Optimized combination of Cervus nippon (Sika deer), Angelica (Dangui), and Rehmannia (Suk-jihwang) mitigates LPS-induced inflammation: exploring signaling pathways through plasma metabolomics.

This study aimed to determine the optimal combination of three anti-inflammatory materials [i.e., Cervus nippon Temminck (CT), Angelica gigas Nakai (AN), and Rehmannia glutinosa (RG)] for the strongest anti-inflammatory potential. Eighteen combinations of the three materials were tested in LPS-stimulated RAW264.7 cells via assessing nitric oxide (NO). The best combination from in vitro studies was administered to LPS-treated C57BL/6J mice for five days. Subsequently, plasma metabolites were profiled by bioinformatics analyses and validations. As results, 2, 20, and 50 µg/mL of CT, AN, and RG (TM) were the most effective combination suppressing inflammation. In mice, TM mitigated hepatic inflammatory markers. Similarly, the metabolomics indicated that TM may suppress NF-κB signaling pathway, thereby alleviating hepatic inflammation. TM also decreased systemic and hepatic pro-inflammatory cytokines. Collectively, we found the optimal combination of TM for mitigating inflammation; thus further studies on safety, mechanisms, and clinical models are warranted for human applications. Supplementary Information: The online version contains supplementary material available at 10.1007/s10068-023-01476-x.

Synthesis of the C28-C41 Side Chain of (Proposed) Neaumycin B: A Contiguous Stereohextet.

The C28-C41 side-chain of the proposed structure of neaumycin B, which encompasses a contiguous stereohextet, is prepared in 8 steps (longest linear sequence). Convergency is maximized via Williams' Felkin-Anh-selective triorganozincate-mediated vinylation of an α,ß-stereogenic aldehyde. The relative stereochemical assignment of the C33-C35 stereotriad was accomplished via the 13C NMR analysis of the related acetonide. Relative stereochemistry of C33 carbinol and C36-C37 glycidol was determined by comparative NOE analysis of the related diastereomeric furans.

N-O Bond Activation by Energy Transfer Photocatalysis.

A radical shift toward energy transfer photocatalysis from electron transfer photocatalysis under visible-light photoirradiation is often due to the greener prospects of atom and process economy. Recent advances in energy transfer photocatalysis embrace unique strategies for direct small-molecule activation and sometimes extraordinary chemical bond formation in the absence of additional/sacrificial reagents. Selective energy transfer photocatalysis requires careful selection of substrates and photocatalysts for a perfect match with respect to their triplet energies while having incompatible redox potentials to prevent competitive electron transfer pathways. Substrates containing labile N-O bonds are potential targets for generating reactive key intermediates via photocatalysis to access a variety of functionalized molecules. Typically, the differential electron densities of N and O heteroatoms have been exploited for generation of either N- or O-centered radical intermediates from the functionalized substrates by the electron transfer pathway. However, the latest developments involve direct N-O bond homolysis via energy transfer to generate both N- and O-centered radicals for their subsequent utilization in diverse organic transformations, also in the absence of sacrificial redox reagents. In this Account, we highlight our key contributions in the field of N-O bond activation via energy transfer photocatalysis to generate reactive radical intermediates, with coverage of useful mechanistic insights. More specifically, well-designed N-O bond-containing substrates such as 1,2,4-oxadiazolines, oxime esters, N-indolyl carbonates, and N-enoxybenzotriazoles were successfully utilized in versatile transformations involving selective energy transfer over electron transfer from photocatalysts with high triplet state energy. Direct access to reactive N-, O-, and C-centered (if decarboxylation follows) radical intermediates was achieved for diverse cross-couplings and rearrangement processes. In particular, a variety of open-shell nitrogen reactive intermediates, including N(sp2) and N(sp3) radicals and nitrenes, have been utilized. Notably, diversified transformations of identical substrates have been achieved through careful control of the reaction conditions. 1,2,4-Oxadiazolines were converted into spiro-azolactams through iminyl intermediates in the presence of 1O2, benzimidazoles, or sulfoximines with external sulfoxide reagent through triplet nitrene intermediates under inert conditions. Besides, oxime esters underwent either intramolecular C(sp3)-N radical-radical coupling or intermolecular C(sp3)-N radical-radical coupling by a combined energy transfer-hydrogen atom transfer strategy. Furthermore, a series of electrochemical and photophysical experiments as well as computational studies were performed to substantiate the proposed selective energy-transfer-driven reaction pathways. We hope that this Account will serve as a guide for the rational design of selective energy transfer processes through the activation of further labile chemical bonds.

Peroxiredoxin 3 deficiency induces cardiac hypertrophy and dysfunction by impaired mitochondrial quality control.

Mitochondrial quality control (MQC) consists of multiple processes: the prevention of mitochondrial oxidative damage, the elimination of damaged mitochondria via mitophagy and mitochondrial fusion and fission. Several studies proved that MQC impairment causes a plethora of pathological conditions including cardiovascular diseases. However, the precise molecular mechanism by which MQC reverses mitochondrial dysfunction, especially in the heart, is unclear. The mitochondria-specific peroxidase Peroxiredoxin 3 (Prdx3) plays a protective role against mitochondrial dysfunction by removing mitochondrial reactive oxygen species. Therefore, we investigated whether Prdx3-deficiency directly leads to heart failure via mitochondrial dysfunction. Fifty-two-week-old Prdx3-deficient mice exhibited cardiac hypertrophy and dysfunction with giant and damaged mitochondria. Mitophagy was markedly suppressed in the hearts of Prdx3-deficient mice compared to the findings in wild-type and Pink1-deficient mice despite the increased mitochondrial damage induced by Prdx3 deficiency. Under conditions inducing mitophagy, we identified that the damaged mitochondrial accumulation of PINK1 was completely inhibited by the ablation of Prdx3. We propose that Prdx3 interacts with the N-terminus of PINK1, thereby protecting PINK1 from proteolytic cleavage in damaged mitochondria undergoing mitophagy. Our results provide evidence of a direct association between MQC dysfunction and cardiac function. The dual function of Prdx3 in mitophagy regulation and mitochondrial oxidative stress elimination further clarifies the mechanism of MQC in vivo and thereby provides new insights into developing a therapeutic strategy for mitochondria-related cardiovascular diseases such as heart failure.

Gas chromatography-mass spectrometry analyses of encapsulated stable perovskite solar cells.

Although perovskite solar cells have produced remarkable energy conversion efficiencies, they cannot become commercially viable without improvements in durability. We used gas chromatography-mass spectrometry (GC-MS) to reveal signature volatile products of the decomposition of organic hybrid perovskites under thermal stress. In addition, we were able to use GC-MS to confirm that a low-cost polymer/glass stack encapsulation is effective in suppressing such outgassing. Using such an encapsulation scheme, we produced multi-cation, multi-halide perovskite solar cells containing methylammonium that exceed the requirements of the International Electrotechnical Commission 61215:2016 standard by surviving more than 1800 hours of the Damp Heat test and 75 cycles of the Humidity Freeze test.

Acetic Acid Assisted Crystallization Strategy for High Efficiency and Long-Term Stable Perovskite Solar Cell.

Improving the quality of perovskite poly-crystalline film is essential for the performance of associated solar cells approaching their theoretical limit efficiency. Pinholes, unwanted defects, and nonperovskite phase can be easily generated during film formation, hampering device performance and stability. Here, a simple method is introduced to prepare perovskite film with excellent optoelectronic property by using acetic acid (Ac) as an antisolvent to control perovskite crystallization. Results from a variety of characterizations suggest that the small amount of Ac not only reduces the perovskite film roughness and residual PbI2 but also generates a passivation effect from the electron-rich carbonyl group (C=O) in Ac. The best devices produce a PCE of 22.0% for Cs0.05FA0.80MA0.15Pb(I0.85Br0.15)3 and 23.0% for Cs0.05FA0.90MA0.05Pb(I0.95Br0.05)3 on 0.159 cm2 with negligible hysteresis. This further improves device stability producing a cell that maintained 96% of its initial efficiency after 2400 h storage in ambient environment (with controlled relative humidity (RH) <30%) without any encapsulation.

Organophotocatalytic Arene Functionalization: C-C and C-B Bond Formation.

Organophotocatalytic C-C and C-B bond formation reactions of aryl halides have been developed in the presence of an organophotosensitizer, 3,7-di([1,1'-biphenyl]-4-yl)-10-(4-(trifluoromethyl)phenyl)-10H-phenoxazine that has highly negative reduction potential at its photoexcited state. The developed reaction conditions are mild and allow the intermolecular C-C bond formation of the generated aryl radical with electron-rich (hetero)arenes and C-B bond formation with bis(pinacolato)diboron.

Fluoroalkenylation of boronic acids via an oxidative Heck reaction.

A fluoroalkenylation of boronic acids with fluoroalkyl alkenes has been developed. The Pd-catalyzed oxidative Heck coupling reaction proceeds under an oxygen atmosphere at room temperature, in the absence of a base and/or a ligand, showing excellent practicality of the process. This simple transformation is highly stereoselective to provide only E-isomers. In addition to the general approach using alkenes with functionalized fluoroalkyl reagents, this method, by transferring an aromatic system to the electron-deficient fluoroalkyl alkene, provides an efficient alternative method to yield valuable organofluorines.

The Impact of a Dynamic Two-Step Solution Process on Film Formation of Cs0.15 (MA0.7 FA0.3 )0.85 PbI3 Perovskite and Solar Cell Performance.

This paper provides deep understanding of the formation mechanism of perovskite film fabricated by sequential solution-based methods. It compares two sequential spin-coating methods for Cs0.15 (MA0.7 FA0.3 )0.85 PbI3 perovskite. First is the "static process," with a stoppage between the two spin-coating steps (1st PbI2 -CsI-dimethyl sulfoxide (DMSO)-dimethylformamide (DMF) and 2nd methylammonium iodide (MAI)-formamidinium iodide (FAI)-isopropyl alcohol). Second is the "dynamic process," where the 2nd precursor is dispensed while the substrate is still spinning from the 1st step. For the first time, such a dynamic process is used for Cs0.15 (MA0.7 FA0.3 )0.85 PbI3 perovskite. Characterizations reveal improved film formation with the dynamic process due to the "retainment" of DMSO-complex necessary for the intermediate phase which i) promotes intercalation between precursors and ii) slows down perovskite crystallization for full conversion. The comparison on as-deposited perovskite before annealing indicates a more ordered film using this dynamic process. This results in a thicker, more uniform film with higher degree of preferred crystal orientation and higher carrier lifetime after annealing. Therefore, dynamic-processed devices present better performance repeatability, achieving a higher average efficiency of 17.0% compared to static ones (15.0%). The new insights provided by this work are important for perovskite solar cells processed sequentially as the process has greater flexibility in resolving solvent incompatibility, allowing separate optimizations and allowing different deposition methods.

Light- and bias-induced structural variations in metal halide perovskites.

Organic-inorganic metal halide perovskites have gained considerable attention for next-generation photovoltaic cells due to rapid improvement in power conversion efficiencies. However, fundamental understanding of underlying mechanisms related to light- and bias-induced effects at the nanoscale is still required. Here, structural variations of the perovskites induced by light and bias are systematically investigated using scanning probe microscopy techniques. We show that periodically striped ferroelastic domains, spacing between 40 to 350 nm, exist within grains and can be modulated significantly under illumination as well as by electric bias. Williamson-Hall analysis of X-ray diffraction results shows that strain disorder is induced by these applied external stimuli. We show evidence that the structural emergence of domains can provide transfer pathways for holes to a hole transport layer with positive bias. Our findings point to potential origins of I-V hysteresis in halide perovskite solar cells.

Visible-Light-Promoted Synthesis of Fluoroalkylated Oximes.

A method has been developed for the synthesis of fluoroalkylated oximes, potential fluoroalkyl building-blocks for the synthesis of various organofluorine compounds, from easily available amino substrates and fluoroalkylated alkenes. tBuONO was utilized both as a diazotizing agent and as a NO radical source for the oxime synthesis in the process, and the use of a photocatalyst under visible-light irradiation increased the efficiency of the reaction. Various fluoroalkylated oximes were prepared by a tandem process of aryl radical addition to fluoroalkylated alkene and consecutive oxime generation process, albeit in moderate yields. This differentiated approach, transferring an aromatic system into an electron-deficient fluoroalkylated alkene, expands the scope of substrates where electron-poor aromatic systems could be utilized.

Extended Study of Visible-Light-Induced Photocatalytic [4 + 2] Benzannulation: Synthesis of Polycyclic (Hetero)Aromatics.

Herein we report an extended study of [4 + 2] benzannulation reactions of 2-(hetero)aryl-substituted anilines with alkynes by visible light photocatalysis. The method requires the use of tBuONO as a diazotizing agent and 0.3 mol % of fac-Ir(ppy)3 as a photocatalyst at room temperature. The reaction proceeded in a chemo- and regioselective manner with high functional group tolerance under mild conditions allowing the preparation of a wide variety of polycyclic (hetero)aromatic compounds, including phenanthrenes, in moderate to high yields. This procedure is amenable to gram-scale synthesis of 9-phenylphenanthrene.

Self-Position of Au NPs in Perovskite Solar Cells: Optical and Electrical Contribution.

Metallic nanoparticles (NPs) exhibit a localized surface plasmon resonance (LSPR) and act as scattering centers and subwavelength antennas, so metallic NPs can be incorporated into perovskite solar cells (PSCs) to effectively improve the light absorption of light harvesting devices. Here, we have embedded Au nanoparticles (NPs) into the hole transport layer (HTL) of the PSCs to investigate the photovoltaic effect of the PSCs with Au NPs. Interestingly, it was found that Au NPs dispersed spiro-OMeTAD HTL solution could naturally end up located near the perovskite layer as the result of the spin-coating step. Solar cell performance observations indicate that the LSPR and electrical effects of Au NPs enhance the photovoltaic response of PSCs, in spite of a slight decrease in the open-circuit voltage (VOC), by causing an incredible improvement in the photocurrent density as a dominant factor.