Analysis of melatonin using a pH- and temperature-responsive aqueous chromatography system

A new method for the qualitative and quantitative analysis of an intracerebral hormone, such as melatonin, has been proposed, utilizing newly designed copolymers that include ion-exchange groups. These copolymers responded to both the temperature and the pH, and the copolymers were modified with cross-linked hydrogel applied onto aminopropyl silica beads. The products were evaluated as HPLC packing materials for a pH- and temperature-responsive chromatography. The property of the surface of the stationary phase was altered from hydrophilic to hydrophobic, and from charged to non-charged by changes in both the temperature and the pH. In the chromatographic system, we investigated how to change the retention of melatonin by varying the temperature. A pH- and temperature-responsive chromatography is expected to be useful for the separation of pharmaceuticals and biomolecules.     

First total synthesis of antitumor natural product (+)- and (-)-pericosine A: determination of absolute stereo structure

The first total synthesis of (+)- and (-)-pericosine A has been achieved, enabling the revision and determination of the absolute configuration of this antitumor natural product as methyl (3S,4S,5S,6S)-6-chloro-3,4,5-trihydroxy-1-cyclohexene-1-carboxylate. Every step of this total synthesis proceeded well with excellent stereoselectivity. Structures of the intermediates in crucial steps were confirmed by detailed 2D NMR analysis.     

Transient dimerization and conformational change of a BLUF protein: YcgF

The photochemical reaction dynamics of YcgF, a BLUF protein, were investigated by the pulsed laser-induced transient grating (TG) technique. The TG signal showed three reaction time constants: 2.7 micros, 13 micros, and 2 ms. The fastest was tentatively attributed to relaxation of the excited triplet state of the chromophore, flavin adenine dinucleotide (FAD), and the others represented conformational changes of the protein. The TG signal provided clear evidence that the diffusion coefficient (D) of the photoproduct (3.8x10(-11) m2 s-1) was significantly less than that of the reactant (8.3x10(-11) m2 s-1), with a time constant of 2 ms at a protein concentration of 700 microM. Interestingly, the rate constant increased in proportion to the concentration of the protein, indicating that protein dimerization was one of the main reactions occurring after photoexcitation. The significant reduction in D indicates that a conformational change leading to an increase in interactions with water molecules occurs upon formation of the signaling state. The 13 mus dynamics was attributed to the conformational change that induced transient dimerization. This conformational change might be an essential process for the creation of the signaling state. A detailed scheme for the photochemical reaction of YcgF is proposed.     

Copper-catalyzed enantioselective substitution of allylic carbonates with diboron: an efficient route to optically active alpha-chiral allylboronates

A method for the synthesis of alpha-chiral allylboronates featuring the Cu(I)-catalyzed enantioselective substitution of readily available allylic carbonates with a diboron is described. Using this method, various alpha-chiral allylboronates, including functionalized allylboronates, were successfully synthesized, with high enantiomeric purity.     

Impairment in Physical Function and Mental Status in a Survivor of Severe COVID-19 at Discharge from an Acute Care a Hospital: A Case Report

Background: Early mobilization and rehabilitation interventions should be provided to patients who survived severe COVID-19 to improve their physical function and activities of daily living (ADL). However, their physical and mental status at discharge has not been well described in Japan. We report the intervention provided for a survivor of severe COVID-19 and his physical and mental status at discharge from an acute care hospital. Case Report: A 62-year-old man was admitted to our emergency department with a diagnosis of COVID-19 with severe acute respiratory dysfunction. He had complicated intensive care unit-acquired weakness (ICU-AW) and delirium during mechanical ventilation therapy. Rehabilitation intervention was initiated on the seventh day post-admission and was gradually performed according to his respiratory and hemodynamic status. As a result of the rehabilitation intervention, ICU-AW and cognitive function gradually improved. On hospital day 37, he independently performed basic ADL and was discharged. However, he lost approximately 9% of his body weight at discharge. In addition, his hand grip strength and six-minute walking distance were lower and shorter than the reference values, respectively. His mental component summary of the Short Form-8™ was lower than the national standard deviation for the Japanese population. Conclusion: Although survivors of severe COVID-19 who undergo early rehabilitation can be discharged from an acute care hospital, they may have several impairments in their physical and mental status, including muscle function, diffusion capacity, exercise tolerance, and health-related quality of life.     

Supramolecular photocatalysts fixed on the inside of the polypyrrole layer in dye sensitized molecular photocathodes: application to photocatalytic CO2 reduction coupled with water oxidation

The development of systems for photocatalytic CO₂ reduction with water as a reductant and solar light as an energy source is one of the most important milestones on the way to artificial photosynthesis. Although such reduction can be performed using dye-sensitized molecular photocathodes comprising metal complexes as redox photosensitizers and catalyst units fixed on a p-type semiconductor electrode, the performance of the corresponding photoelectrochemical cells remains low, e.g., their highest incident photon-to-current conversion efficiency (IPCE) equals 1.2%. Herein, we report a novel dye-sensitized molecular photocathode for photocatalytic CO₂ reduction in water featuring a polypyrrole layer, [Ru(diimine)₃]²⁺ as a redox photosensitizer unit, and Ru(diimine)(CO)₂Cl₂ as the catalyst unit and reveal that the incorporation of the polypyrrole network significantly improves reactivity and durability relative to those of previously reported dye-sensitized molecular photocathodes. The irradiation of the novel photocathode with visible light under low applied bias stably induces the photocatalytic reduction of CO₂ to CO and HCOOH with high faradaic efficiency and selectivity (even in aqueous solution), and the highest IPCE is determined as 4.7%. The novel photocathode is coupled with n-type semiconductor photoanodes (CoO_x/BiVO₄ and RhO_x/TaON) to construct full cells that photocatalytically reduce CO₂ using water as the reductant upon visible light irradiation as the only energy input at zero bias. The artificial Z-scheme photoelectrochemical cell with the dye-sensitized molecular photocathode achieves the highest energy conversion efficiency of 8.3 × 10⁻²% under the irradiation of both electrodes with visible light, while a solar to chemical conversion efficiency of 4.2 × 10⁻²% is achieved for a tandem-type cell using a solar light simulator (AM 1.5, 100 mW cm⁻²).

A novel dye-sensitized molecular photocathode with polypyrrole networks exhibits high efficiency and durability for photocatalytic CO₂ reduction by using water as reductant and visible light as energy.     

Entropy Based Student’s t-Process Dynamical Model

Volatility, which represents the magnitude of fluctuating asset prices or returns, is used in the problems of finance to design optimal asset allocations and to calculate the price of derivatives. Since volatility is unobservable, it is identified and estimated by latent variable models known as volatility fluctuation models. Almost all conventional volatility fluctuation models are linear time-series models and thus are difficult to capture nonlinear and/or non-Gaussian properties of volatility dynamics. In this study, we propose an entropy based Student’s t-process Dynamical model (ETPDM) as a volatility fluctuation model combined with both nonlinear dynamics and non-Gaussian noise. The ETPDM estimates its latent variables and intrinsic parameters by a robust particle filtering based on a generalized H-theorem for a relative entropy. To test the performance of the ETPDM, we implement numerical experiments for financial time-series and confirm the robustness for a small number of particles by comparing with the conventional particle filtering.