 Sv Bq-1. These results suggest that OBT, present in some ingested ingredients, gives higher doses than the current dose coefficient value of 4.2 × 10-11 Sv Bq-1.

Estimation of dietary 14C dose coefficient using 13C-labelled compound administration analysis.

Carbon-14 released from nuclear facilities has been assessed to contribute significantly to the radiation dose that people are exposed to through the food chain. However, the current dose coefficient for members of public, which is the ratio of the 50-year committed effective dose to ingested 1 Bq 14C, recommended by the International Commission on Radiological Protection (ICRP) is not based on experimental human metabolic data for 14C in nutrients and diet. Therefore, to validate the coefficient, we administered 13C-labelled nutrients consisting of four amino acids, three fatty acids, and one monosaccharide to volunteers as substitutes for 14C labelled nutrients and measured the 13C concentration in various excreta samples. Although metabolic models were constructed from the excretion data, a significant fraction of administered 13C was not recovered from some nutrients. The dose coefficients of 14C in uniformly labelled Japanese diet, which were estimated under several assumptions about the unrecoverable fraction, varied from (6.2 ± 0.9) × 10-11 to (8.9 ± 4.4) × 10-10 Sv Bq-1 and were approximately comparable to the current value of 5.8 × 10-10 Sv Bq-1 recommended by the ICRP. Further studies are necessary to elucidate the metabolism of 14C in various nutrients in the unrecoverable fraction.

Physical activity is reduced prior to ventricular arrhythmias in patients with a wearable cardioverter defibrillator.

INTRODUCTION: The utility of accelerometer-based activity data to identify patients at risk of sustained ventricular tachycardia (VT) or ventricular fibrillation (VF) has not previously been investigated. The aim of the current study was to determine whether physical activity is associated with manifesting spontaneous sustained VT/VF requiring emergent defibrillation in patients with an ejection fraction of ≤35%. METHODS: Patients consecutively prescribed a wearable cardioverter defibrillator (WCD) from April 2015 to May 2018 were included. Shock data and 4 weeks of physical activity data, beginning with the first week of WCD wear, were analyzed. RESULTS: Based on the ROC curve outcome generated from 4057 patients, average daily step count during the first week accurately predicted those patients with sustained VT/VF compared to those without (shocked (n = 81) vs nonshocked (n = 3976) area under the curve, c-index = 0.71, 95% CI = 0.65-0.77, P < .001). An average cutoff of 3637 daily steps during week 1 separated the groups. Patients who averaged fewer than 3637 steps per day during the first week of WCD use were 4.3 times more likely to experience a shock than those who walked more than 3637 steps per day (OR = 4.29, 95% CI = 2.58-7.15, P < .001). DISCUSSION: Average daily step counts are lower in WCD patients who manifest spontaneous VT/VF. Whether these findings represent a causal or correlational relationship, future studies to encourage a minimum daily step count in high-risk patients may impact the incidence of sustained VT/VF.

Development of a 1-week cycle menu for an Advanced Life Support System (ALSS) utilizing practical biomass production data from the Closed Ecology Experiment Facilities (CEEF).

Productivities of 29 crops in the Closed Ecology Experiment Facilities (CEEF) were measured. Rice and soybean showed higher productivities than these given by the Advanced Life Support System Modeling and Analysis Project Baseline Values and Assumption Document (BVAD), but productivities of some other crops, such as potato and sweet potato, were lower. The cultivation data were utilized to develop a 1-week cycle menu for Closed Habitation Experiment. The menu met most of the nutritional requirements. Necessary cultivation area per crew was estimated to be 255 m2. Results from this study can be used to help design the future Advanced Life Support System (ALSS) including the CEEF.

Quantitating intracellular oxygen tension in vivo by phosphorescence lifetime measurement.

Hypoxia appears to have an important role in pathological conditions in many organs such as kidney; however, a method to quantify intracellular oxygen tension in vivo has not been well established. In this study, we established an optical method to quantify oxygen tension in mice kidneys using a cationic lipophilic phosphorescence probe, BTPDM1, which has an intracellular oxygen concentration-sensitive phosphorescence lifetime. Since this probe is distributed inside the tubular cells of the mice kidney, we succeeded in detecting acute renal hypoxic conditions and chronic kidney disease. This technique enabled us to estimate intracellular partial pressures of oxygen in vivo by extrapolating the calibration curve generated from cultured tubular cells. Since intracellular oxygen tension is directly related to cellular hypoxic reactions, such as the activation of hypoxia-inducible factors, our method will shed new light on hypoxia research in vivo.

A thiamin derivative inhibits oxidation of exogenous glucose at rest, but not during exercise.

Thiamin (vitamin B(1)) is known to activate carbohydrate metabolism in part through activation of pyruvate dehydrogenase. The purpose of this study was to investigate the effect of thiamin tetrahydrofurfuryl disulfide (TTFD), a thiamin derivative, on utilization of exogenous glucose by measuring oxidation of (13)C-glucose at rest and during prolonged exercise in mice under normal dietary conditions. Mice orally ingested TTFD (0.1 mg/g BW [body weight]) and (13)C-glucose (0.8 mg/g BW) or (13)C-lactate (0.1 mg/g BW) plus glucose (0.8 mg/g BW) at rest or before endurance running. The average percent of (13)C atoms in total (12)C+(13)C ((13)C atom%) in expired air after ingestion of (13)C-glucose at rest was significantly lower in the TTFD group than in the control group. No significant difference was found in (13)C atom% in expired air after ingestion of (13)C-glucose and prolonged exercise. In addition, no significant effect of TTFD was found in expired (13)C atom% after ingestion of (13)C-lactate plus glucose at rest. TTFD also had no effect on concentrations of muscle or liver glycogen at rest. These results suggest that TTFD, which is a thiamin derivative, decreases oxidation of exogenous glucose at rest, but not during exercise.