Organoboron-thiophene-based polymer electrodes for high-performance lithium-ion batteries.

Polymer electrodes are drawing widespread attention to the future generation of lithium-ion battery materials. However, weak electrochemical performance of organic anode materials still exists, such as low capacity, low rate performance, and low cyclability. Herein, we successfully constructed a donor-acceptor thiophene-based polymer (PBT-1) by introducing an organoboron unit. The charge delocalization and lower LUMO energy level due to the unique structure enabled good performance in electrochemical tests with a reversible capacity of 405 mA h g-1 at 0.5 A g-1 and over 10 000 cycles at 1 A g-1. Moreover, electron paramagnetic resonance (EPR) spectra revealed that the unique stable spin system in the PBT-1 backbone during cycling provides a fundamental explanation for the highly stable electrochemical performance. This work offers a reliable reference for the design of organic anode materials and expands the potential application directions of organoboron chemistry.

Organoboron flank-substituted donor-acceptor polymer anode with ultra-long cycling stability for lithium ion batteries.

The tunable structure and other properties of organic materials suggest that they can potentially solve the shortcomings of traditional anodes such as graphite. We successfully introduced an organoboron unit into the thiophene-based polymer PBT-2 to construct a donor-acceptor polymer anode. The charge delocalization and LUMO energy level resulting from the unique structure of this material enabled good redox activity and a very stable electrochemical performance in electrochemical tests, with a reversible capacity of 262 mA h g-1 at 0.5 A g-1 and >10 000 cycles at 1 A g-1 with a decay of 0.056‰ per cycle. Accordingly, targeted structural design to overcome the shortcomings of active units such as thiophene can effectively regulate their electrochemical performance, providing a solution for the development of high-performance anode materials for use in lithium ion batteries.

Bidentate selenium-based chalcogen bond catalyzed cationic polymerization of p-methoxystyrene.

The application of selenium-based non-covalent bond catalysis in living cationic polymerization has rarely been reported. In this work, the cationic polymerization of p-methoxystyrene (pMOS) was performed using a bidentate selenium bond catalyst - a new water-tolerant Lewis acid catalyst. A polymer with controllable molecular weight and narrow molecular weight distribution can be obtained at room temperature, with a maximum molecular weight of 23.3 kDa. This selenium bond compound can also catalyze the controllable cationic polymerization of p-methoxy styrene under environmental conditions. By changing the monomer feeding ratio, a secondary feeding experiment and DFT analysis, it is shown that the selenium bond catalyst can induce polymer chain growth by reversibly activating dormant covalent bonds (C-OH).

Tetrabutylammonium Halides as Selectively Bifunctional Catalysts Enabling the Syntheses of Recyclable High Molecular Weight Salicylic Acid-Based Copolyesters.

To synthesize high molecular weight poly(phenolic ester) via a living ring-opening polymerization (ROP) of cyclic phenolic ester monomers remains a critical challenge due to serious transesterification and back-biting reactions. Both phenolic ester bonds in monomer and polymer chains are highly active, and it is difficult so far to distinguish them. In this work, an unprecedented selectively bifunctional catalytic system of tetra-n-butylammonium chloride (TBACl) was discovered to mediate the syntheses of high molecular weight salicylic acid-based copolyesters via a living ROP of salicylate cyclic esters (for poly(salicylic methyl glycolide) (PSMG), Mn =361.8 kg/mol, Ð<1.30). Compared to previous catalysis systems, the side reactions were suppressed remarkably in this catalysis system because phenolic ester bond in monomer can be selectively cleaved over that in polymer chains during ROP progress. Mechanistic studies reveal that the halide anion and alkyl-quaternaryammonium cation work synergistically, where the alkyl-quaternaryammonium cation moiety interacts with the carbonyl group of substrates via non-classical hydrogen bonding. Moreover, these salicylic acid-based copolyesters can be recycled to dimeric monomer under solution condition, and can be recycled to original monomeric monomers without catalyst under sublimation condition.

Efficient Access to Sequence-Controlled Poly(α-hydroxy acids) with Ax(BC)yDz-Type and Ax(BC)yAz-Type Triblock Structures via Self-Switchable Ring-Opening Polymerization of Monomer Mixtures.

Synthesizing block-sequence-controlled poly(α-hydroxy acids) of three or four α-hydroxy acids remains challenging in one step. In this study, a strategy was employed using three monomers of O-carboxyanhydrides (OCAs) consisting of one α-hydroxy acid (A), asymmetric cyclic diester (B and C, two different α-hydroxy acids of B and C), and symmetric cyclic diester (one α-hydroxy acid of D) with remarkably different activities toward a stereoselective, regioselective, and chemoselective initiator of a zirconium complex. Then, via a self-switchable approach, these monomers can be copolymerized in a well-controlled block sequence of Ax(BC)yDz and Ax(BC)yAz without an external stimulus. Moreover, upon addition of more monomer mixtures during the copolymerization process, more complicated sequence-controlled poly(α-hydroxy acids) can be achieved with up to 15 blocks.

Replacing CC Unit with B←N Unit in Isoelectronic Conjugated Polymers for Enhanced Photocatalytic Hydrogen Evolution.

Three linear isoelectronic conjugated polymers PCC, PBC, and PBN are synthesized by Suzuki-Miyaura polycondensation for photocatalytic hydrogen (H2 ) production from water. PBN presented an excellent photocatalytic hydrogen evolution rate (HER) of 223.5 µmol h-1 (AQY420  = 23.3%) under visible light irradiation, which is 7 times that of PBC and 31 times that of PCC. The enhanced photocatalytic activity of PBN is due to the improved charge separation and transport of photo-induced electrons/holes originating from the lower exciton binding energy (Eb ), longer fluorescence lifetime, and stronger built-in electric field, caused by the introduction of the polar B←N unit into the polymer backbone. Moreover, the extension of the visible light absorption region and the enhancement of surface catalytic ability further increase the activity of PBN. This work reveals the potential of B←N fused structures as building blocks as well as proposes a rational design strategy for achieving high photocatalytic performance.

Monomer-Promoting Asymmetric Kinetic Resolution-Alternating Copolymerization To Afford AAB-Type Copolyesters.

Living copolymerization of mixed monomers can enrich the diversity of copolymer materials with well-defined performance via controlling both monomers and stereosequences. However, periodic sequence-controlled living copolymerization of same-type monomers with more than two components in synthetic polymer science remains a challenge. In this work, a new method of monomer-promoting asymmetric kinetic resolution-alternating copolymerization can let a tricomponent mixture of l-lactide (S,S-LA or l-LA) and two enantiomeric isomers of racemic tropic acid cyclic esters (tropicolactone) be polymerized into sequence-controlled -(ASASBS)n- type biodegradable copolyesters (the subscript S presents the configuration and A and B present lactic acid units and tropic acid units, respectively), and diblock copolymers of -(ASASBS)n-b-(ARARBR)n- can further be obtained upon addition of R,R-LA (d-LA). Compared to previous asymmetric kinetic resolutions of racemic chemicals via polymerization or organic reactions, no enantiopure catalyst/initiator is required in this system. After the resolution and alternating copolymerization of S,S-LA and rac-tropicolactone, the ee value of unreacted tropicolactone can reach 99.4%. The alternating probability between tropicolactone and lactide monomers is more than 96% in periodic sequence polymers of -(ASASBS)n-. The tetracomponent mixture of rac-lactide and rac-tropicolactone can be copolymerized into an alternating copolymer with a -((ASASBS)x-ran-(ARARBR)y)n- structure, in which the stereoselective linkage probability of 95% after S,S-lactide (R,R-lactide) followed by S-tropicolactone (R-tropicolactone) keeps very high too.

Two-Step Redox in Polyimide: Witness by In Situ Electron Paramagnetic Resonance in Lithium-ion Batteries.

Organic materials are promising candidates for future rechargeable batteries, owing to their high natural abundance and rapidly redox reaction. Elaborating the charge/discharge process of organic electrode is critical to unveil the fundamental redox mechanism of lithium-ion batteries (LIBs), but monitoring of this process is still challenging. Here, we report a nondestructive electron paramagnetic resonance (EPR) technique to real-time detect the electron migration step within polyimide cathode. From in situ EPR tests, we vividly observe a classical redox reaction along with two-electron transfer which only shows one pair of peaks in the cyclic voltammetry curve. The radical anion and dianion intermediates are detailed delineation at redox sites in EPR spectra, which can be further confirmed through density functional theory calculations. This approach is especially crucial to elaborate the correlation behind electrochemical and molecular structure for multistep organic-based LIBs.

Enhanced Built-in Electric Field Promotes Photocatalytic Hydrogen Performance of Polymers Derived from the Introduction of B←N Coordination Bond.

High concentrations of active carriers on the surface of a semiconductor through energy/electron transfer are the core process in the photocatalytic hydrogen production from water. However, it remains a challenge to significantly improve photocatalytic performance by modifying simple molecular modulation. Herein, a new strategy is proposed to enhance the photocatalytic hydrogen evolution performance using boron and nitrogen elements to construct B←N coordination bonds. Experimental results show that polynaphthopyridine borane (PNBN) possessing B←N coordination bonds shows a hydrogen evolution rate of 217.4 µmol h-1 , which is significantly higher than that of the comparison materials 0 µmol h-1 for polyphenylnaphthalene (PNCC) and 0.66 µmol h-1 for polypyridylnaphthalene (PNNC), mainly attributed to the formation of a strong built-in electric field that promotes the separation of photo-generated electrons/holes. This work opens up new prospects for the design of highly efficient polymeric photocatalysts at the molecular level.

Synthesis of Linear to Cyclic Polylactide via a One-Pot Step-Wise Ring-Opening Polymerization and Back-Biting Reaction of Ring Closure Using Magnesium Complexes.

The controllable synthesis of cyclic polylactide remains a challenging topic so far. In this work, a new strategy of one-pot step-wise ring-opening polymerization (ROP) followed by a back-biting reaction of ring closure was reported, in which one magnesium atrane-like complex {N,N-bis[3,5-di-cumyl-2-benzyloxy]-[2-(2-aminoethoxy)ethoxy]magnesium} was utilized to initiate the ROP of lactide using 4-dimethylaminopyridine as a co-catalyst; then, macrocyclic polylactides were liberated out via increasing temperature after complete depletion of the monomer in which a back-biting reaction was utilized as a ring-closure method. The living feature at the first ROP stage can be proved well by the controllable molecular weights ranging from 3.10 to 34.70 kDa and narrow molecular weight distributions of linear polylactides obtained after quenching the reaction. The final cyclic polylactides with molecular weights (vs polystyrene) ranging from 2.50 to 16.10 kDa can be achieved too after the back-biting reaction of ring closure. Although a shoulder peak at the gel permeation chromatography profile appears when the ratio of monomer:initiator is high up to 100:1 or 200:1, this system is suitable for the controllable syntheses of cyclic polylactides with desirable modest molecular weights.

Piperlongumine increases the sensitivity of bladder cancer to cisplatin by mitochondrial ROS.

BACKGROUND: The development of cisplatin resistance often results in cisplatin inefficacy in advanced or recurrent bladder cancer. However, effective treatment strategies for cisplatin resistance have not been well established. METHODS: Gene expression was measured by qRT-PCR and Western blotting. CCK-8 assay was performed to detect cell survival. The number of apoptotic cells was determined using the Annexin V-PI double-staining assay. The level of reactive oxygen species (ROS) was measured using 2',7'-dichlorodihydrofluorescein diacetate fluorescent dye, and the ATP level was detected using an ATP measurement kit. RESULTS: The expression of receptor-interacting protein kinase 1 (RIPK1), a key regulator of necroptosis, gradually decreased during cisplatin resistance. We first used piperlongumine (PL) in combination with cisplatin to act on cisplatin-resistant BC cells and found that PL-induced activation of RIPK1 increased the sensitivity of T24 resistant cells to cisplatin treatment. Furthermore, we revealed that PL killed T24 cisplatin-resistant cells by triggering necroptosis, because cell death could be rescued by the mixed lineage kinase domain-like (MLKL) protein inhibitor necrotic sulfonamide or MLKL siRNA, but could not be suppressed by the apoptosis inhibitor z-VAD. We further explored the specific mechanism and found that PL activated RIPK1 to induce necroptosis in cisplatin-resistant cells by stimulating mitochondrial fission to produce excessive ROS. CONCLUSIONS: Our results demonstrated the role of RIPK1 in cisplatin-resistant cells and the sensitization effect of the natural drug PL on bladder cancer. These may provide a new treatment strategy for overcoming cisplatin resistance in bladder cancer.

Reductive Alkylation of Alkenyl Acetates with Alkyl Bromides by Nickel Catalysis.

Catalytic alkylation of stable alkenyl C-O electrophiles is synthetically appealing, but studies to date have typically focused on the reactions with alkyl Grignard reagents. We report herein a cross-electrophile reaction of alkenyl acetates with alkyl bromides. This work has enabled a new method for the synthesis of aliphatic alkenes from alkenyl acetates to be established that can be used to add more structural complexity and molecular diversity with enhanced functionality tolerance. The method allows for a gram-scale reaction and modification of biologically active molecules, and it affords access to useful building blocks. Preliminary mechanistic studies reveal that the NiI species plays an essential role for the success of the coupling of these two reactivity-mismatched electrophiles.

lncRNA HLA Complex Group 18 (HCG18) Facilitated Cell Proliferation, Invasion, and Migration of Prostate Cancer Through Modulating miR-370-3p/DDX3X Axis.

Long non-coding RNAs (lncRNAs) have been reported to exert critical functions in the malignant development of many cancers. lncRNA HLA complex group 18 (HCG18) has been confirmed to have a promoting effect on various cancers. However, whether HCG18 functions in PC is still unclear. Therefore, the current study aimed at unveiling the role of HCG18 in PC progression and its regulatory mechanism on the biological behaviors of PC. Here, RT-qPCR was utilized to detect HCG18 expression, and then, functional experiments were conducted to verify the effects of HCG18 on PC cell proliferation, migration, invasion, and apoptosis. According to the results, HCG18 was significantly up-regulated in PC cells and it facilitated cell proliferation, migration, and invasion in PC. Furthermore, a series of mechanism experiments were carried out to verify the relationship among HCG18, miR-370-3p, and DEAD-box helicase 3 X-linked(DDX3X) in PC cells. Final rescue assays showed that DDX3X overexpression could reverse the inhibitory function of silencing HCG18 on PC progression. In summary, our study showed that lncRNA HCG18 accelerated cell proliferation, invasion, and migration of PC via up-regulating DDX3X through sponging miR-370-3p, providing a novel finding about PC-related regulatory mechanism.

Nanostructured Lateral Boryl Substitution Conjugated Donor-Acceptor Oligomers for Visible-Light-Driven Hydrogen Production.

Poor charge separation is the main factor that limits the photocatalytic hydrogen generation efficiency of organic conjugated polymers. In this work, a series of linear donor-acceptor (D-A) type oligomers are synthesized by a palladium-catalyzed Sonogashira-Hagihara coupling of electron-deficient diborane unit and different dihalide substitution sulfur functionalized monomers. Such diborane-based A unit exerts great impact on the resulting oligomers, including distinct semiconductor characters with isolated lowest unoccupied molecular orbital (LUMO) orbits locating in diborane-containing fragment, and elevated LUMO level higher than water reduction potential. Relative to A-A type counterpart, the enhanced dipole polarization effect in D-A oligomers facilitates separation of photogenerated charge carriers, as evidenced by notably prolonged electron lifetime. Owing to π-π stacking of rigid backbone, the oligomers can aggregate into an interesting 2D semicrystalline nanosheet (≈2.74 nm), which is rarely reported in linear polymeric photocatalysts prepared by similar carbon-carbon coupling reaction. Despite low surface area (30.3 m2 g-1 ), such ultrathin nanosheet D-A oligomer offers outstanding visible light (λ > 420 nm) hydrogen evolution rate of 833 µmol g-1 h-1 , 14 times greater than its A-A analogue (61 µmol g-1 h-1 ). The study highlights the great potential of using boron element to construct D-A type oligomers for efficient photocatalytic hydrogen generation.

Isotactic-Alternating, Heterotactic-Alternating, and ABAA-Type Sequence-Controlled Copolyester Syntheses via Highly Stereoselective and Regioselective Ring-Opening Polymerization of Cyclic Diesters.

Synthesizing different types of sequence-controlled copolyesters can enrich the diversity of copolyesters and modify their properties more precisely, but it is still a challenge to synthesize a complicated sequence-controlled copolyester using different hydroxy acids in a living polymerization manner. In this work, a highly regioselective and stereoselective catalytic system was developed to synthesize biorenewable and biodegradable copolyesters of mandelic acid and lactic acid with isotactic-alternating, heterotactic-alternating, and ABAA-type precise and complicated sequences. Because of the regular incorporation of mandelic acid into polylactide, these sequence-controlled copolymers of mandelic acid and lactic acid show higher glass-transition temperatures than polylactide and a random copolymer. A stereocomplexation interaction between two opposite enantiomeric isotactic polymer chains was also discovered in the isotactic-alternating copolymer.

Ring-Opening Alternating Copolymerization of O-Carboxyanhydrides of Lactic Acid and Malic Acid Using Hafnium Alkoxide Initiators with Different Stereo Selectivities and Activities.

Monomer sequence controllable syntheses of copolymers, including copolyesters, remain a challenge in polymer science. Although alternating sequence-controlled copolymerization of O-carboxyanhydrides (OCAs) can be achieved via using syndioselective initiators, the alternating copolymerization of lactic acid-derived O-carboxyanhydride (LacOCA) with other monomers still suffers from a lack of highly syndioselective initiators. In this work, a highly syndioselective system for the ring-opening polymerization (ROP) of LacOCA was achieved using a bulky amine tris(phenolate) hafnium alkoxide initiator with a high Pr value of 0.91. However, the stereoselectivities of amine tris(phenolate) hafnium alkoxide initiators for the ROP of malic acid O-carboxyanhydride (MalOCA) change to be modestly or lowly isoselective. Interestingly, despite the different stereoselectivities of this system for the two different monomers, the high syndioselectivity of the initiator for the ROP of LacOCA and the low activity of MalOCA in the ROP allow comparatively high rates of cross-propagation; consequently, the ring-opening alternating copolymerization (ROAP) of LacOCA and MalOCA was achieved successfully.

Highly isoselective ring-opening polymerization of rac-O-carboxyanhydrides using a zinc alkoxide initiator.

The stereoselective ring-opening polymerization (ROP) of O-carboxyanhydrides (OCAs) remains a major challenge due to the easy epimerization of monomers. In this work, using a zinc alkoxide initiator, highly efficient ROP of enantiopure 5-methyl-1,3-dioxolane-2,4-dione (LacOCA), 5-benzyl-1,3-dioxolane-2,4-dione (PheOCA), and 5-(4-(benzyloxy)benzyl)-1,3-dioxolane-2,4-dione (Try(Bn)OCA) was achieved without obvious epimerization. Moreover, highly isoselective ROP of rac-LacOCA, rac-PheOCA, and rac-Try(Bn)OCA was successful with the highest isoselectivity of Pm = 0.97 at -70 °C.

Isoselective Ring-Opening Polymerization of rac-Lactide Catalyzed by Sodium/potassium Tetradentate Aminobisphenolate Ion-paired Complexes.

Two sodium/potassium tetradentate aminobisphenolate ion-paired complexes were synthesized and structurally characterized. These ion-paired complexes are efficient catalysts for the ring-opening polymerization of rac-lactide (rac-LA) in the presence of 5 equivalents BnOH as an initiator and the side reaction of epimerization can be suppressed well at low temperatures. The polymerizations are controllable, affording polylactides with desirable molecular weights and narrow molecular weight distributions; the highest molecular weight can reach 50.1 kg mol-1 in this system, and a best isoselectivity of Pm =0.82 was achieved. Such polymerizations have rarely been reported for isoselective sodium/potassium complexes without crown ether as an auxiliary ligand. The solid structures suggest that BnOH can be activated by an interaction with the anion of sodium/potassium complex via a hydrogen bond and that the monomer is activated by coordination to sodium/potassium ion.

Tubular morphology preservation and doping engineering of Sn/P-codoped hematite for photoelectrochemical water oxidation.

Tubular hematite with high-concentration, uniform doping is regarded as a promising material for photoelectrochemical water oxidation. However, the high-temperature annealing commonly used for activating doped hematite inevitably causes deformation of the tubular structure and an increase in the trap states. In the present work, Sn-doped tubular hematite on fluorine-doped tin oxide (FTO) is successfully obtained at 750 °C from a Sn-coated FeOOH tube precursor. Sn/P codoping, which is rarely considered for hematite, is also achieved via a gas phase reaction in phosphide atmosphere. The tubular morphology allows the dopant to diffuse from both the inner and outer surfaces, thus decreasing the doping profile in the radial direction. The even distribution of Sn and P synergetically increases the carrier density of hematite by one order of magnitude, which shortens the width of the depletion layer to ca. 2.3 nm (compared with 19.3 nm for the pristine sample) and leads to prolonged carrier lifetime and efficient charge separation. In addition, this codoping protocol does not introduce additional surface trap states, as evidenced by the increased charge injection efficiency and surface kinetic analysis using intensity modulated photocurrent spectroscopy (IMPS). As a result, the morphology- and doping-engineered hematite exhibits photocurrents of 0.9 mA cm-2 at 1.23 V and 3.8 mA cm-2 at 2.0 V vs. RHE under AM 1.5 G illumination (100 mW cm-2) in 1.0 M NaOH, representing 4.5-fold and 4.8-fold enhancements, respectively, compared with the photocurrents of undoped hematite. The present method is shown to be effective for preparing multi-element-doped hematite nanotubes and may find broad application in the development of other nanotubular photoelectrodes with or without doping for efficient and robust water oxidation.

Diradical Anion of Potassium Aggregate: Reduction of Dimer Boroxide Complex.

Crystalline aggregates containing metal cation clusters "wrapped" by reduced hydrocarbon anions have been presented. Initially, a dimeric complex (2) possessing a bimetallic K2O2 core was synthesized from the reaction between an anthracene substituted boronic acid (2-(anthracen-9-yl)phenyl)(hydroxy)(mesityl)borane (1-H) and KN(SiMe3)2 in THF solution. The B-O bond length (1.281(4) Å) in complex 2 is comparable to those observed in oxoboranes, indicating this may be a double bond, which is supported by its Wiberg bond order (1.9) predicted by density functional theory calculations. Subsequently, potassium aggregate complexes, diradical 3 and dihydro anion 4, were obtained through the reduction reactions of dimeric complex 2 and 1-H, respectively. They exhibit similar K3O2B2 aggregate structures, but differ significantly in the geometry of the anthracene units. Complex 3 features a triplet diradical character with planar anthracene units that carry the unpaired electrons, while the anthracene groups in complex 4 display a puckered structure due to the addition of hydrogen atoms.