Shortwave infrared absorbing and fluorescent BODIPY J-aggregates for high-contrast imaging.

J-Aggregates hold significant promise for high-resolution shortwave infrared (SWIR) imaging, yet achieving robust SWIR absorption and emission simultaneously has been hindered by hypsochromic shifts in absorption and emission quenching caused by undesirable H- and random aggregation. To address this, we developed highly fluorescent BODIPY J-aggregates exhibiting absorption and emission spanning 1000-1600 nm. A key innovation was the implementation of a zig-zag molecular design, which effectively suppressed H-aggregation and minimized intermolecular interactions, thereby enabling anti-quenching SWIR emission.

Photoredox catalytic asymmetric dearomative [3 + 2] cycloaddition of isoquinolines with enones.

Asymmetric dearomative photocycloaddition has emerged as a transformative strategy for the enantioselective construction of complex three-dimensional molecular architectures from simple planar aromatic precursors. While significant progress has been made in this field, the scope has largely been confined to electron-rich and electron-neutral aromatic systems. Herein, we present a breakthrough with the development of the direct asymmetric dearomative photocycloaddition involving electron-deficient isoquinolines.

Optimization of aquaculture wastewater treatment systems: based on the isolation of the strain Acinetobacter sp. LF10.

A highly efficient denitrifying bacterial strain (Acinetobacter sp. LF10) was isolated in this study, strain LF10 efficiently removed ammonium (98.02 ± 0.

The ConPET Mechanism Remains Veiled: Reply to "Unlocking the ConPeT Mechanism".

In this journal, a Correspondence by Ventura, Cozzi, and Ceroni reported time-resolved absorption spectroscopy studies in the electron transfer process from cyanoarene photocatalyst 3,4,5,6-tetrakis(diphenyl amino)phthalonitrile (4DPAPN) in the presence of tetrabutylammonium oxalate (TBAOx). This was used as a model reaction to investigate the mechanism of consecutive photoinduced electron transfer (ConPET) in our previously reported asymmetric [3+2] photocycloaddition. They proposed a new electron transfer pathway in which the electron from the excited state of the radical anion 4DPAPN* solvated in acetonitrile.

Photocatalytic Asymmetric Oxidation of Phosphines with Water.

P-chiral tertiary phosphine oxides (TPOs) hold significant synthetic value due to their capacity to serve as versatile precursors for a wide range of valuable P-chiral phosphorus-containing compounds. However, the direct asymmetric oxidation of readily available phosphines into these TPOs remains a substantial challenge, as no efficient and practical methods have been reported to date. In this study, we present the first catalytic asymmetric approach to access P-chiral TPOs through a photoredox-mediated radical process.

Bioactive constituents from Salacia obovatilimba as potential in vitro hSGLT2 inhibitors.

Sixteen compounds including twelve previously undescribed sesquiterpenes were isolated from Salacia obovatilimba. Based on HRESIMS, IR, NMR and electronic circular dichroism (ECD) spectroscopic analysis, the previously undescribed compounds were characterized as twelve undescribed dihydro-β-agarofuran sesquiterpenoids (compounds 1-12). The structures of compounds 1 and 6 were confirmed by single-crystal X-ray diffraction.

[A new nor-clerodane diterpenoid from Croton lauioides].

The chemical constituents of the chloroform extract of the 90% methanol extract obtained from the dried branches and leaves of Croton lauioides were investigated. By using silica gel column chromatography, C_(18 )column chromatography, MCI column chromatography, and semi-preparative high-performance liquid chromatography(HPLC), six compounds were isolated. Their structures were identified as lauioidine(1), 2α-methoxy-8α-hydroxy-6-oxogermacra-1(10),7(11)-dien-8,12-olide(2), myrrhanolide B(3), gossweilone(4), 6β,7β-epox-4α-hydroxyguaian-10-ene(5), and 4(15)-eudesmane-1β,5α-diol(6) by analyzing the HR-ESI-MS, IR, ECD, 1D NMR and 2D NMR data, as well as their physicochemical properties.

Photochemical Synthesis of α-Substituted Vinylazaarenes Enabled by Thia-Paternò-Büchi Reactions.

The thia-Paternò-Büchi reaction represents a significant approach for accessing thio compounds, such as thia-cyclobutanes and the corresponding thiols generated upon ring-opening of thia-cyclobutanes. Herein, we report a novel paradigm of this classical reaction wherein thiols can undergo further elimination to form olefins. Consequently, under visible-light irradiation, 2-azaarenethiones react efficiently with various α-Bpin-substituted olefins, yielding synthetically valuable α-substituted vinylazaarenes in high yields.

Triplet Energy Transfer-Based Deracemization of Axially Chiral Alkenes Enabled by a Dual Catalyst System.

Photochemical deracemization has been recognized as a highly efficient strategy in asymmetric synthesis. Consequently, several pivotal chiral photosensitizers have been developed to participate in energy transfer (EnT)-based mechanisms. Nevertheless, the limited diversity of catalyst types and the pronounced spatial effects of photosensitizer moieties on enantioselectivity present an inherent challenge, thereby significantly restricting the substrate scope.

Outer membrane vesicles of Glaesserlla parasuis activate the endosomal cGAS-STING-IRF3 pathway through nucleic acid payload delivery: a biological perspective on host defense protocol optimization.

Glaesserlla parasuis (G. parasuis), a Gram-negative pathogen responsible for Glässer's disease, employs outer membrane vesicles (OMVs) as sophisticated nanoscale effectors to modulate host‒pathogen interplay. While bacterial OMVs are recognized as critical mediators of virulence dissemination, their functional orchestration in G.

Dynamic Photoacoustic Imaging of Mobile Cu(II) in Vivo via Catalytic Radical Cation Formation.

Copper dyshomeostasis is associated with various diseases, making in vivo spatiotemporal imaging of mobile Cu(II) dynamics crucial for understanding pathophysiological mechanisms. However, imaging mobile Cu(II) dynamics remains a long-standing challenge due to the limitations of conventional probes in distinguishing between mobile and bound Cu(II). Herein, we developed a design strategy based on catalytic arylamine radical cation formation, enabling the creation of photoacoustic probes with superior sensitivity and micron-resolution imaging capabilities in the short-wave infrared region, specifically in response to mobile Cu(II).

Precise construction of spiro stereocenters enantioselective radical addition through modulating photocatalysis from redox to energy transfer.

Chiral hydrogen-bonding catalysis has been successfully applied in a wide range of asymmetric photocatalytic radical-based reactions. However, it faces intrinsic challenges in the reactions that rely on oxidative quenching to initiate transformations. A critical issue arises from the formation of anionic side intermediates, which preferentially interact with protons from chiral catalysts, undermining the essential enantiocontrol required for effective product formation.

[A new triterpenoid from Elephantopus scaber].

The chemical constituents of the petroleum ether extract derived from the 90% ethanol extract of Elephantopus scaber were investigated. By silica gel column chromatography, C_(18), MCI column chromatography and semi-preparative high performance liquid chromatography, ten compounds were isolated. Their structures were identified as 3β-hydroxy-6β,7β-epoxytaraxeran-14-ene(1), 3β-hydroxyolean-12-en-28-oic acid(2), D-friedoolean-14-ene-3β,7α-diol(3), 3β-hydroxy-11α-methoxyolean-12-ene(4), 3β-hydroxyolean-11,13(18)-diene(5), 11α-hydroxy-β-amyrin(6), betulinic acid(7), 3β-hydroxy-30-norlupan-20-one(8), 6-acetonylchelerythrine(9), and 4',5'-dehydrodiodictyonema A(10) by analysis of the 1D NMR, 2D NMR, MS, and IR spectral data.

Visible-light-driven enantioselective protonation: a new Frontier in asymmetric catalysis.

Enantioselective protonation represents a direct and effective method for constructing tertiary carbon stereocenters, which are prevalent in natural products and bioactive compounds. However, achieving catalytic asymmetric protonation has long posed challenges due to difficulties in controlling stereoselectivity. The small size of protons and their rapid transfer rates complicate the selective delivery to active intermediates, resulting in convoluted reaction pathways and pronounced background reactions.

Chiral Lewis Acid-Catalyzed Intramolecular [2 + 2] Photocycloaddition: Enantioselective Synthesis of Azaarene-Functionalized Azabicyclo[2.1.1]hexanes and Bicyclo[1.1.1]pentanes.

We present an asymmetric intramolecular [2 + 2] photocycloaddition reaction enabled by a dual catalyst system involving DPZ as a photosensitizer and chiral Sc(III) complex, leading to azaarene-functionalized 2-azabicyclo[2.2.1]hexanes (aza-BCHs).

Kinetic Resolution of Racemic Radicals in Asymmetric Photoredox Minisci Reactions with Azaarenes for Precise Construction of Two Non-adjacent Stereocenters.

Despite the significant potential of photocatalysis as a robust synthetic tool, the high reactivity of radicals often presents challenges in achieving optimal chemoselectivity. In this study, we demonstrate that this inherent limitation can be strategically harnessed for asymmetric photoredox catalysis. By utilizing a chiral catalyst to facilitate kinetic resolution between the two enantiomers of racemic radical intermediates, one enantiomer selectively undergoes the desired transformation, while noncatalytic side reactions deplete the other enantiomer.

Asymmetric copper-catalyzed hydrophosphinylation of ethynylazaarenes to access -chiral 2-azaaryl-ethylphosphine oxides.

We report a cost-effective approach for the enantioselective hydrophosphinylation of ethynylazaarenes utilizing a chiral copper catalytic platform. This strategy efficiently converts racemic secondary phosphine oxides (SPOs) into -chiral tertiary phosphine oxides (TPOs) bearing functionalized olefin substituents with azaarene moieties, achieving high yields and exceptional enantioselectivities. These adducts serve as crucial intermediates in the development of valuable chiral 1,5-hybrid ,-ligands.

Chiral Primary Amine-Catalyzed Asymmetric Photochemical Reactions of Pyridotriazoles with Boronic Acids to Access Triarylmethanes.

Imine-containing azaarene-based triarylmethanes are vital molecular motifs that are prevalent in a wide array of bioactive compounds. Recognizing the limitations of current synthetic methodologies─marked by a scarcity of examples and difficulties in flexible functional group modulation─we have developed an efficient and modular asymmetric photochemical strategy employing pyridotriazoles and boronic acids as substrates. Utilizing novel chiral diamine-derived pyrroles and primary amines as catalysts, we successfully synthesized a diverse range of triarylmethanes with high yields and excellent enantioselectivities.

Catalytic asymmetric photocycloaddition reactions mediated by enantioselective radical approaches.

The use of olefins in the construction of cyclic compounds represents a powerful strategy for advancing the pharmaceutical industry. Photocycloaddition has attracted significant interest from chemists due to its ability to exploit simple and readily available olefins along with their reaction patterns under mild conditions. Moreover, the sustainable and versatile pathways for generating highly reactive intermediates can greatly enrich both substrate diversity and reaction patterns.

From Radical Coupling to Enantioselective Controlled Protonation: Advancing Precise Construction of Stereocenters.

Recent advancements in green and sustainable platforms, particularly visible light-driven photocatalysis, have spurred significant progress in radical chemistry, enabling the efficient synthesis of important molecules from simple and readily available feedstocks under mild conditions. However, the rapid orbital flipping and high reactivity of radicals pose substantial challenges for achieving precise enantiocontrol in stereocenter formation via radical coupling. In this study, we present a generic and efficient strategy that modulates this elusive approach, facilitating enantiocontrollable protonation through 1,3-boron migration.

Asymmetric Photoredox Catalytic Minisci-Type Reactions of α-Bromide Amides.

An asymmetric photoredox catalytic Minisci-type reaction between α-bromide amides and imine-containing azaarenes has been successfully developed. This catalyst system employs a chiral phosphoric acid alongside 3DPAFIPN as a photosensitizer. The reaction produces a diverse array of valuable amides, featuring azaarene-substituted tertiary carbon stereocenters at the β-position, in high yields (up to 85%) and good to excellent enantioselectivities (up to >99% enantiomeric excess (ee)).

Evolutionary insights and expression patterns of sex-related gene families in the zig-zag eel Mastacembelus armatus.

The zig-zag eel exhibits both sexual dimorphism and sex reversal, making it crucial to understand the mechanisms of sex determination and differentiation. Additionally, the wild populations of the zig-zag eel are significantly declining, emphasizing the need for urgent conservation efforts. In this study, we identified 7 Dmrt, 62 HMG-box, and 73 TGF-β family members in the zig-zag eel genome.

Chromosome-level genome assembly of the ratmouth barbel, Ptychidio jordani.

The ratmouth barbel (Ptychidio jordani) is a critically endangered freshwater fish from the Cyprinidae family, primarily due to overfishing and habitat disruption. To address the challenges of its shrinking wild populations and the difficulties in artificial reproduction, we sequenced, assembled, and annotated a high-quality chromosome-level genome of P. jordani using next-generation short-read sequencing, third-generation long-read sequencing, and Hi-C sequencing.

Motion Planning and Control with Environmental Uncertainties for Humanoid Robot.

Humanoid robots are typically designed for static environments, but real-world applications demand robust performance under dynamic, uncertain conditions. This paper introduces a perceptive motion planning and control algorithm that enables humanoid robots to navigate and operate effectively in environments with unpredictable kinematic and dynamic disturbances. The proposed algorithm ensures synchronized multi-limb motion while maintaining dynamic balance, utilizing real-time feedback from force, torque, and inertia sensors.