Synthesis of Photoresponsive Fast Self-healing Polyolefin Composites by Nickel-Catalyzed Copolymerization of Ethylene and Lignin Cluster Monomers.

Polymers may suffer from sudden mechanical damages during long-term use under various harsh operating environments. Rapid and real-time self-healing will extend their service life, which is particularly attractive in the context of circular economy. In this work, a lignin cluster polymerization strategy (LCPS) was designed to prepare a series of lignin functionalized polyolefin composites with excellent mechanical properties through nickel catalyzed copolymerization of ethylene and lignin cluster monomers. These composites can also achieve rapid self-healing within 30 seconds under a variety of extreme usage environments (underwater, seawater, extremely low temperatures as low as -60 °C, organic solvents, acid alkali solvents, etc.), which is of great significance for real-time self-healing of sudden mechanical damage. More importantly, the dynamic cross-linking network within these composites enable great re-processability and amazing sealing performances.

Synthesis of Polar-functionalized Isotactic Polypropylenes Using Commercial Heterogeneous Ziegler-Natta Catalyst.

The efficient synthesis of polar-functionalized polypropylenes with high molecular weight and high stereoregularity represents a challenging task. This challenge becomes even more daunting when pursuing an industrially preferred heterogeneous process. This study demonstrated the realization of these goals through the use of commercial heterogeneous Ziegler-Natta catalysts in the copolymerization of propylene with ionic cluster polar monomers. The results revealed high copolymerization activity (∼1.1 × 107 g mol-1 h-1), moderate polar monomer incorporation ratios (∼4.9 mol %), high copolymer molecular weight (Mw > 105 g mol-1), high stereoregularity ([mmmm] ∼ 96%), and high melting temperature range (150-162 °C). The utilization of ionic cluster polar monomers improved the thermal stability as well as stereoselectivity of the catalyst. Moreover, the Ziegler-Natta catalyst can homopolymerize ionic cluster polar monomers with high activities (>104 g mol-1 h-1). The resulting polar-functionalized isotactic polypropylenes (iPP) exhibited superior tensile strength, impact strength, creep resistance, transparency, and crystallinity compared with nonpolar iPP. This enhancement was attributable to the dual roles of the ionic cluster polar monomer unit, serving as both a transparent nucleating agent and a dynamic cross-linking functionality. Furthermore, the polar-functionalized iPP exhibited improved compatibility with polar materials, offering benefits for applications in composites, recycling of mixed plastic wastes, 3D printing, and other fields. This study offered a comprehensive solution for the future industrial production of polar-functionalized iPP via copolymerization, bridging the gap between an efficient and practical copolymerization process from a synthetic chemistry perspective and enhanced material properties from an application perspective.

Advanced brain aging in Parkinson's disease with cognitive impairment.

Patients with Parkinson's disease and cognitive impairment (PD-CI) deteriorate faster than those without cognitive impairment (PD-NCI), suggesting an underlying difference in the neurodegeneration process. We aimed to verify brain age differences in PD-CI and PD-NCI and their clinical significance. A total of 94 participants (PD-CI, n = 27; PD-NCI, n = 34; controls, n = 33) were recruited. Predicted age difference (PAD) based on gray matter (GM) and white matter (WM) features were estimated to represent the degree of brain aging. Patients with PD-CI showed greater GM-PAD (7.08 ± 6.64 years) and WM-PAD (8.82 ± 7.69 years) than those with PD-NCI (GM: 1.97 ± 7.13, Padjusted = 0.011; WM: 4.87 ± 7.88, Padjusted = 0.049) and controls (GM: -0.58 ± 7.04, Padjusted = 0.004; WM: 0.88 ± 7.45, Padjusted = 0.002) after adjusting demographic factors. In patients with PD, GM-PAD was negatively correlated with MMSE (Padjusted = 0.011) and MoCA (Padjusted = 0.013) and positively correlated with UPDRS Part II (Padjusted = 0.036). WM-PAD was negatively correlated with logical memory of immediate and delayed recalls (Padjusted = 0.003 and Padjusted < 0.001). Also, altered brain regions in PD-CI were identified and significantly correlated with brain age measures, implicating the neuroanatomical underpinning of neurodegeneration in PD-CI. Moreover, the brain age metrics can improve the classification between PD-CI and PD-NCI. The findings suggest that patients with PD-CI had advanced brain aging that was associated with poor cognitive functions. The identified neuroimaging features and brain age measures can serve as potential biomarkers of PD-CI.

Outer-Shell Self-Supported Nickel Catalysts for the Synthesis of Polyolefin Composites.

In situ heterogeneous olefin polymerization has attracted much attention for the synthesis of polyolefin composites. However, the complicated syntheses of specially designed catalysts or the detrimental effects of interactions between catalyst and solid supports pose great challenges. In this contribution, an outer-shell self-supporting strategy was designed to heterogenize nickel catalysts on different fillers via precipitation homopolymerization of ionic cluster type polar monomer. These catalysts demonstrated high activity, good product morphology control, and stable performances in ethylene polymerization and copolymerization. Moreover, various polyolefin composites with great mechanical and customized properties can be efficiently synthesized.

Amine-Imine Nickel Catalysts with Pendant O-Donor Groups for Ethylene (Co)Polymerization.

The introduction of a secondary interaction is an efficient strategy to modulate transition-metal-catalyzed ethylene (co)polymerization. In this contribution, O-donor groups were suspended on amine-imine ligands to synthesize a series of nickel complexes. By adjusting the interaction between the nickel metal center and the O-donor group on the ligands, these nickel complexes exhibited high activities for ethylene polymerization (up to 3.48 × 106 gPE·molNi-1·h-1) with high molecular weight up to 5.59 × 105 g·mol-1 and produced good polyethylene elastomers (strain recovery (SR) = 69-81%). In addition, these nickel complexes can catalyze the copolymerization of ethylene with vinyl acetic acid, 6-chloro-1-hexene, 10-undecylenic, 10-undecenoic acid, and 10-undecylenic alcohol to prepare the functionalized polyolefins.

Cationic P,O-Coordinated Nickel(II) Catalysts for Carbonylative Polymerization of Ethylene: Unexpected Productivity via Subtle Electronic Variation.

Transition-metal-catalyzed copolymerization of ethylene with carbon monoxide affords polyketones materials with excellent mechanical strength, photodegradability, surface and barrier properties. Unlike the widely used and rather expensive Pd catalysts, Ni-catalyzed carbonylative polymerization is very difficult since the strong binding affinity of CO to Ni deactivates the highly electrophilic metal center easily. In this study, various cationic P,O-coordinated Ni complexes were synthesized using the electronic modulation strategy, and the catalyst with strong electron-donating substituents exhibits an excellent productivity of 104  g polymer (g Ni)-1 , which represents a rare discovery that a Ni complex could operate with such exceptional efficiency in comparison with Pd catalysts. Notably, those Ni catalysts were also efficient for terpolymerization of ethylene, propylene with CO for producing commercial polyketone materials with low melting temperatures and easy processibility.

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).

Photoresponsive Palladium and Nickel Catalysts for Ethylene Polymerization and Copolymerization.

In this contribution, we install an azobenzene functionality in olefin polymerization catalysts and use light to modulate their properties via photoinduced trans-cis isomerization of the azobenzene moiety. The initially targeted azobenzene-functionalized α-diimine palladium and nickel catalysts are not photoresponsive. To address this issue, an imine-amine system bearing interrupted conjugation with the metal center, and a sandwich-type α-diimine system bearing an azobenzene unit at a position covalently far from the metal center were prepared and studied. We demonstrate that light can be used to tune their properties in ethylene polymerization and copolymerization with polar comonomers, enabling light-induced control of the polymerization processes, polymer microstructures and polymer properties. More interestingly, the light-mediated property changes were attributed to ligand electronic effects in one system and ligand steric effects in the other.

Hydrogen-Bonding-Induced Heterogenization of Nickel and Palladium Catalysts for Copolymerization of Ethylene with Polar Monomers.

The practical synthesis of polar-functionalized polyolefins using transition-metal-catalyzed copolymerization of olefins with polar monomers is a challenge; the use of heterogeneous catalysts is little explored. Herein, we report the synthesis of heterogeneous naphthoquinone-based nickel (Ni/SiO2 ) and palladium (Pd/SiO2 ) catalysts through hydrogen bonding interactions of the ligands with the silica surface. Ni/SiO2 exhibits high activities (up to 2.65×106  g mol-1 h-1 ) during the copolymerization of ethylene with 5-hexene-1-yl-acetate, affording high-molecular-weight (Mn up to 630 000) polar-functionalized semicrystalline polyethylene (comonomer incorporation up to 2.8 mol %), along with great morphology control. The resulting copolymers possess improved surface properties and great mechanical properties. Pd/SiO2 can mediate ethylene copolymerization with polar monomers with moderate activity to produce high-molecular-weight copolymers with tunable comonomer incorporation.

A Self-Supporting Strategy for Gas-Phase and Slurry-Phase Ethylene Polymerization using Late-Transition-Metal Catalysts.

The polyolefin industry is dominated by gas-phase and slurry-phase polymerization using heterogeneous catalysts. In contrast, academic research is focused on homogeneous systems, especially for late-transition-metal catalysts. The heterogenization of homogeneous catalysts is a general strategy to provide catalyst solutions for existing industrial polyolefin synthesis. Herein, we report an alternative, potentially general strategy for using homogeneous late-transition-metal catalysts in gas-phase and slurry-phase polymerization. In this self-supporting strategy, catalysts with moderate chain-walking capabilities produced porous polymer supports during gas-phase ethylene polymerization. Chain walking, in which the metal center can move up and down the polymer chain during polymerization, ensures that the metal center can travel along the polymer chain to find suitable sites for ethylene enchainment. This strategy enables simple heterogenization of catalysts on solid supports for slurry-phase polymerization. Most importantly, various branched ultra-high-molecular-weight polyethylenes can be prepared under various polymerization conditions with proper catalyst selection.

A simple and versatile nickel platform for the generation of branched high molecular weight polyolefins.

The development of high-performance transition metal catalysts has long been a major driving force in academic and industrial polyolefin research. Late transition metal-based olefin polymerization catalysts possess many unique properties, such as the ability to generate variously branched polyolefins using only ethylene as the feedstock and the capability of incorporating polar functionalized comonomers without protecting agents. Here we report the synthesis and (co)polymerization studies of a simple but extremely versatile α-imino-ketone nickel system. This type of catalyst is easy to synthesize and modify, and it is thermally stable and highly active during ethylene polymerization without the addition of any cocatalysts. Despite the sterically open nature, these catalysts can generate branched Ultra-High-Molecular-Weight polyethylene and copolymerize ethylene with a series of polar comonomers. The versatility of this platform has been further demonstrated through the synthesis of a dinuclear nickel catalyst and the installation of an anchor for catalyst heterogenization.

Concerted steric and electronic effects on α-diimine nickel- and palladium-catalyzed ethylene polymerization and copolymerization.

For transition metal-based olefin polymerization catalysts, ligand steric and electronic effects can strongly influence important catalytic properties. However, the simultaneous tuning of both steric and electronic effects has not been explored in most of the previous studies. In this contribution, a strategy to tune the ligand electronic and steric effects in a concerted fashion is reported. In such a system, both dibenzhydryl groups and multiple methoxy/fluoro groups were installed in α-diimine ligands. In addition to strongly influencing ligand electronics, the methoxy/fluoro groups can interact with the dibenzhydryl groups and efficiently increase ligand sterics. In ethylene polymerization, this concurrent tuning of electronic and steric effects can lead to simultaneous enhancement of several parameters (activity, stability, polymer molecular weight, melting point, branching density) for both the nickel and palladium catalysts. The effectiveness of this strategy is highly attractive for future studies in other catalytic systems.

Aluminum Tralen Complex Meditated Reversible-Deactivation Radical Polymerization of Vinyl Acetate.

The AlIII(tralen)Cl complex (tralenH2 = N,N'-di(cyclohepta-2,4,6-trien-1-one-2-yl)-1,2-diaminobenzene) has been synthesized and applied to mediate the reversible-deactivation radical polymerization (RDRP) of vinyl monomers. The polymerization of unconjugated monomers such as vinyl acetate (VAc) and N-vinylpyrrolidone (NVP) with AlIII(tralen)Cl showed the living characters of linearly increased molecular weight with conversion and formation of block copolymer. However, the control manners in the polymerization of conjugated monomers like acrylates and styrene were limited. The electron paramagnetic resonance (EPR) spectrum indicated that AlIII(tralen)BArF (BArF = tetrakis(3,5-trifluormethylphenyl)borate) and propagating radicals formed a paramagnetic dormant species, possibly PVAc-AlIII(tralen)BArF, via the single-electron transfer to the tralen ligand.

Direct and Tandem Routes for the Copolymerization of Ethylene with Polar Functionalized Internal Olefins.

Transition metal catalyzed ethylene copolymerization with polar monomers is a highly challenging reaction. After decades of research, the scope of suitable comonomer substrates has expanded from special to fundamental polar monomers and, recently, to 1,1-disubstituted ethylenes. Described in this contribution is a direct and tandem strategy to realize ethylene copolymerization with various 1,2-disubstituted ethylenes. The direct route is sensitive to sterics of both the comonomers and the catalyst. In the tandem route, ruthenium-catalyzed ethenolysis can convert 1,2-disubstituted ethylenes into terminal olefins, which can be subsequently copolymerized with ethylene to afford polar functionalized polyolefins. The one-pot, two-step tandem route is highly versatile and efficient in dealing with challenging substrates. This work is a step forward in terms of expanding the substrate scope for transition metal catalyzed ethylene copolymerization with polar-functionalized comonomers.

Cardioprotective effect of electroacupuncture in cardiopulmonary bypass through apelin/APJ signaling.

Aim Acupuncture, particularly electroacupuncture (EA), can improve the clinical outcomes of cardiopulmonary bypass (CPB) patients; however, the mechanisms remain unclear. This study aimed to examine the effects of EA pre-treatment on myocardial injury after CPB and investigate its potential mechanisms. MAIN METHODS: Male Sprague-Dawley rats were subjected to CPB and divided into Control (sham-operated), CPB, and EA (CPB + EA) groups. In the EA group, rats were treated with EA at the "PC6" acupoint for 30 min before being subjected to CPB. At 0.5, 1, and 2 h after CPB, the expression levels of plasma cardiac troponin I (cTnI) and lactate dehydrogenase (LDH), and myeloperoxidase (MPO) activity, TNFα, IL-1ß, reduced glutathione (GSH), oxidized glutathione (GSSH), and the ratio of GSH/GSSH in the myocardial tissue were measured. Apoptosis was detected by terminal deoxynucleotidyl transferase dUTP nick-end labelling (TUNEL) staining. The expression of cleaved caspase-3 was detected by immunofluorescence. The expression of apelin, APJ, AKT, p-Akt, ERK1/2, and p-ERK1/2 was determined using western blotting. KEY FINDINGS: Decreased myocardial injury marker levels, myocardial apoptosis, oxidative stress, and the inflammatory response were found in the EA group compared with the CPB group. The expression levels of apelin, APJ, and p-Akt/AKT were increased in the EA group, and the p-ERK1/2/ERK1/2 level was decreased. SIGNIFICANCE: This study showed that EA pre-treatment can protect the heart from damage following CPB, which might be mainly mediated by restoring the apelin/APJ signaling pathway.

Emerging Palladium and Nickel Catalysts for Copolymerization of Olefins with Polar Monomers.

Transition-metal-catalyzed copolymerization of olefins with polar monomers represents a challenge because of the large variety of substrate-induced side reactions. However, this approach also holds the potential for the direct synthesis of polar functionalized polyolefins with unique properties. After decades of research, only a few catalyst systems have been found to be suitable for this reaction. Some major advances in catalyst development have been made in the past five years. This Minireview summarizes some of the recent progress in the extensively studied Brookhart and Drent catalyst systems, as well as emerging alternative palladium and nickel catalysts.

Position Makes the Difference: Electronic Effects in Nickel-Catalyzed Ethylene Polymerizations and Copolymerizations.

A series of phosphine-sulfonate ligands and the corresponding nickel complexes are prepared and characterized. These ligands are specifically designed to bear systematically varied electron-donating and -withdrawing substituents (H, OMe, NMe2, CF3, and Me). More importantly, these substituents are installed at different positions on the ligand framework, namely, the para-position of the phenylphosphino group (position X), and para to the arylsulfonate group of the main ligand (position Y). These nickel complexes are highly active single-component catalysts for the polymerization of ethylene. An electron-donating substituent at position X or an electron-withdrawing substituent at position Y is beneficial to the properties of these nickel catalysts. Specifically, the catalyst bearing the NMe2 substituent at position X exhibits high stability and high activity (3.3 × 106 g mol-1 h-1), and catalyzes the formation of polyethylene of high molecular weight ( Mn 405 000) and high melting point ( Tm 138.5 °C). This catalyst also mediates the efficient copolymerizations of ethylene with methyl 10-undecenoate, 6-chloro-1-hexene, and trimethoxyvinylsilane.

A Versatile Ligand Platform for Palladium- and Nickel-Catalyzed Ethylene Copolymerization with Polar Monomers.

The ability to carry out transition-metal-catalyzed copolymerizations of olefins with polar monomers is a great challenge in the field of olefin polymerization. Palladium has been the dominant player in this field, while its low-cost nickel counterpart has only achieved very limited success. We report the synthesis and evaluation of a highly versatile platform based on diphosphazane monoxide ligands. Both palladium and nickel catalysts bearing these ligands mediate the copolymerization of ethylene with a number of fundamental polar monomers.

Synthesis of silicon-functionalized polyolefins by subsequent cobalt-catalyzed dehydrogenative silylation and nickel-catalyzed copolymerization.

Metal catalyzed olefin hydrosilylation and metal mediated olefin polymerization are both of great academic and industrial importance. In this article, these two aspects are combined to prepare silicon-functionalized polyolefin materials. First, pyridine-diimine cobalt-catalyzed dehydrogenative silylations of various terminal olefins with alkylsilanes lead to the formation of a variety of allylsilanes at high yields. Then, the allylsilanes are copolymerized with ethylene using an α-diimine nickel catalyst, leading to the formation of branched polyolefins with high molecular weight and moderate comonomer incorporation. This subsequent catalytic process is an efficient strategy for the synthesis of silicon-functionalized polyolefins using widely available and inexpensive starting materials.