Photocatalytic, Oxidative Cleavage of C-C Bond in Lignin Models and Native Lignin.

It is challenging to realize the selective C-C bond cleavage of lignin ß-O-4 linkages for production of high-value aromatic chemicals due to its intrinsic inertness and complex structure. Here we report a light-driven, chlorine-radical-based protocol to realize the oxidative C-C bond cleavage in various lignin model compounds catalyzed by commercially available TPT and CaCl2, achieving high conversion and good to high product yields at room temperature. Mechanistic studies reveal that the preferential activation of Cß-H bond facilitates the oxidation and C-C bond cleavage of lignin ß-O-4 model via chlorine radical. Furthermore, this method is also applicable to the depolymerization of natural lignin extracts, furnishing the aromatic oxygenates from the cleavage of Cα-Cß bonds. This study provides experimental foundations to the depolymerization and valorization of lignin into high value-added aromatic compounds.

Topology Controlled All-(Meth)acrylic Thermoplastic Elastomers by Multi-Functional Lewis Pairs-Mediated Polymerization.

It remains challenging to synthesize all-(meth)acrylic triblock thermoplastic elastomers (TPEs), due to the drastically different reactivities between the acrylates and methacrylates and inevitable occurrence of side reactions during polymerization of acrylates. By taking advantage of the easy structural modulation features of N-heterocyclic olefins (NHOs), we design and synthesize strong nucleophilic tetraphenylethylene-based NHOs varying in the number (i.e. mono-, dual- and tetra-) of initiating functional groups. Its combination with bulky organoaluminum [iBuAl(BHT)2] (BHT=bis(2,6-di-tBu-4-methylphenoxy)) constructs Lewis pair (LP) to realize the living polymerization of both acrylates and methacrylates, furnishing polyacrylates with ultrahigh molecular weight (Mn up to 2174 kg ⋅ mol-1) within 4 min. Moreover, these NHO-based LPs enable us to not only realize the control over the polymers' topology (i.e. linear and star), but also achieve triblock star copolymers in one-step manner. Mechanical studies reveal that the star triblock TPEs exhibit better mechanical properties (elongation at break up to 1863 % and tensile strength up to 19.1 MPa) in comparison with the linear analogs. Moreover, the presence of tetraphenylethylene group in the NHOs entitled the triblock TPEs with excellent AIE properties in both solution and solid state.

Direct synthesis of sila-benzoazoles through hydrosilylation and rearrangement cascade reaction of benzoazoles and silanes.

Sila-isosteres have attracted increasing attention due to their potential application in a variety of fields and their different properties compared to their carbon-containing analogs. However, the preparation of these silicon-containing compound remains challenging and thus the development of alternative synthetic methodologies is desirable. Here, we employ B(C6F5)3 as catalyst to enable the synthesis of highly functionalized sila-benzoazoles via hydrosilylation and rearrangement cascade reaction of benzoazoles and commercially available silanes. This strategy also exhibits remarkable features such as 100% atom-economy, good functional group tolerance, broad substrate scope, easy scale-up and good catalytic performance, demonstrating its potential application in sila-isostere synthesis.

Recyclable cyclic bio-based acrylic polymer via pairwise monomer enchainment by a trifunctional Lewis pair.

The existing catalyst/initiator systems and methodologies used for the synthesis of polymers can access only a few cyclic polymers composed entirely of a single monomer type, and the synthesis of such authentic cyclic polar vinyl polymers (acrylics) devoid of any foreign motifs remains a challenge. Here we report that a tethered B-P-B trifunctional, intramolecular frustrated Lewis pair catalyst enables the synthesis of an authentic cyclic acrylic polymer, cyclic poly(γ-methyl-α-methylene-γ-butyrolactone) (c-PMMBL), from the bio-based monomer MMBL. Detailed studies have revealed an initiation and propagation mechanism through pairwise monomer enchainment enabled by the cooperative and synergistic initiator/catalyst sites of the trifunctional catalyst. We propose that macrocyclic intermediates and transition states comprising two catalyst molecules are involved in the catalyst-regulated ring expansion and eventual cyclization, forming authentic c-PMMBL rings and concurrently regenerating the catalyst. The cyclic topology of the c-PMMBL polymers imparts an ~50 °C higher onset decomposition temperature and a much narrower degradation window compared with their linear counterparts of similar molecular weight and dispersity, while maintaining high chemical recyclability.

CO2 Fixation and PCHC Depolymerization by a Dinuclear ß-Diketiminato Zinc Complex.

The production of cyclic carbonates and (or) polycarbonates from the coupling of carbon dioxide (CO2 ) with epoxides is a practical strategy for CO2 fixation. Chemically recycling of the polycarbonates is also urgently needed for sustainable development of plastics. Here a dinuclear ß-diketiminato (BDI) methyl zinc complex((BDI-ZnMe)2 , 1) is reported to achieve not only selective cyclic carbonates from cycloaddition of CO2 to meso-CHO in the presence of cocatalyst, but also effective depolymerization of PCHC into trans-CHC. The trans-CHC can be further transformed into cis-CHC, thus demonstrating great application potentials of this strategy in CO2 fixation and chemical recycling of plastics.

An Arbitrarily Regulated Monomer Sequence in Multi-Block Copolymer Synthesis by Frustrated Lewis Pairs.

Rapid access to sequence-controlled multi-block copolymers (multi-BCPs) remains as a challenging task in the polymer synthesis. Here we employ a Lewis pair (LP) composed of organophosphorus superbase and bulky organoaluminum to effectively copolymerize the mixture of methacrylate, cyclic acrylate, and two acrylates, into well-defined di-, tri-, tetra- and even a hepta-BCP in one-pot one-step manner. The combined livingness, dual-initiation and CSC feature of Lewis pair polymerization enable us to achieve not only a trihexaconta-BCP with the highest record in 8 steps by using four-component monomer mixture as building blocks, but also the arbitrarily-regulated monomer sequence in multi-BCP, simply by changing the composition and adding order of the monomer mixtures, thus demonstrating the powerful capability of our strategy in improving the efficiency and enriching the composition of multi-BCP synthesis.

Associations between the HDL-C/ApoA-I ratio and fasting glucose levels differ by glucose deciles, HDL-C/ApoA-I ratio ranges and sex.

AIMS: To learn how high-density lipoprotein cholesterol (HDL-C) and apolipoprotein A-I (ApoA-I) are associated with fasting blood glucose (FBG). METHODS: A cross-sectional study was performed in 97,801 males and 70,773 females without known disease. RESULTS: The ratio of HDL-C/ApoA-I is more stable for predicting fasting glucose levels than HDL-C or ApoA-I alone. In subjects with HDL-C/ApoA-I ≤ 0.9, HDL-C/ApoA-I ratios were negatively associated with FBG levels, with similar patterns between sexes, and the associations gradually strengthened along with the deciles of FBG increase. In subjects with HDL-C/ApoA-I > 0.9, FBG remained at relatively lower levels in both sexes, while the associations between the FBG level and the HDL-C/ApoA-I ratio turned from negative in the lowest five deciles to positive in the highest two deciles of FBG levels in males. Adjustment for known confounders only slightly attenuated the above association patterns. Subpopulations with HDL-C/ApoA-I ≤ 0.9 were distributed in the higher ranges of triglyceride (TG), non-HDL-C, total cholesterol (TC) and ApoA-I levels and lower ranges of HDL-C levels. CONCLUSIONS: The HDL-C/ApoA-I ratio sorted TG, non-HDL-C, TC, ApoA-I and HDL-C levels and hence might combine more coordinating metabolic characteristics of these lipids in association with blood glucose homeostasis.

Selective visualization of cyanide in food, living cells and zebrafish by a mitochondria targeted NIR-emitting fluorescent probe.

Cyanide is a highly toxic substance, and the detection of cyanide in the environment and food samples is critical to public health care. Herein, we rationally designed a mitochondria-targeted near-infrared fluorescent probe BTC for ratiometric monitoring of CN- in water, food, living cells, and zebrafish. BTC exhibits a remarkable colorimetric ratiometric fluorescence response to CN- with high selectivity, low detection limit (54.3 nM), and large Stokes shift. The cyanide sensing mechanism was demonstrated by NMR and ESI-MS analysis and density functional theory (DFT). More importantly, BTC was used for efficient naked-eye colorimetric detection of CN- in sprouting potatoes, almonds, and ginkgo fruit samples. Further, the BTC is capable of situ tracking and imaging cyanide in mitochondria of SMMC-7721 cells and in zebrafish via dual emission channels, and was prepared into a kit for convenient and visual on-site sensing of cyanide in food samples.

A sustainable approach for the synthesis of recyclable cyclic CO2-based polycarbonates.

It is highly desirable to reduce the environmental pollution related to the disposal of end-of-life plastics. Polycarbonates derived from the copolymerization of CO2 and epoxides have attracted much attention since they can enable CO2-fixation and furnish biorenewable and degradable polymeric materials. So far, only linear CO2-based polycarbonates have been reported and typically degraded to cyclic carbonates. Here we synthesize a homogeneous dinuclear methyl zinc catalyst ((BDI-ZnMe)2, 1) to rapidly copolymerize meso-CHO and CO2 into poly(cyclohexene carbonate) (PCHC) with an unprecedentedly cyclic structure. Moreover, in the presence of trace amounts of water, a heterogeneous multi-nuclear zinc catalyst ((BDI-(ZnMe2·xH2O)) n , 2) is prepared and shows up to 99% selectivity towards the degradation of PCHC back to meso-CHO and CO2. This strategy not only achieves the first case of cyclic CO2-based polycarbonate but also realizes the complete chemical recycling of PCHC back to its monomers, representing closed-loop recycling of CO2-based polycarbonates.

Boron-Based Lewis Pairs Catalyzed Living, Regioselective, and Topology-Controlled Polymerization of (E, E)-Alkyl Sorbates.

It remains as a great challenge to realize living and controlled polymerization of renewable monomers by the boron-based Lewis pairs. Here, strong nucleophilic N-heterocyclic olefins (NHOs) or N-heterocyclic carbenes (NHCs) as Lewis bases, and boron-based compounds as Lewis acids, are employed to construct LPs for polymerization of alkyl sorbates, including (E, E)-methyl sorbate and (E, E)-ethyl sorbate. Systematic investigation reveals that the combinations of B(C6 F5 )3  with appropriate acidity and steric hindrance, and strong nucleophilic NHOs promote living and controlled polymerization of alkyl sorbates in 100% 1,4-addition manner, furnishing polymers with predicted molecular weight (Mw up to 56.6 kg mol-1 ) and narrow molecular weight distribution (D as low as 1.12). Furthermore, topology analysis shows that NHC1/B(C6 F5 )3  LP produce PMS possessing cyclic structure.

Single-Step Expeditious Synthesis of Diblock Copolymers with Different Morphologies by Lewis Pair Polymerization-Induced Self-Assembly.

Lewis pair polymerization has demonstrated its unique advantages and powerful capability in polymer synthesis. Here we employ strong nucleophilic N-heterocyclic olefin (NHO) and bulky organoaluminum to construct a frustrated Lewis pair, which can realize the compounded sequence control (CSC) copolymerization and self-assembly the mixture of dimethylaminoethyl acrylate and fluoride-functionalized methacrylate into diblock copolymers (di-BCPs) nano-assemblies through polymerization-induced self-assembly in one-pot, single-step manner within minutes. These di-BCPs were characterized by 1 H and 13 C NMR, GPC, DSC, and TEM. By utilizing appropriate solvophilic block and solvophobic block, such Lewis pair polymerization-induced self-assembly strategy enables the expeditious, room-temperature synthesis of di-BCP nanoparticles with different morphologies, including spheres, worms, vesicles, and even fibers, thus suggesting the great application potential of such method in the future.

Dicyanoisophorone-based fluorescent probe with large Stokes shift for ratiometric detection and imaging of exogenous/endogenous hypochlorite in cell and zebrafish.

A novel dicyanoisophorone-based red-emissive fluorescence probe (YT) with large Stokes shift (230 nm) was synthesized for rapid (<20 s) and selective detection of hypochlorite ions in nearly 100% aqueous medium. YT responded to hypochlorite ions via the ClO--promoted oxidative deprotection of thioacetal, leading to a red shift in its fluorescence maximum from 590 nm to 640 nm accompanied by naked-eye color change from orange to red. The emission response of the probe toward ClO- presented a good linear relationship in the 5-160 µM concentration range, with the LOD of 4.64 µM. Further, the probe YT was successfully employed in exogenous and LPS-induced endogenous imaging of ClO- in live cells and zebrafish, demonstrating its potential applications in biological science.

One-Step Synthesis of Lignin-Based Triblock Copolymers as High-Temperature and UV-Blocking Thermoplastic Elastomers.

This work utilizes frustrated Lewis pairs consisting of tethered bis-organophosphorus superbases and a bulky organoaluminum to furnish the highly efficient synthesis of well-defined triblock copolymers via one-step block copolymerization of lignin-based syringyl methacrylate and n-butyl acrylate, through di-initiation and compounded sequence control. The resulting thermoplastic elastomers (TPEs) exhibit microphase separation and much superior mechanical properties (elongation at break up to 2091 %, tensile strength up to 11.5 MPa, and elastic recovery up to 95 % after 10 cycles) to those of methyl methacrylate-based TPEs. More impressively, lignin-based tri-BCPs can maintain TPEs properties up to 180 °C, exhibit high transparency and nearly 100 % UV shield, suggesting potential applications in temperature-resistant and optical devices.

Lewis Pair Catalyzed Regioselective Polymerization of (E,E)-Alkyl Sorbates for the Synthesis of (AB)n Sequenced Polymers.

In this contribution, Lewis pairs (LPs) composed of N-heterocyclic olefins (NHOs) with different steric hindrance and nucleophilicity as Lewis bases (LBs) and Al-based compounds with comparable acidity but different steric hindrance as Lewis acids (LAs) were applied for 1,4-selective polymerization of (E,E)-methyl sorbate (MS) and (E,E)-ethyl sorbate (ES). The effects of steric hindrance, electron-donating ability, and acidity of LPs on MS and ES polymerization were systematically investigated. High catalytic activity and high initiation efficiency can be achieved, leading to the formation of PMS with 100 % 1,4-selectivity, tunable molecular weight (Mw up to 333 kg mol-1 ), and narrow molecular weight distribution (MWD). Block copolymerization of ES and methyl methacrylate (MMA) was also realized. Meanwhile, this system can be applied to other homologous conjugated diene substrates. Furthermore, simple chemical reactions can efficiently convert PMS to different polymers with strict (AB)n sequence structures, such as poly(sorbic acid), poly(propylene-alt-methyl acrylate), poly(propylene-alt-acrylic acid), poly(propylene-alt-allyl alcohol), and poly(ethylene-alt-2-butylene).

Dual-initiating and living frustrated Lewis pairs: expeditious synthesis of biobased thermoplastic elastomers.

Biobased poly(γ-methyl-α-methylene-γ-butyrolactone) (PMMBL), an acrylic polymer bearing a cyclic lactone ring, has attracted increasing interest because it not only is biorenewable but also exhibits superior properties to petroleum-based linear analog poly(methyl methacrylate) (PMMA). However, such property enhancement has been limited to resistance to heat and solvent, and mechanically both types of polymers are equally brittle. Here we report the expeditious synthesis of well-defined PMMBL-based ABA tri-block copolymers (tri-BCPs)-enabled by dual-initiating and living frustrated Lewis pairs (FLPs)-which are thermoplastic elastomers showing much superior mechanical properties, especially at high working temperatures (80-130 °C), to those of PMMA-based tri-BCPs. The FLPs consist of a bulky organoaluminum Lewis acid and a series of newly designed bis(imino)phosphine superbases bridged by an alkyl linker, which promote living polymerization of MMBL. Uniquely, such bisphosphine superbases initiate the chain growth from both P-sites concurrently, enabling the accelerated synthesis of tri-BCPs in a one-pot, two-step procedure. The results from mechanistic studies, including the single crystal structure of the dually initiated active species, detailed polymerizations, and kinetic studies confirm the livingness of the polymerization and support the proposed polymerization mechanism featuring the dual initiation and subsequent chain growth from both P-sites of the superbase di-initiator.

Highly Isoselective Ring-Opening Polymerization of rac-Lactide Using Chiral Binuclear Aluminum Catalyst.

The microstructure can significantly affect the physical and mechanical properties of polymers. Five chiral binuclear aluminum methyl complexes (rac1 to rac5) are synthesized by using chiral binaphthalene diamine ligand and characterized by both 1 H and 13 C NMR spectroscopy. The crystal structures of rac3 and rac5 are also identified by single crystal X-ray diffraction. In the presence of i PrOH initiator, these aluminum complexes catalyze the ring-opening polymerization (ROP) of rac-lactide (rac-LA) in a controlled manner and produce polymers with high to excellent isoselectivity (Pm up to 0.93). Even with a catalyst loading as low as 0.1%, polylactide with a Pm of 0.83 can still be obtained. Kinetic studies reveal the first-order dependence on monomer concentration whereas kinetic resolution polymerization provides the evidence to support that these binuclear aluminum catalysts catalyzed ROP of rac-LA adopts enantiomorphic site control mechanism. Furthermore, this strategy can also be applied to the ROP of both ε-caprolactone and δ-valeroactone.

Controllable, Bidirectional Water/Organic Vapors Responsive Actuators Fabricated by One-Step Thiol-Ene Click Polymerization.

It is challenging to synthesize stimuli-responsive materials with the well-balanced performance of fast stimulus-response speed, good mechanical strength, multi-functionality, and deformation diversity as well. This work reports a facile, one-step thiol-ene click polymerization strategy for preparation of water/acetone vapor-responsive hierarchical films, by using diallyl terephthalate (P) as hydrophobic ene-monomer, 1,4-diallyl-1,4-diazabicyclo [2.2.2]octane-1,4-diium bromide (B) as hydrophilic ene-monomer, and pentaerythritol tetra(3-mercaptopropionate) (PETMP) as thiol monomer. Besides, by taking advantage of the specific hydrophilic/hydrophobic induction effect of substrate and adjusting the molar ratio of P to B, P60 B40 -HPI film is fabricated on hydrophilic substrate "with plasma treatment" whereas P80 B20 -HPO film is obtained on hydrophobic substrate "without plasma treatment". Their "upper-dense and lower-porous" structural feature ensured the excellent combination of fast stimuli-response speed endowed by the porous structure and good mechanical strength enhanced by the upper dense surface. Both films are bidirectional water/acetone vapor-responsive materials, but their bending directions responding to the stimuli factors are completely opposite. This strategy showed great potential in the development of smart stimuli-responsive materials.

Rapid and Scalable Access to Sequence-Controlled DHDM Multiblock Copolymers by FLP Polymerization.

An immortal N-(diphenylphosphanyl)-1,3-diisopropyl-4,5-dimethyl-1,3-dihydro-2H-imidazol-2-imine/diisobutyl (2,6-di-tert-butyl-4-methylphenoxy) aluminum (P(NIi Pr)Ph2 /(BHT)Ali Bu2 )-based frustrated Lewis pair (FLP) polymerization strategy is presented for rapid and scalable synthesis of the sequence-controlled multiblock copolymers at room temperature. Without addition of extra initiator or catalyst and complex synthetic procedure, this method enabled a tripentacontablock copolymer (n=53, k=4, dpn =50) to be achieved with the highest reported block number (n=53) and molecular weight (Mn =310 kg mol-1 ) within 30 min. More importantly, this FLP polymerization strategy provided access to the multiblock copolymers with tailored properties by precisely adjusting the monomer sequence and block numbers.

Highly efficient cyclotrimerization of isocyanates using N-heterocyclic olefins under bulk conditions.

With a catalyst loading as low as 0.005%, high to excellent yields of isocyanurates could be achieved from N-heterocyclic olefin mediated organocatalytic cyclotrimerization of a wide range of isocyanates under bulk conditions. Experimental details coupled with structural characterization of the key intermediates led to comprehensive mechanistic studies of cyclotrimerization.

Lewis pairs polymerization of polar vinyl monomers.

The globally increasing demands for polymer materials stimulate the significantly intense attention focused on the Lewis pair polymerization (LPP) of various polar vinyl monomers catalyzed by Lewis pairs (LPs) composed of Lewis acid (LA) and Lewis base (LB). According to the degree of interaction between LA and LB, LPs could be divided into classical Lewis adduct (CLA), interacting Lewis pair (ILP) and frustrated Lewis pair (FLP). Regulation of the Lewis basicity, Lewis acidity, and steric effects of these LPs has a significant impact on the polymer chain initiation, propagation and termination as well as chain transfer reaction during polymerization. Compared with other polymerization strategies, LPP has shown several unique advantages towards the polymerization of polar vinyl monomers such as high activity, control or livingness, mild conditions, and complete chemo- or regioselectivity. We will comprehensively review the recent advances achieved in the LPP of polar vinyl monomers according to the classification of the employed LPs based on different LAs, by highlighting the key polymerization results, polymerization mechanisms as well as the currently unmet challenges and the future research directions of LPP chemistry.