Stereoselective Synthesis of Amphoteric α-Haloalkenyl Boronates by Halogenative Semipinacol Rearrangement of B(MIDA)-Propargylic Alcohols.

The facile synthesis of stereo-defined and transformable functionality-enriched building blocks is of great importance in modern organic chemistry, as it allows the rapid and divergent assembly of complex molecules. Herein a halogen electrophile (N-bromosuccinimide and N-iodosuccinimide) initiated semipinacol rearrangement reaction of B(MIDA)-propargylic alcohols (MIDA=N-methyliminodiacetyl) by aryl migration towards the synthesis of amphoteric α-haloalkenyl boronates in moderate to good yields with excellent stereoselectivities is reported. The value of the products is evidenced by their ability to undergo divergent conversions to polysubstituted alkenes through manipulation of the C-B and C-X (X=Br, I) bonds and the carbonyl group.

General Synthesis of N-CF3 Heteroaryl Amides via Successive Fluorination and Acylation of Sterically Hindered Isothiocyanates.

We report the one-pot synthesis of N-CF3 heteroaryl amides (NTFMHA) from heteroaryl carboxylic acids and sterically hindered isothiocyanates, including various amino acid analogues, in the presence of AgF. The key to this reaction is the utilization of free heteroaryl acyl chlorides, rather than their corresponding hydrochloride salts. This method represents a complementary method of our previous work and enables modification to a variety of previously inaccessible structures, including α-tertiary amines and N-CF3-modified pharmaceuticals.

Pyrrolidinium-Based Hyperbranched Anion Exchange Membranes with Controllable Microphase Separated Morphology for Alkaline Fuel Cells.

It is well acknowledged that the microphase-separated morphology of anion exchange membranes (AEMs) is of vital importance for membrane properties utilized in alkaline fuel cells. Herein, a rigid macromolecule poly(methyldiallylamine) (PMDA) is incorporated to regulate the microphase morphology of hyperbranched AEMs. As expected, the hyperbranched poly(vinylbenzyl chloride) (HB-PVBC) is guided to distribute along PMDA chains, and longer PMDA cha leads to a more distinct microphase morphology with interconnected ionic channels. Consequently, high chloride conductivity of 10.49 mS cm-1 at 30 °C and suppressed water swelling ratio lower than 30% at 80 °C are obtained. Furthermore, the ß-H of pyrrolidinium cations in the non-antiperiplanar position increases the energy barrier of ß-H elimination, leading to conformationally disfavored Hofmann elimination and increased alkaline stability. This strategy is anticipated to provide a feasible way for preparing hyperbranched AEMs with clear microphase morphology and good overall properties for alkaline fuel cells.

Grafting of Maleic Anhydride onto Poly(vinylidene fluoride) Using Reactive Extrusion.

Poly(vinylidene fluoride) was grafted with maleic anhydride through reactive extrusion by using diisopropyl benzene peroxide as an initiator and 9-vinyl anthracene as a stabilizer. Effects of various parameters on grafting degree were investigated including the amounts of monomer, initiator and stabilizer. The maximum extent of grafting achieved was 0.74%. The graft polymers were characterized using FTIR, water contact angle, thermal, mechanical and XRD studies. Improved hydrophilic and mechanical properties were observed for graft polymers.

Boryl-Dictated Site-Selective Intermolecular Allylic and Propargylic C-H Amination.

For internal alkenes possessing two or more sets of electronically and sterically similar allylic protons, the site-selectivity for allylic C-H functionalization is fundamentally challenging. Previously, the negative inductive effect from an electronegative atom has been demonstrated to be effective for several inspiring regioselective C-H functionalization reactions. Yet, the use of an electropositive atom for a similar purpose remains to be developed. α-Aminoboronic acids and their derivatives have found widespread applications. Their current syntheses rely heavily on functional group manipulations. Herein we report a boryl-directed intermolecular C-H amination of allyl N-methyliminodiacetyl boronates (B(MIDA)s) and propargylic B(MIDA)s to give α-amino boronates with an exceptionally high level of site-selectivities (up to 300:1). A wide variety of highly functionalized secondary and tertiary α-amino boronates are formed in generally good to excellent yields, thanks to the mildness of the reaction conditions. The unsaturated double and triple bonds within the product leave room for further decorations. Mechanistic studies reveal that the key stabilization effect of the B(MIDA) moiety on its adjacent developing positive charge is responsible for the high site-selectivity and that a closed transition state might be involved, as the reaction is fully stereoretentive. An activation effect of B(MIDA) is also found.

Propelling microdroplets generated and sustained by liquid-liquid phase separation in confined spaces.

Flow transport in confined spaces is ubiquitous in technological processes, ranging from separation and purification of pharmaceutical ingredients by microporous membranes and drug delivery in biomedical treatment to chemical and biomass conversion in catalyst-packed reactors and carbon dioxide sequestration. In this work, we suggest a distinct pathway for enhanced liquid transport in a confined space via propelling microdroplets. These microdroplets can form spontaneously from localized liquid-liquid phase separation as a ternary mixture is diluted by a diffusing poor solvent. High speed images reveal how the microdroplets grow, break up and propel rapidly along the solid surface, with a maximal velocity up to ∼160 µm s-1, in response to a sharp concentration gradient resulting from phase separation. The microdroplet propulsion induces a replenishing flow between the walls of the confined space towards the location of phase separation, which in turn drives the mixture out of equilibrium and leads to a repeating cascade of events. Our findings on the complex and rich phenomena of propelling droplets suggest an effective approach to enhanced flow motion of multicomponent liquid mixtures within confined spaces for time effective separation and smart transport processes.

Surface Nanodroplets: Formation, Dissolution, and Applications.

Droplets at solid-liquid interfaces play essential roles in a broad range of fields, such as compartmentalized chemical reactions and conversions, high-throughput analysis and sensing, and super-resolution near-field imaging. Our recent work has focused on understanding and controlling the nanodroplet formation on solid surfaces in ternary liquid mixtures. These surface nanodroplets resemble tiny liquid lenses with a typical height of <1 µm and a volume of subfemtoliters. The solvent exchange is based on the process of displacing a droplet liquid solution by a poor solvent to create a transient oversaturation for droplet formation. A quantitative understanding of growth dynamics of surface nanodroplets in ternary liquid mixtures not only provides insight into the liquid-liquid phase separation induced by solvent addition in general but also has made it possible to control the droplet size well. This review article will summarize our findings in the last ∼5 years from the research with our collaborators. The first part will explain the fundamental aspects that are key to the formation and stability of surface nanodroplets. In the second part, we will highlight the applications of nanodroplets in chemical analysis and functional surface fabrication and finally point out future directions in droplet-based applications.

Electron Donor-Acceptor Complex Enabled Decarboxylative Sulfonylation of Cinnamic Acids under Visible-Light Irradiation.

Visible-light-induced decarboxylative sulfonylation of cinnamic acids with aryl sulfonate phenol esters enabled by the electron donor-acceptor complex is developed. The method offers a mild and green approach for the synthesis of vinyl sulfones with excellent functional group compatibility under photocatalyst and oxidant-free conditions.

Rhodium-Catalyzed PIII -Directed ortho-C-H Borylation of Arylphosphines.

Transition-metal-mediated metalation of an aromatic C-H bond that is adjacent to a tertiary phosphine group in arylphosphines via a four-membered chelate ring was first discovered in 1968. Herein, we overcome a long-standing problem with the ortho-C-H activation of arylphosphines in a catalytic fashion. In particular, we developed a rhodium-catalyzed ortho-selective C-H borylation of various commercially available arylphosphines with B2 pin2 through PIII -chelation-assisted C-H activation. This discovery is suggestive of a generic platform that could enable the late-stage modification of readily accessible arylphosphines.

An Olefinic 1,2-Boryl-Migration Enabled by Radical Addition: Construction of gem-Bis(boryl)alkanes.

A series of in situ formed alkenyl diboronate complexes from alkenyl Grignard reagents (commercially available or prepared from alkenyl bromides and Mg) with B2 Pin2 (bis(pinacolato)diboron) react with diverse alkyl halides by a Ru photocatalyst to give various gem-bis(boryl)alkanes. Alkyl radicals add efficiently to the alkenyl diboronate complexes, and the adduct radical anions undergo radical-polar crossover, specifically, a 1,2-boryl-anion shift from boron to the α-carbon sp2 center. This transformation shows good functional-group compatibility and can serve as a powerful synthetic tool for late-stage functionalization in complex compounds. Measurements of the quantum yield reveal that a radical-chain mechanism is operative in which the alkenyl diboronates acts as reductive quencher for the excited state of the photocatalyst.

Synthesis of 2-methylbenzoxazoles directly from N-phenylacetamides catalyzed by palladium acetate.

A method to synthesize 2-methylbenzoxazoles directly from N-phenylacetamides catalyzed by Pd(OAc)2 in the presence of K2S2O8 and TfOH has been developed. The desired products were obtained in moderate to excellent yields. This approach provides a facile procedure to prepare benzoxazoles with available substrates. It is found that TfOH is the key factor for this cyclization reaction. A plausible mechanism of the reaction is proposed according to the control reactions and the literature.

Monte Carlo simulations of the phase separation of a copolymer blend in a thin film.

Monte Carlo simulations were carried out to study the phase separation of a copolymer blend comprising an alternating copolymer and/or block copolymer in a thin film, and a phase diagram was constructed with a series of composed recipes. The effects of composition and segregation strength on phase separation were discussed in detail. The chain conformation of the block copolymer and alternating copolymer were investigated with changes of the segregation strength. Our simulations revealed that the segment distribution along the copolymer chain and the segregation strength between coarse-grained beads are two important parameters controlling phase separation and chain conformation in thin films of a copolymer blend. A well-controlled phase separation in the copolymer blend can be used to fabricate novel nanostructures.

Aqueous manganese dioxide ink for paper-based capacitive energy storage devices.

We report a simple approach based on a chemical reduction method to synthesize aqueous inorganic ink comprised of hexagonal MnO2 nanosheets. The MnO2 ink exhibits long-term stability and continuous thin films can be formed on various substrates without using any binder. To obtain a flexible electrode for capacitive energy storage, the MnO2 ink was printed onto commercially available A4 paper pretreated with multiwalled carbon nanotubes. The electrode exhibited a maximum specific capacitance of 1035 F g(-1) (91.7 mF cm(-2)). Paper-based symmetric and asymmetric capacitors were assembled, which gave a maximum specific energy density of 25.3 Wh kg(-1) and a power density of 81 kW kg(-1). The device could maintain a 98.9% capacitance retention over 10 000 cycles at 4 A g(-1). The MnO2 ink could be a versatile candidate for large-scale production of flexible and printable electronic devices for energy storage and conversion.

YTHDC1 inhibits autophagy-dependent NF-κB signaling by stabilizing Beclin1 mRNA in macrophages.

BACKGROUND: YTHDC1, a key m(6)A nuclear reader, plays a crucial role in regulating mRNA splicing, export, and stability. However, the functional significance and regulatory mechanisms of YTHDC1 in inflammatory bowel disease (IBD) remain to be explored. METHODS: We established a dextran sulfate sodium (DSS)-induced murine colitis model in vivo and LPS/IFN-γ-stimulated macrophage inflammation in vitro. The expression of YTHDC1 was determined. Colocalization of YTHDC1 and macrophages was assayed by immunofluorescence staining. LV-YTHDC1 or shYTHDC1 lentiviruses were applied for YTHDC1 overexpression or inhibition. For NF-κB inhibition, JSH-23 was utilized. The interaction of YTHDC1 and Beclin1 mRNA was determined by RIP, and the m6A modification of Beclin1 was confirmed by MeRIP. RESULTS: In DSS-induced colitis and LPS/IFN-γ-treated RAW264.7 macrophages, we observed a significant downregulation of YTHDC1. Overexpression of YTHDC1 resulted in decreased levels of iNOS, CD86, and IL-6 mRNA, along with inhibited NF-κB activation in LPS/IFN-γ-treated RAW264.7 cells. Conversely, downregulation of YTHDC1 promoted iNOS expression and inhibited autophagy. Additionally, the effect of YTHDC1 knockdown on CD86 and IL-6 mRNA induced by LPS/IFN-γ was abolished by the NF-κB inhibitor JSH-23. Mechanistically, YTHDC1 interacted with Beclin1 mRNA, thereby stabilizing Beclin1 mRNA and enhancing Beclin1 expression and autophagy. These effects ultimately led to the inhibition of NF-κB signaling in LPS/IFN-γ-challenged macrophages. CONCLUSIONS: YTHDC1 inhibited the macrophage-mediated inflammatory response by stabilizing Beclin1 mRNA, which may be a potential therapeutic target for the treatment of IBD.

NHC-Au-Catalyzed Isomerization of Propargylic B(MIDA)s to Allenes and Double Isomerization of Alkynes to 1,3-Dienes.

The synthesis of allenyl boronates is an important yet challenging topic in organic synthesis. Reported herein is an NHC-gold-catalyzed 1,3-H shift toward allenyl boronates synthesis from simple propargylic B(MIDA)s. Mechanistic studies suggest dual roles of the boryl moiety in the reaction: to activate the substrate for isomerization and at the same time, to prevent the allene product from further isomerization. These effects should be a result of α-anion stabilization and α-cation destabilization conferred by the B(MIDA) moiety, respectively. The NHC-Au catalyst, which is commercially available, is also found to be reactive in alkyne-to-1,3-diene isomerization reactions in an atom-economic and base-free manner.

Enhanced in-plane thermal conductivity of polyimide-based composites via in situ interfacial modification of graphene.

Interfacial thermal resistance is the main barrier restricting the heat dissipation of thermal management materials in electronic equipment. The interface structure formed by covalent bonding is an effective way to promote interfacial heat transfer. Herein, an integrated composite with multi-aspect covalent bonding beneficial for heat transmission is constructed by polyimide (PI) polymerization with maleimide modified graphene nanosheets (M@GNS). The interfacial structure with low thermal resistance built by covalent bonding and oriented graphene arrangement initiated by the coating process makes the in-plane thermal conductivity of the composite as high as 16.10 W m-1 K-1. Finite element simulation and 1000 bending tests are carried out to further verify the performance advantages of the integrated structure in the internal thermal diffusion and long-term use of the composite. M@GNS/PI with integrated structure provides extra heat transfer channels for heat dissipation, possibly providing an effective way to address the traditional thermal accumulation issue of electronic devices.

Regioselective Electrophilic Addition to Propargylic B(MIDA)s Enabled by ß-Boron Effect.

Electrophilic addition reaction to alkynes is of fundamental importance in organic chemistry, yet the regiocontrol when reacting with unsymmetrical 1,2-dialkyl substituted alkynes is often problematic. Herein, it is demonstrated that the rarely recognized ß-boron effect can confer a high level of site-selectivity in several alkyne electrophilic addition reactions. A broad range of highly functionalized and complex organoborons are thus formed under simple reaction conditions starting from propargylic MIDA (N-methyliminodiacetic acid) boronates. These products are demonstrated to be valuable building blocks in organic synthesis. In addition to the regiocontrol, this study also observes a drastic rate enhancement upon B(MIDA) substitution. Theoretical calculation reveals that the highest occupied molecular obital (HOMO) energy level of propargylic B(MIDA) is significantly raised by 0.3 eV, and the preferential electrophilic addition to the γ position is due to its higher HOMO orbital coefficient and more negative natural bond orbital (NBO) charge compared to the ß position. This study demonstrates the potential of utilizing the ß-boron effect in stereoelectronic control of chemical transformations, which can inspire further research in this area.

Simultaneous photothermal and photocatalytic MOF- derived C/TiO2 composites for high-efficiency solar driven purification of sewage.

Solar-driven water evaporation is a promising technology of freshwater production to address the water scarcity. However, the photothermal material and the distilled water would be contaminated in the evaporation of wastewater including organic pollutants. In this work, MOF-derived C/TiO2 composites (carbonized UiO-66-NH2 (Ti)) with simultaneous photothermal and photocatalytic functions are designed for producing freshwater from sewage. With advantageous features of porous structure with large specific area, excellent sunlight absorption and super-hydrophilicity, the carbonized UiO-66-NH2 (Ti) layer exhibits high water evaporation efficiency of 94% under 1.0 sun irradiation. Meanwhile, the layer can simultaneously decompose the organic pollutants with degradation efficiency of 92.7% in the underlying water during solar-driven water evaporation. This bifunctional material will provide a new approach for solar-driven water evaporation and photocatalytic degradation of organic pollutant synergistically.

Correction to "Facile Synthesis of Vertically Arranged CNTs for Efficient Solar-Driven Interfacial Water Evaporation".

[This corrects the article DOI: 10.1021/acsomega.2c06706.].

Glutathione-depletion reinforced enzyme catalytic activity for photothermal assisted bacterial killing by hollow mesoporous CuO.

The emergence and prevalence of drug-resistant bacteria caused by the overuse of antibiotics pose new challenges to the treatment of bacterial infections. In this work, hollow mesoporous CuO nanozymes (HM-CuO nanozymes) as excellent antibacterial agents were prepared by a template method. The synthesized HM-CuO nanozymes exhibit peroxidase-like catalytic activity, which can efficiently catalyze H2O2 to generate toxic reactive oxygen species (ROS), causing fatal damage to bacteria. Moreover, the hyperthermia of HM-CuO produced by photothermal therapy (PTT) not only effectively kills bacteria but also enhances the catalytic activity of nanozymes and produces more ROS. Moreover, the HM-CuO nanozymes have a glutathione (GSH)-depleting function to effectively consume GSH in bacteria and generate Cu(I) with higher catalytic effect, which can significantly improve the sterilization effect and produce a 100% inhibitory rate against E. coli and S. aureus. Overall, the HM-CuO nanozymes with strong peroxidase-like catalytic activity, excellent photothermal performance and GSH consumption ability offer a promising synergistic strategy for clinical bacterial infection.