Sustainable Engineered Designs and Manufacturing of Waste Derived Graphenes Reinforced Polypropylene Composite for Automotive Interior Parts.

The automotive sector is actively pursuing a lightweighting strategy as a means to urgently decrease greenhouse gas emissions, which are a significant driver of climate change. The development of lightweight composite structures has been identified as crucial for enhancing part performance while mitigating negative environmental impacts and adopting energy-efficient manufacturing methods. This comprehensive study aimed to decrease the main reinforcement content of talc in commercial compounds while integrating graphene derived from waste polypropylene (PP) grown on talc and graphene nanoplatelet obtained from waste tires by upcycling processes into the PP compound.

Exosomes encapsulated in hydrogels for effective central nervous system drug delivery.

The targeted delivery of pharmacologically active molecules, metabolites, and growth factors to the brain parenchyma has become one of the major challenges following the onset of neurodegeneration and pathological conditions. The therapeutic effect of active biomolecules is significantly impaired after systemic administration in the central nervous system (CNS) because of the blood-brain barrier (BBB). Therefore, the development of novel therapeutic approaches capable of overcoming these limitations is under discussion.

Exploiting Visible-Light Induced Radical to Cation Transformation Pathway for Reactivity Enhanced Electrophilic Aromatic Substitution Polymerization of Heteroaromatics.

A straightforward approach is employed to synthesize methylene-bridged poly(hetero aromatic)s based on furan, pyrrole, thiophene, and thiophene derivatives. The process involves an electrophilic aromatic substitution reaction facilitated by a visible light-initiated system consisting of manganese decacarbonyl and an iodonium salt. The approach mainly relies on the formation of halomethylium cation, the attack of this cation to heteroaromatic, regeneration of methylium cation on the heteroaromatic, and reactivity differences between halomethylium and heteroaromatic methylium cations for successful polymerizations.

Combining Step-Growth and Chain-Growth Polymerizations in One Pot: Light-Induced Fabrication of Conductive Nanoporous PEDOT-PCL Scaffold.

A novel method based on light-induced fabrication of a poly (3,4-ethylenedioxythiophene)-polycaprolactone (PEDOT-PCL) scaffold using phenacyl bromide (PAB) as a single-component photoinitiator is presented. HBr released from the step-growth polymerization of EDOT is utilized as an in situ catalyst for the chain-growth polymerization of ε-caprolactone. Detailed investigations disclose the formation of a self-assembled nanoporous electroconductive scaffold (1.

Visible Light Induced Degradation of Poly(methyl methacrylate-co-methyl α-chloro acrylate) Copolymer at Ambient Temperature.

Poly(methyl methacrylate) (PMMA) is a well-known and widely used commodity plastic. High production amount of PMMA causes excessive waste creation that highlights the necessity of recycling. Conventional recycling methods require elevated temperatures to induce degradation or depolymerization.

Photoinitiated Cationic Ring-Opening Polymerization of Octamethylcyclotetrasiloxane.

Photochemical techniques have recently been revitalized as they can readily be adapted to different polymerization modes to yield a wide range of complex macromolecular structures. However, the implementation of the photoinduced cationic methods in the polymerization of cyclic siloxane monomers has scarcely been investigated. Octamethylcyclotetrasiloxane (D4) is an important monomer for the synthesis of polydimethylsiloxane (PDMS) and its copolymers.

Coumarinacyl Anilinium Salt: A Versatile Visible and NIR Photoinitiator for Cationic and Step-Growth Polymerizations.

A coumarinacyl anilinium () salt, facilely synthesized via a one-pot reaction, is shown to be a versatile visible and NIR photoinitiator for cationic and step-growth polymerizations. salt exhibits superior photoinitiation performance as compared to commercial iodonium salt in cationic polymerization. Upon visible-light irradiation, this salt undergoes hemolytic and heterolytic cleavage and subsequent electron transfer and hydrogen abstraction reactions, forming reactive species capable of initiating cationic polymerization of epoxides and vinyl monomers.

An unusual zig-zag 2D copper(I) coordination polymer as an outstanding catalyst for azide-alkyne "click" chemistry at room temperature.

A straightforward method for the synthesis of a two-dimensional (2D) new copper(I) coordination polymer, namely Cu(bzpdc), containing the ligand benzophenone 4,4'-dicarboxylate, and its effective use as catalyst for the azide-alkyne click chemistry at room temperature is reported. Zig-zag formation caused by cuprophilic interactions resulted in an unprecedented crystal structure with a very high copper content (45.5% by weight).

Dimanganese decacarbonyl catalyzed visible light induced ambient temperature depolymerization of poly(methyl methacrylate).

Recent years have witnessed an enormous development in photoinduced systems, opening up possibilities for advancements in industry and academia in terms of green chemistry providing environmentally friendly conditions and spatiotemporal control over the reaction medium. A vast number of research have been conducted on photoinduced systems focusing on the development of new polymerization methods, although scarcely investigated, depolymerization of the synthesized polymers by photochemical means is also possible. Herein, we provide a comprehensive study of visible light induced dimanganese decacarbonyl (Mn(CO)) assisted depolymerization system for poly(methyl methacrylate) with chlorine chain end prepared by Atom Transfer Radical Polymerization.

Visible Light Induced High Resolution and Swift 3D Printing System by Halogen Atom Transfer.

3D printing technology offers solutions for numerous needs in industry and the daily life of individuals. In recent years, most research efforts have focused on this technology as the market share has grown and requirements have become specified in their related fields. In this work, a novel visible light induced 3D printing system with high resolution and short printing time using dimanganese decacarbonyl (Mn (CO) ) in combination with organic halides is reported.

Phenacyl Bromide as a Single-Component Photoinitiator: Photoinduced Step-Growth Polymerization of N-Methylpyrrole and N-Methylindole.

The synthesis of step-growth polymers by photoinduced methods is a challenging issue in synthetic chemistry. Here, we report a single component near UV responsive photopolymerization system for step-growth polymerization of N-methylpyrrole (MPyr) and N-methylindole (MIn) by using phenacyl bromide (PAB). The obtained high molecular weight conjugated polymers were characterized by spectral and chromatographic methods.

Synthesis of Block Copolymers by Mechanistic Transformation from Reversible Complexation Mediated Living Radical Polymerization to the Photoinduced Radical Oxidation/Addition/Deactivation Process.

A versatile strategy for the fabrication of block copolymers by the combination of two discrete living polymerization techniques─reversible complexation mediated living radical polymerization (RCMP) and photoinduced radical oxidation addition deactivation (PROAD) processes─is reported. First, RCMP is conducted to yield poly(methyl methacrylate) with iodide end groups (PMMA-I). In the following step, PMMA-I is used as macroinitiator for living PROAD cationic polymerization of isobutyl vinyl ether.

Expanding the Scope of 2D Black Phosphorus Catalysis to the Near-Infrared Light Initiated Free Radical Photopolymerization.

In the drive toward the development of efficient and stable inorganic semiconductor materials with broadband solar absorption ability to induce various photochemical processes is a highly attractive research field. In this study, two-dimensional (2D) few-layer black phosphorus (BP) exfoliated in a solvent is utilized as photocatalyst to initiate the polymerization of various monomers under visible and near-IR (NIR) light irradiation. Upon the light exposure, few-layer BP generates excited electrons and holes, which undergo electron transfer reactions with the onium salts to form free radicals capable of initiating free radical polymerization.

Fluorescent bioassay for SARS-CoV-2 detection using polypyrene-g-poly(ε-caprolactone) prepared by simultaneous photoinduced step-growth and ring-opening polymerizations.

The construction of a rapid and easy immunofluorescence bioassay for SARS-CoV-2 detection is described. We report for the first time a novel one-pot synthetic approach for simultaneous photoinduced step-growth polymerization of pyrene (Py) and ring-opening polymerization of ε-caprolactone (PCL) to produce a graft fluorescent copolymer PPy-g-PCL that was conjugated to SARS-CoV-2-specific antibodies using EDC/NHS chemistry. The synthesis steps and conjugation products were fully characterized using standard spectral analysis.

Photoinduced Controlled/Living Polymerizations.

The application of photochemistry in polymer synthesis is of interest due to the unique possibilities offered compared to thermochemistry, including topological and temporal control, rapid polymerization, sustainable low-energy processes, and environmentally benign features leading to established and emerging applications in adhesives, coatings, adaptive manufacturing, etc. In particular, the utilization of photochemistry in controlled/living polymerizations often offers the capability for precise control over the macromolecular structure and chain length in addition to the associated advantages of photochemistry. Herein, the latest developments in photocontrolled living radical and cationic polymerizations and their combinations for application in polymer syntheses are discussed.

Exfoliated black phosphorous-mediated CuAAC chemistry for organic and macromolecular synthesis under white LED and near-IR irradiation.

The development of long-wavelength photoinduced copper-catalyzed azide-alkyne click (CuAAC) reaction routes is attractive for organic and polymer chemistry. In this study, we present a novel synthetic methodology for the photoinduced CuAAC reaction utilizing exfoliated two-dimensional (2D) few-layer black phosphorus nanosheets (BPNs) as photocatalysts under white LED and near-IR (NIR) light irradiation. Upon irradiation, BPNs generated excited electrons and holes on its conduction (CB) and valence band (VB), respectively.

Visible Light Induced Conventional Step-Growth and Chain-Growth Condensation Polymerizations by Electrophilic Aromatic Substitution.

A novel visible light induced step-growth polymerization by electrophilic aromatic substitution between photochemically generated carbocations and dimethoxybenzene nucleophile is described. Conventional step-growth polymerization and chain-growth condensation polymerization (CCP) mechanisms are presented. It is found that by changing the molar ratios of the monomers slightly, the CCP mechanism becomes operative and relatively higher molecular weight polymers are obtained because of the higher reactivity of the end groups of the intermediates and oligomers than that of the monomers.

A Novel Photoinduced Ligation Approach for Cross-Linking Polymerization, Polymer Chain-End Functionalization, and Surface Modification Using Benzoyl Azides.

Various ligation processes have recently become a powerful tool in synthetic polymer chemistry. Herein, the use of a new photochemical ligation process as a versatile approach for the cross-linking polymerization, functionalization of polymer chain ends, and surface modification of various materials such as silica and graphene oxide, is demonstrated. The process is based on the formation of urethane linkages by the reaction of photochemically in situ generated isocyanates from benzoyl azides with hydroxyl moieties in the presence of organobase, bicyclo[2.

Phenacyl Phenothiazinium Salt as a New Broad-Wavelength-Absorbing Photoinitiator for Cationic and Free Radical Polymerizations.

A novel broad-wavelength-absorbing photoinitiator based on phenacyl phenothiazinium hexafluroantimonate (P-PTh) possessing both phenacyl and phenothiazine chromophoric groups was reported. P-PTh absorbs light at UV, Visible and Near-IR region. Photophysical, photochemical, and computational investigations revealed that P-PTh in solution decomposes at all wavelengths by homolytic and heterolytic cleavages and generates cationic and radical species, which could efficiently initiate cationic and free radical polymerizations.

Visible light induced step-growth polymerization by electrophilic aromatic substitution reactions.

A novel visible light induced step-growth polymerization to form poly(phenylene methylene) by electrophilic aromatic substitution reactions is described. The effect of different nucleophilic aromatic molecules on polymerization has been investigated. The possibility of combining step-growth polymerization with conventional free radical and free radical promoted cationic polymerizations through photoinduced chain-end activation has been demonstrated.

Experimental and Numerical Investigation of Flow and Alignment Behavior of Waste Tire-Derived Graphene Nanoplatelets in PA66 Matrix during Melt-Mixing and Injection.

Homogeneous dispersion of graphene into thermoplastic polymer matrices during melt-mixing is still challenging due to its agglomeration and weak interfacial interactions with the selected polymer matrix. In this study, an ideal dispersion of graphene within the PA66 matrix was achieved under high shear rates by thermokinetic mixing. The flow direction of graphene was monitored by the developed numerical methodology with a combination of its rheological behaviors.

Visible Light Induced Step-Growth Polymerization by Substitution Reactions.

A new visible light induced step-growth polymerization of dibromoxylene, and diols using dimanganese decacarbonyl and diphenyliodonium salt is described. The polymerization is suggested to proceed by substitution reaction between dixylenium cations formed upon visible light irradiation in the presence of dimanganese decacarbonyl and diphenyl iodonium salt. For the described substitution reaction with diols as nucleophilic component, the scope of the process is studied.

Photopolymerization of Macroscale Black 3D Objects Using Near-Infrared Photochemistry.

The efficiency of the photopolymerization technology significantly decreases when the color of materials blackens, which is contributed by the limitations of light penetration. Herein, we demonstrate rapid generation of black 3D objects up to the centimeter level in size based on melanin using near-infrared (NIR) photochemistry. Melanin, of a low absorption coefficient in the NIR range, allows thorough penetration of the 980 nm light to induce emission from upconversion nanoparticles (UCNPs) for initiating UCNP-assisted photopolymerization (UCAP).

N-Acyl Dibenzazepine Chemistry as Versatile Approach for Photoreversible Thiol-Ene Networks.

It is herein reported that a facile application of N-acyl dibenzazepine (ADBA) photochemistry for preparing photoreversible ADBA based thiol-ene networks. Crosslinking of the ADBA thiol-ene networks is successfully achieved by UV induced dimerization of ADBA groups at wavelengths above 300 nm while a subsequent deep UV exposure (λ = 250 nm) results in a well-defined cleavage of the crosslinks. The photochemical bonding and cleavage of the process has been determined and studied in detail by spectroscopic measurements.

Chemiluminescence Induced Cationic Photopolymerization Using Sulfonium Salt.

A visible light cationic photoinitiating system under chemiluminescence irradiation using sulfonium salt is reported. The visible light emitted from the chemiluminescence reactions, absorbed by the sulfonium salt, essentially leads to the formation of protonic acids capable of initiating cationic polymerization of oxirane and vinyl monomers. The process is suitable for the formation of linear polymer chains as well as cross-linked functional networks with aggregation-induced emission property.