Copper-Catalyzed Regioselective Aminothiolation of Aromatic and Aliphatic Alkenes with N-Fluorobenzenesulfonimide and Thiols through Three-Component Radical Coupling

Copper-catalyzed regioselective aminothiolation of terminal and internal alkenes with N-fluorobenzenesulfonimide and thiols has been developed. The three-component reaction is promoted by the addition of dimethyl sulfide. In addition to aromatic alkenes, aliphatic alkenes are subjected to the reaction, affording various aminothiolation adducts as single regioisomers. The radical process is proposed by preliminary mechanistic studies, involving radical trap and radical clock experiments

Synthesis of Benzoisoselenazolone Derivatives by Nickel-Catalyzed Dehydrogenative Direct Selenation of C(sp2)-H Bonds with Elemental Selenium in Air

Nickel-catalyzed direct selenation of benzamides bearing an 8-quinolyl auxiliary with elemental selenium provides benzoisoselenazolones in good yield via carbon-selenium and nitrogen-selenium bond formation under aerobic conditions. In addition to aryl C-H bonds, the method can also be applied to alkenyl C-H bonds, constructing an isoselenazolone skeleton. Simple mechanistic analysis shows that the reaction proceeds through a rate-determining C-H bond cleavage. The obtained benzoisoselenazolones are transformed into various organoselenium compounds and utilized as the catalyst for bromolactonization of alkenoic acids

Development and scale-up of perfusion cell culture process for higer productivity

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Accuracy, repeatability, and reproducibility of T1 and T2 relaxation times measurement by 3D magnetic resonance fingerprinting with different dictionary resolutions

[Objectives] To assess the accuracy, repeatability, and reproducibility of T₁ and T₂ relaxation time measurements by three-dimensional magnetic resonance fingerprinting (3D MRF) using various dictionary resolutions. [Methods] The ISMRM/NIST phantom was scanned daily for 10 days in two 3 T MR scanners using a 3D MRF sequence reconstructed using four dictionaries with varying step sizes and one dictionary with wider ranges. Thirty-nine healthy volunteers were enrolled: 20 subjects underwent whole-brain MRF scans in both scanners and the rest in one scanner. ROI/VOI analyses were performed on phantom and brain MRF maps. Accuracy, repeatability, and reproducibility metrics were calculated. [Results] In the phantom study, all dictionaries showed high T₁ linearity to the reference values (R² > 0.99), repeatability (CV 0.98), repeatability (CV < 6%), and reproducibility (CV ≤ 4%) for T₂ measurement. The volunteer study demonstrated high T1 reproducibility of within-subject CV (wCV) < 4% by all dictionaries with the same ranges, both in the brain parenchyma and CSF. Yet, reproducibility was moderate for T₂ measurement (wCV < 8%). In CSF measurement, dictionaries with a smaller range showed a seemingly better reproducibility (T₁, wCV 3%; T₂, wCV 8%) than the much wider range dictionary (T₁, wCV 5%; T₂, wCV 13%). Truncated CSF relaxometry values were evident in smaller range dictionaries. [Conclusions] The accuracy, repeatability, and reproducibility of 3D MRF across various dictionary resolutions were high for T₁ and moderate for T₂ measurements. A lower-resolution dictionary with a well-defined range may be adequate, thus significantly reducing the computational load. [Key Points] • A lower-resolution dictionary with a well-defined range may be sufficient for 3D MRF reconstruction. • CSF relaxation times might be underestimated due to truncation by the upper dictionary range. • Dictionary with a higher upper range might be advisable, especially for CSF evaluation and elderly subjects whose perivascular spaces are more prominent

Atropisomeric Chiral Diiododienes (Z,Z)-2,3-Di(1-iodoalkylidene)tetralins : Synthesis, Enantiomeric Resolution, and Application in Asymmetric Catalysis

The C2-symmetric tetralin-fused 1,4-diiodo-1,3-butadiene derivatives, (Z,Z)-2,3-di(1-iodoalkylidene)tetralin 1a-c, are atropisomeric and can be resolved into the two persistent axially chiral enantiomers by HPLC on a chiral stationary phase. The enantiomerically pure compounds can serve as chiral organocatalysts for dearomatizing spirolactonization to show good performances in up to 73 % ee

Obliquity of an Earth-like planet from frequency modulation of its direct imaged lightcurve: mock analysis from general circulation model simulation

Direct-imaging techniques of exoplanets have made significant progress recently, and will eventually enable to monitor photometric and spectroscopic signals of earth-like habitable planets in the future. The presence of clouds, however, would remain as one of the most uncertain components in deciphering such direct-imaged signals of planets. We attempt to examine how the planetary obliquity produce different cloud patterns by performing a series of GCM (General Circulation Model) simulation runs using a set of parameters relevant for our Earth. Then we use the simulated photometric lightcurves to compute their frequency modulation due to the planetary spin-orbit coupling over an entire orbital period, and attempt to see to what extent one can estimate the obliquity of an Earth-twin. We find that it is possible to estimate the obliquity of an Earth-twin within the uncertainty of several degrees with a dedicated 4 m space telescope at 10 pc away from the system if the stellar flux is completely blocked. While our conclusion is based on several idealized assumptions, a frequency modulation of a directly-imaged earth-like planet offers a unique methodology to determine its obliquity.Comment: 29 pages, 18 figures, accepted for publication in Ap

Low-Intensity Resistance Training with Moderate Blood Flow Restriction Appears Safe and Increases Skeletal Muscle Strength and Size in Cardiovascular Surgery Patients:A Pilot Study

We examined the safety and the effects of low-intensity resistance training (RT) with moderate blood flow restriction (KAATSU RT) on muscle strength and size in patients early after cardiac surgery. Cardiac patients (age 69.6 +/- 12.6 years, n = 21, M = 18) were randomly assigned to the control (n = 10) and the KAATSU RT group (n = 11). All patients had received a standard aerobic cardiac rehabilitation program. The KAATSU RT group additionally executed low-intensity leg extension and leg press exercises with moderate blood flow restriction twice a week for 3 months. RT-intensity and volume were increased gradually. We evaluated the anterior mid-thigh thickness (MTH), skeletal muscle mass index (SMI), handgrip strength, knee extensor strength, and walking speed at baseline, 5-7 days after cardiac surgery, and after 3 months. A physician monitored the electrocardiogram, rate of perceived exertion, and the color of the lower limbs during KAATSU RT. Creatine phosphokinase (CPK) and D-dimer were measured at baseline and after 3 months. There were no side effects during KAATSU RT. CPK and D-dimer were normal after 3 months. MTH, SMI, walking speed, and knee extensor strength increased after 3 months with KAATSU RT compared with baseline. Relatively low vs. high physical functioning patients tended to increase physical function more after 3 months with KAATSU RT. Low-intensity KAATSU RT as an adjuvant to standard cardiac rehabilitation can safely increase skeletal muscle strength and size in cardiovascular surgery patients.</p

Blood Flow Restriction Increases the Neural Activation of the Knee Extensors During Very Low-Intensity Leg Extension Exercise in Cardiovascular Patients:A Pilot Study

Blood flow restriction (BFR) has the potential to augment muscle activation, which underlies strengthening and hypertrophic effects of exercise on skeletal muscle. We quantified the effects of BFR on muscle activation in the rectus femoris (RF), the vastus lateralis (VL), and the vastus medialis (VM) in concentric and eccentric contraction phases of low-intensity (10% and 20% of one repetition maximum) leg extension in seven cardiovascular patients who performed leg extension in four conditions: at 10% and 20% intensities with and without BFR. Each condition consisted of three sets of 30 trials with 30 s of rest between sets and 5 min of rest between conditions. Electromyographic activity (EMG) from RF, VL, and VM for 30 repetitions was divided into blocks of 10 trials and averaged for each block in each muscle. At 10% intensity, BFR increased EMG of all muscles across the three blocks in both concentric and eccentric contraction phases. At 20% intensity, EMG activity in response to BFR tended to not to increase further than what it was at 10% intensity. We concluded that very low 10% intensity exercise with BFR may maximize the benefits of BFR on muscle activation and minimize exercise burden on cardiovascular patients

Short Physical Performance Battery for cardiovascular disease inpatients : implications for critical factors and sarcopenia

We examined the relationship between Short Physical Performance Battery (SPPB) and clinical and laboratory factors and the effect of sarcopenia and sarcopenic obesity (SO) on clinical and laboratory factors for cardiovascular disease (CVD) inpatients. CVD male (n=318) and female (n=172) inpatients were recruited. A stepwise multiple-regression analysis was performed to predict total SPPB scores and assess clinical and laboratory factors (physical characteristics, functional and morphological assessments, etc.). Each test outcome were compared among sarcopenia, SO and non-sarcopenic groups. To predict total SPPB scores, the predicted handgrip, Controlling Nutritional Status score, % body fat, anterior mid-thigh muscle thickness, standing height and systolic blood pressure were calculated for males and anterior mid-thigh MTH, BMI, knee extension and fat mass were calculated for females. There were no differences in blood pressure, total SPPB scores and functional assessments between sarcopenia and SO groups for CVD male and female inpatients. In conclusion, the physical performance of CVD inpatients can be predicted by nutritional, functional, clinical and anthropometric variables, regardless the gender and the presence of sarcopenia. Furthermore, the presence of sarcopenia has a negative effect on the clinical and laboratory factors, but there is a difference in impact between sarcopenia and SO regardless the gender