Changes in Isoflavone Profile from Soybean Seeds during Cheonggukjang Fermentation Based on High-Resolution UPLC-DAD-QToF/MS: New Succinylated and Phosphorylated Conjugates

In this study, thirty-eight isoflavone derivatives were comprehensively identified and quantified from the raw, steamed and fermented seeds of four selected soybean cultivars based on UPLC-DAD-QToF/MS results with reference to the previously reported LC-MS library and flavonoid database, and summarized by acylated group including glucosides (Glu), malonyl-glucosides (Mal-Glu), acetyl-glucosides (Ac-Glu), succinyl-glucosides (Suc-Glu) and phosphorylated conjugates (Phos) in addition to aglycones. Among them, Suc-Glu and Phos derivatives were newly generated due to fermentation by B. subtilis AFY-2 (cheonggukjang). In particular, Phos were characterized for the first time in fermented soy products using Bacillus species. From a proposed roadmap on isoflavone-based biotransformation, predominant Mal-Glu (77.5–84.2%, raw) decreased rapidly by decarboxylation and deesterification into Ac-Glu and Glu (3.5–8.1% and 50.0–72.2%) during steaming, respectively. As fermentation continued, the increased Glu were mainly succinylated and phosphorylated as well as gradually hydrolyzed into their corresponding aglycones. Thus, Suc-Glu and Phos (17.3–22.4% and 1.5–5.4%, 36 h) determined depending on cultivar type and incubation time, and can be considered as important biomarkers generated during cheonggukjang fermentation. Additionally, the changes of isoflavone profile can be used as a fundamental report in applied microbial science as well as bioavailability research from fermented soy foods.     

An Immobilized‐Dirhodium Hollow‐Fiber Flow Reactor for Scalable and Sustainable C−H Functionalization in Continuous Flow

A scalable flow reactor is demonstrated for enantioselective and regioselective rhodium carbene reactions (cyclopropanation and C?H functionalization) by developing cascade reaction methods employing a microfluidic flow reactor system containing immobilized dirhodium catalysts in conjunction with the flow synthesis of diazo compounds. This allows the utilization of the energetic diazo compounds in a safe manner and the recycling of the dirhodium catalysts multiple times. This approach is amenable to application in a bulk‐scale synthesis employing asymmetric C?H functionalization by stacking multiple fibers in one reactor module. The products from this sequential flow–flow reactor are compared with a conventional batch reactor or flow–batch reactor in terms of yield, regioselectivity, and enantioselectivity.     

Time-resolved plasma diagnostics and mass removal during single-pulse laser ablation

Laser ablation processes occurring over several orders of magnitude in time were investigated by using time-resolved spectroscopy, shadowgraphs and interferograms. A picosecond ablation plasma was measured with an electron density on the order of 10²⁰ cm^-3 originating from the breakdown of air. The longitudinal expansion of this plasma was suppressed due to the development of a strong space-charge field. At post-pulse times, the lateral (radial) expansion of the plasma was found to follow the relation, r~t^1/2, consistent with the expansion from an instantaneous line source of energy. The electron number density and temperature were deduced by measuring spectroscopic emission-line broadening during the early phase (30-300 ns) of a mass (atomic/ionic) plasma. These properties were measured as a function of the delay time and irradiance. Possible mechanisms such as inverse bremsstrahlung and self-regulation were used to describe the data before an explosion threshold of 20 GW/cm². The laser self-focusing and critical temperature are discussed to explain dramatic changes in these properties after the irradiance threshold. On the microsecond time scale, the surface explodes and large (>7m) particles are ejected. Mass removed from single-crystal silicon by high power (10⁹-10¹¹ W/cm²) single-pulse laser ablation is studied by measuring the crater morphology. Time-resolved shadowgraph images show that the rapid increase in the crater depth at the threshold corresponds to large-size droplets leaving the surface. This rapid growth of the crater volume is attributed to explosive boiling.     

Azide-assisted cross-linked sulfonated poly(ether sulfone)s as stable and highly conductive membranes with low methanol diffusion coefficients

Novel cross-linked sulfonated poly(ether sulfone)s, prepared by azide-assisted thermal irradiation, show not only low methanol permeability but also exceptionally high proton conductivity with oxidative and hydrolytic stability.     

Design,Synthesis and Biological Evaluation of 1,3,5-Triazine Derivatives Targeting hA1 and hA3 Adenosine Receptor

Adenosine mediates various physiological activities in the body. Adenosine receptors (ARs) are widely expressed in tumors and the tumor microenvironment (TME), and they induce tumor proliferation and suppress immune cell function. There are four types of human adenosine receptor (hARs): hA₁, hA_2A, hA_2B, and hA₃. Both hA₁ and hA₃ AR play an important role in tumor proliferation. We designed and synthesized novel 1,3,5-triazine derivatives through amination and Suzuki coupling, and evaluated them for binding affinities to each hAR subtype. Compounds 9a and 11b showed good binding affinity to both hA₁ and hA₃ AR, while 9c showed the highest binding affinity to hA₁ AR. In this study, we discovered that 9c inhibits cell viability, leading to cell death in lung cancer cell lines. Flow cytometry analysis revealed that 9c caused an increase in intracellular reactive oxygen species (ROS) and a depolarization of the mitochondrial membrane potential. The binding mode of 1,3,5-triazine derivatives to hA₁ and hA₃ AR were predicted by a molecular docking study.     

Changing emission of divalent samarium doped into barium octoborate as a function of firing time

Barium octoborate has been synthesized by air firing of co-precipitated borates with additional boric acid. During the firing process, samarium ions doped into the matrix are reduced to the divalent state. Two different divalent samarium emission spectra have been observed from the material as a function of the firing history, even though the structure, as identified by powder X-ray diffraction remained consistent. A minor barium pentaborate impurity, in conjunction with significant thermal variability in the strength of the divalent samarium emission generated by the different sites in the two borate materials, appears to give rise to this phenomenon.     

Characterization of amiodarone metabolites and impurities using liquid chromatography/atmospheric pressure chemical ionization mass spectrometry

Using the high performance liquid chromatography/atmospheric pressure chemical ionization tandem mass spectrometry (HPLC/APCI-MS/MS) technique, together with established trends from the literature, the structures of metabolites and impurities of amiodarone, an anti-arrhythmic drug, have been assigned. By comparing analyses of products of incubation with rat liver microsomes with controls in which glucose 6-phosphate dehydrogenase was omitted, metabolites could be distinguished from impurities. Structures for the two proposed metabolites and four impurities are proposed.     

Enantioselective Iridium‐Catalyzed Allylation of Acetylenic Ketones via 2‐Propanol‐Mediated Reductive Coupling of Allyl Acetate: C14‐C23 of Pladienolide D

Highly enantioselective catalytic reductive coupling of allyl acetate with acetylenic ketones occurs in a chemoselective manner in the presence of aliphatic or aromatic ketones. This method was used to construct C14‐C23 of pladienolide D in half the steps previously required.