Transfer Agent Research Articles

Copolymerization of CO2 and Cyclohexene Oxide in the Presence of Functional Transfer Agents Provides Telechelic Polycarbonates: Synthesis of CO2‐Containing Macromonomers and Macroinitiators

AbstractOne possible way to store the excess CO2 present in atmosphere is to use it as a reagent for the synthesis of commodities. In particular, CO2 and epoxides can be copolymerized to produce a large variety of polycarbonates which appear very promising in various application fields. Further, the addition of an appropriate transfer agent in the reaction mixture promotes the formation of telechelic polycarbonates which can be used where specific functional polymers are necessary. In this work, (hydroxyethyl) methacrylate and 2‐hydroxyethyl‐2‐bromoisobutyrate species are exploited as transfer agents in the copolymerization of CO2 and cyclohexene oxide, in the presence of a macrocyclic phenolate dimagnesium catalyst. The effect of the transfer agent concentration on the polycarbonate characteristics is evaluated. Finally, the obtained telechelic polycarbonates are used as macromonomers and macroinitiators in the synthesis of statistical and block copolymers.

Antimicrobial Activity of Copolymer Structures from Bio-Based Monomers.

The urgent need for new antimicrobial compounds has led scientists to explore antimicrobial peptides (AMPs) and antimicrobial polymers as solutions for multidrug resistance. In this study, we synthesized copolymers with cationic and hydrophobic moieties by free-radical polymerization (FRP) using a chain transfer agent to control molecular weights. The potential of natural products as part of the hydrophobic moiety was evaluated, along with variations in their monomer content (13-25%) and the molecular weight (MW) of the copolymer (5000-20,000 g·mol-1). Hydrophobicity was evaluated using the theoretical Log Poct values and surface areas (SAs). Biological assays included antimicrobial activity against Escherichia coli and Staphylococcus aureus standard strains, hemolytic activity in red blood cells (RBC), and cytotoxicity tests against HEK293T cells. Keys findings indicate that copolymers with tropolone moieties, lower MWs, and an optimal balance between hydrophobic and cationic moieties show a promising basis for future generations of antimicrobials.

Catalytic Syntheses of Thiol-End-Functionalized ROMP Polymers.

Thiol-functionalized polymers have become a crucial class of materials due to their distinct chemical properties and versatile reactivity, leading to a broad spectrum of applications. Herein, we report the straightforward syntheses of a wide range of thiol-end-functionalized ring-opening metathesis polymerization (ROMP) polymers exploiting our previously reported catalytic ROMP mechanisms using suitable chain transfer agents. All the synthesized polymers were characterized via SEC, 1H NMR spectroscopy and MALDI-ToF mass spectrometry techniques. Furthermore, the existence of thiol groups on the polymer chains was verified through the well-established thiol coating reaction on gold nanoparticle surfaces. We believe this method of synthesizing thiol-end-functionalized ROMP polymers (using a reduced amount of ruthenium metal compared to conventional living ROMP) will be of great importance to materials science and biochemical research.

Double Hydrophilic Hyperbranched Copolymer-Based Lipomer Nanoparticles: Copolymer Synthesis and Co-Assembly Studies

Double hydrophilic, random, hyperbranched copolymers were synthesized via reversible addition–fragmentation chain transfer (RAFT) polymerization of oligo(ethylene glycol) methyl ether methacrylate (OEGMA) and 2-(dimethylamino)ethyl methacrylate (DMAEMA) utilizing ethylene glycol dimethacrylate (EGDMA) as the branching agent. The resulting copolymers were characterized in terms of their molecular weight and dispersity using size exclusion chromatography (SEC), and their chemical structure was confirmed using FT-IR and 1H-NMR spectroscopy techniques. The choice of the two hydrophilic blocks and the design of the macromolecular structure allowed the formation of self-assembled nanoparticles, partially due to the pH-responsive character of the DMAEMA segments and their interaction with -COOH end groups remaining from the chain transfer agent. The copolymers showed pH-responsive properties, mainly due to the protonation–deprotonation equilibria of the DMAEMA segments. Subsequently, a nanoscopic polymer–lipid (lipomer) mixed system was formulated by complexing the synthesized copolymers with cosmetic amphiphilic emulsifiers, specifically glyceryl stearate (GS) and glyceryl stearate citrate (GSC). This study aims to show that developing lipid–polymer hybrid nanoparticles can effectively address the limitations of both liposomes and polymeric nanoparticles. The effects of varying the ionic strength and pH on stimuli-sensitive polymeric and mixed polymer–lipid nanostructures were thoroughly investigated. To achieve this, the structural properties of the hybrid nanoparticles were comprehensively characterized using physicochemical techniques providing insights into their size distribution and stability.

Mechanistic Insights into the cis-Selective Catalytic Ring-Opening Metathesis Polymerization.

Cis-selective ring-opening metathesis polymerization (ROMP) with the commercial Grubbs "nitrato catalyst" has shown promise for synthesizing stereoregular materials, but it comes with the drawback of losing control over the molecular weight due to the poor initiation rate of the catalyst and the need for stoichiometric ruthenium complex loading. To address these issues, we developed a chain transfer polymerization method that allows for the catalytic synthesis of polymers while controlling the degree of polymerization. This allowed us to produce shorter polymers with exceptional chain-end control. Analysis of the polymers revealed a novel double monomer addition mechanism for this catalyst. MALDI-ToF mass spectrometric measurements showed that when using small monomers like norbornene, the polymer chains contained only odd numbers of monomers. In contrast, the polymerization of norbornene-imide-type monomers shows a major distribution with odd numbers of monomers along with a minor distribution of even numbers. This unique distribution of polymer chain types had not been previously observed in ROMP. We explain this phenomenon by the chiral nature of the catalyst that yields two isomeric catalytic species with dissimilar reactivities toward monomer and chain transfer agents.

Antithrombotic Agents After Free Tissue Transfer in the Pediatric and Adolescent Population.

Even for the experienced microsurgeon, free tissue transfer in pediatric patients is challenging, and large patient series remain scarce in the literature. Moreover, the added value of antithrombotic agents in pediatric free tissue transfer remains unclear. We conducted a retrospective outcome analysis of pediatric free tissue transfer with respect to postoperative antithrombotic treatment at our tertiary academic center. All patients aged 0 to 18 years who underwent free tissue transfer from 1998 to 2022 were included in the study. Seventy patients received 73 free tissue transfers. The most common indications were facial paralysis, trauma, and tumor (49.3%, 21.9%, and 20.5%, respectively). The most common recipient sites were the head and neck (56.1%) and lower extremity (32.8%). We observed a flap revision rate of 12.5% of the cases and one flap loss (1.4%). 58.9% of the population received post-operative antithrombotic agents. The rate of flap revision surgery was similar (11.6% and 10.0%, respectively), with and without antithrombotic treatment (p>0.05). There were no major bleeding complications or deep vein thrombosis. The antithrombotic treatment did not seem to affect the flap revision rate or the bleeding complications in our cohort. Hence, the data do not support the routine administration of antithrombotic treatment in pediatric free flap reconstruction. However, these findings should be solidified in prospective randomized trials.

Synthesis and Binding Properties of High-Affinity Histidine-Bearing Polymers for Wood Lignin.

The pursuit of molecules capable of binding to wood lignin is pivotal for advancing lignin degradation technology, particularly when combined with lignin degradation catalysts. In this study, synthetic polymers bearing histidine moieties, demonstrating remarkable affinity for wood lignin are reported. These polymers, featuring varying degrees of histidine substitution in the form of histidine methyl esters, are synthesized through controlled radical polymerization of an activated ester-bearing monomer, employing a fluorescein-labeled chain transfer agent and subsequent postpolymerization amidation with histidine methyl ester. The binding properties of these histidine-bearing polymers with milled wood lignin under aqueous conditions are investigated. Qualitative assessment of lignin-binding capabilities involve spectroscopic analysis of changes in absorbance of visible light and fluorescence intensity. Furthermore, quantitative evaluation is conducted through surface plasmon resonance measurements to determine the binding parameters of the polymers with wood lignin. Notably, polymers with higher histidine substitution exhibit enhanced binding affinity compared to those with lower histidine substitution levels.

Precise Control of Molecular Weight Characteristics of Charge-Shifting Poly(2-(N,N-Dimethylamino)Ethylacrylate) Synthesized by Reversible Addition-Fragmentation Chain Transfer Polymerization.

Poly(2-(N,N-dimethylamino)ethyl acrylate) (PDMAEA) is a promising charge-shifting polycation with the capacity to form a range of morphologically distinct polyelectrolyte assemblies. Nevertheless, the basic character of the monomer and its hydrolytic instability impedes its controlled synthesis to higher molecular weight (MW). Herein, the reversible addition-fragmentation chain transfer polymerization of DMAEA is reported using a tert-butanol/V70 initiator/trithiocarbonate-based chain transfer agent (CTA) polymerization setup. The CTA instability is demonstrated in the presence of the unprotonated tertiary amino group of the DMAEA monomer, which limits the control over the conversion and MW of the polymer. In contrast, the shielding of the amino groups by their protonation leads to polymerization with high conversions and excellent control over MWs of polymer up to 100000g mol-1. Hydrolytic degradation study at pH values ranging from 5 to 9 reveals that both basic and protonated PDMAEA undergo a pH-dependent hydrolysis. The proposed polymerization conditions provide a means of synthesizing PDMAEA with well-controlled characteristics, which are beneficial for controlling the complexation processes during the formation of various polyelectrolyte assemblies.

A novel label-free impedance biosensor for KRAS G12C mutations detection based on PET-RAFT and ROP synergistic signal amplification

The KRAS G12C mutations, as crucial biomarkers, are closely associated with non-small cell lung cancer. Here, a novel label-free electrochemical biosensor with synergistic signal amplification of photocell energy transfer-reversible addition fragmentation chain transfer (PET-RAFT) and ring-opening polymerization (ROP) was developed for the first time for sensitive detection of KRAS G12C mutations. Specifically, hairpin DNA (hDNA), which act as biomolecular probe, was self-assembled on Au electrode surface by Au-S bond. 4-cyano-4-[(dodecylsulfanylthiocarbonyl) sulfanyl] pentanoic acid (CDTPA), the chain transfer agent of PET-RAFT reaction, was then attached to hDNA via amide bond. After that, the target DNA (tDNA) was captured on the electrode surface by complementary base pairing with hDNA. Subsequently, large numbers of electro-active monomers N-acryloxysuccinimide (NAS) were successfully grafted to the electrode surface via PET-RAFT reaction, which provided plenty of junction sites for doxorubicin-polycaprolactone (Dox-PCL) synthesized by ROP. Finally, the Dox-PCL was connected to the electrode surface by ester bond, significantly amplifying the electrochemical signal. Under optimized conditions, the biosensor has a wide linear detection range of 0.1 pM to 1 μM, with a detection limit of 86.9 fM. Attribute to its high sensitivity, specificity, reproducibility and stability, this biosensor possesses considerable potential in early diagnosis of disease and biomedical research.

A Systematic Study on Biobased Epoxy-Alcohol Networks: Highlighting the Advantage of Step-Growth Polyaddition over Chain-Growth Cationic Photopolymerization.

Vanillyl alcohol has emerged as a widely used building block for the development of biobased monomers. More specifically, the cationic (photo-)polymerization of the respective diglycidyl ether (DGEVA) is known to produce materials of outstanding thermomechanical performance. Generally, chain transfer agents (CTAs) are of interest in cationic resins not only because they lead to more homogeneous polymer networks but also because they strikingly improve the polymerization speed. Herein, the aim is to compare the cationic chain-growth photopolymerization with the thermally initiated anionic step-growth polymerization, with and without the addition of CTAs. Indeed, CTAs lead to faster polymerization reactions as well as the formation of more homogeneous networks, especially in the case of the thermal anionic step-growth polymerization. Resulting from curing above the TG of the respective anionic step-growth polymer, materials with outstanding tensile toughness (>5MJ cm-3) are obtained that result in the manufacture of potential shape-memory polymers.

Cyclic Sulfoximines as Methyl and Perdeuteromethyl Transfer Agents and Their Applications in Photoredox Catalysis.

Benzo[1,3,2]dithiazole-1,1,3-trioxides are bench-stable and easy-to-use reagents. In photoredox catalysis, they generate methyl and perdeuteromethyl radicals which can add to a variety of radical acceptors, including olefins, acrylamides, quinoxalinones, isocyanides, enol silanes, and N-Ts acrylamide. As byproduct, a salt is formed which can be regenerated to the original methylating agent. Flow chemistry provides an option for reaction scale-up further underscoring the synthetic usefulness of these methylation reagents. Mechanistic investigations suggest a single-electron transfer (SET) pathway induced by photoredox catalysis.

Cyclic Sulfoximines as Methyl and Perdeuteromethyl Transfer Agents and Their Applications in Photoredox Catalysis

AbstractBenzo[1,3,2]dithiazole‐1,1,3‐trioxides are bench‐stable and easy‐to‐use reagents. In photoredox catalysis, they generate methyl and perdeuteromethyl radicals which can add to a variety of radical acceptors, including olefins, acrylamides, quinoxalinones, isocyanides, enol silanes, and N‐Ts acrylamide. As byproduct, a salt is formed which can be regenerated to the original methylating agent. Flow chemistry provides an option for reaction scale‐up further underscoring the synthetic usefulness of these methylation reagents. Mechanistic investigations suggest a single‐electron transfer (SET) pathway induced by photoredox catalysis.

Polyalkenamers as Drop-In Additives for Ring-Opening Metathesis Polymerization: A Promising Upcycling Paradigm.

We report a distinct strategy to upcycle waste polyalkenamers such as polybutadiene into new, performance-advantaged materials by using them as drop-in additives for ring-opening metathesis polymerization (ROMP). The polyalkenamers serve as competent chain-transfer agents in ROMPs of common classes of cyclic olefin monomers, facilitating good molecular weight control, allowing low Ru catalyst loadings, and enabling efficient incorporation of the polyalkenamer into the synthesized polymeric material. We successfully demonstrate ROMP using model polyalkenamers and translate these learnings to leverage commercial polybutadiene and acrylonitrile butadiene styrene (ABS) as chain transfer agents for ROMP copolymerizations. Critically, our strategy is shown to be highly efficient and operationally simple, quantitatively incorporating the polyalkenamer and inheriting aspects of its thermomechanical performance. Our results highlight a promising pathway for the upcycling of polyalkenamers and provide an alternative to existing deconstruction and functional upcycling strategies.

Regulating Chlorine and Hydrogen Atom Transfer for Selective Photoelectrochemical C─C Coupling by Cu-coordination Effect at Semiconductor/Electrolyte Interfaces.

Semiconductor-based photoelectrochemical (PEC) organic transformations usually show radical characteristics, in which the reaction selectivity is often difficult to precisely control due to the nonselectivity of radicals. Accordingly, several simple organic reactions (e.g., oxidations of alcohols, aldehydes, and other small molecules) have been widely studied, while more complicated processes like C─C coupling remain challenging. Herein, a synergistic heterogeneous/homogeneous PEC strategy is developed to achieve a controllable radical-induced C─C coupling reaction mediated by the copper-coordination effect at the semiconductor/electrolyte interfaces, which additionally exerts a significant impact on the product regioselectivity. Through experimental studies and theoretical simulations, this study reveals that the copper-chloride complex effectively regulates the formation of chloride radicals, a typical hydrogen atom transfer agent, on semiconductor surfaces and stabilizes the heterogeneous interfaces by suppressing the radical-induced surface passivation. Taking the Minisci reaction (the coupling between 2-phenylquinoline and cyclohexane) as a model, the yield of the target C─C coupling product reaches up to 90% on TiO2 photoanodes with a selectivity of 95% and long-term stability over 100h. Moreover, such a strategy exhibits a broad scope and can be used for the functionalization of various heteroaromatic hydrocarbons.

Determination of Chain Transfer Constants of Alcohols for High‐Pressure Polyethylene Polymerization

AbstractIn low‐density polyethylene (LDPE) production, low‐molecular‐weight species are used as chain transfer agents (CTAs). They reduce the degree of polymerization, which has an impact on the polymer properties, such as processability. To specifically adjust the product properties, a detailed understanding of the transfer kinetics to CTAs is indispensable. Thus, the transfer activity of various primary, secondary, and tertiary alcohols as well as diols was investigated experimentally between 120 °C and 250 °C at 2000 bar. The results were evaluated using the Mayo and chain length distribution (CLD) method, and the latter was found to give more reliable results. It was observed that the hydroxy group systematically increases transfer activity compared to alkanes. Additionally, a linear increase of transfer activity with the number of hydrogen atoms is found.

A proton-coupled electron transfer process from functionalized carbon dots to molecular substrates: the role of pH.

Multiple electron and proton transfers in nanomaterials pose significant demands and challenges across the various fields such as renewable energy, chemical processes, biological applications, and photophysics. In this context, pH-responsive functional group-enriched carbon dots (C-Dots) emerge as superior proton-coupled electron transfer (PCET) agents owing to the presence of multiple functional groups (-COOH, -NH2, and -OH) on the surface and redox-active sites in the core. Here, we elucidate the 2e-/2H+ transfer ability of carboxyl-enriched C-Dots (C-Dot-COOH) and amine-enriched C-Dots (C-Dot-NH2) with molecular 2e-/2H+ acceptor (benzoquinone, BQ) as a function of pKa, facilitated by the formation of new O-H bonds. The ground state and excited state pKa values of different functional groups on the surface of C-Dots are determined using steady-state absorbance and photoluminescence (PL) spectroscopy. The optical spectroscopy and electrochemical studies are employed to comprehend the influence of the surface and core of C-Dots on the proton and electron transfer processes as a function of pH. The cyclic voltammetry analysis reveals a standard Nernstian shift in E1/2 per pH unit of 30 mV, indicating that the functionalized C-Dots hold promise as candidates for the 2e-/2H+ transfer process. The calculated bond dissociation free energy (BDFE) of the electroactive O-H/N-H bonds provides a more nuanced and detailed understanding of PCET thermodynamic landscapes. These findings underscore the potential of nanoscale functionalized C-Dots for facilitating multiple PCET reactions in future energy technologies.

Synergistic enhancement of magic triangle properties of PC tread stocks modified by amine-capped trans-1,4-poly (butadiene-co-isoprene)

The development of high-performance “green tires” with synergistically improved “magic triangle” properties like lower rolling resistance, higher wet-skid resistance and higher abrasion resistance has always been a hot issue. In this work, an effective strategy for developing high-performance “green tires” with simultaneously improved “magic triangle” properties of solution-polymerized styrene-butadiene rubber (SSBR)/cis-1,4-polybutadiene rubber (BR) nanocomposites modified by amine-capped trans-1,4-poly(butadiene-co-isoprene) copolymers (F-TBIR) was proposed. A series of F-TBIR with 10–60 mol% amine-capped efficiency (CE) and 30-90 × 104 weight-average molecular weight (Mw) were synthesized by using heterogeneous TiCl4/MgCl2–Al(i-Bu)3 Ziegler-Natta catalyst with dicyclohexylamine (DCHA) as chain transfer agent (CTA). With the increase in CE of F-TBIR, the silica-filled SSBR/BR/F-TBIR compounds exhibited improved green strength, modulus at 100 % elongation and bound rubber, and their vulcanizates showed synergistically improved “magic triangle” properties like obviously reduced rolling resistance and abrasion loss, and increased wet-skid resistance. It was found that the incorporation of 10 phr F-TBIR3 with CE of 60 mol% and Mw of 32 × 104 resulted in highly expected properties of the SSBR/BR/F-TBIR3 nanocomposite. The contribution mechanism of F-TBIR3 was discussed based on the improvements of polymer network structures and filler network structures. This work is expected to provide an effective strategy to construct the desired network structures for high-performance rubber composites.

Liquid carboxylated nitrile butadiene rubber via metathetic degradation with acrylic acid as chain transfer agent

Liquid carboxylated nitrile butadiene rubber (LXNBR) shows promising application in various fields. Facing the challenges in its preparation via radical emulsion copolymerization, such as gelation, molecular weight and carboxyl group content, novel approach has been developed for the controlled preparation of LXNBR via the metathetic degradation of nitrile butadiene rubber (NBR) with acrylic acid (AA) as chain transfer agent (CTA). Based on the molecular weight and carboxyl group content of the resultant products, the reaction pathway was proposed. Such understanding is expected to prepare LXNBR with designed Mn and carboxyl group content for various applications, by facile adjusting the reaction condition, mainly the feeding mode of AA, NBR concentration and reaction time.

Research on hydrodynamics of the thermal agent flow for the beet pulp filtration drying

The reuse and recycling of secondary raw materials is essential to ensure sustainable development and the rational use of natural resources. One of the most important types of secondary raw materials is plant-based food waste, which is generated in large quantities at food processing plants, including sugar beet pulp, which is a valuable resource for further use. One of the main problems with using beet pulp is its high moisture content, which is ≈ 80 % wt. It is proposed to dry beet pulp by filtration drying, which is highly efficient. The calculation of industrial equipment for filtration drying should take into account the costs of overcoming the hydraulic resistance of a stationary layer of material. The aim of the article was to study the hydrodynamics of the flow of a thermal agent through a stationary layer of beet pulp of different heights and to perform computer modelling of this process. The obtained results will allow predicting the hydraulic resistance of a material layer of different heights and the required pressure drop to ensure the course of the drying process under various possible technological modes. For computer modelling of the flow of a thermal agent through a stationary layer of beet pulp, the porous media method was used in the ANSYS Fluent 2022 R2 software package. The process was simulated on the basis of the Navier-Stokes system of differential equations and the flow continuity equation with the additional use of the Darcy equation to determine the value of the hydraulic resistance of the layer ΔP. Computer simulations of the hydrodynamics of the thermal agent flow through a stationary layer of beet pulp were performed for the range of stationary layer heights H = 90÷110 mm with an interval of 5 mm. The obtained data showed a relative average deviation of 2.19 % from the experimental data, which indicates a high accuracy of calculations in this range. The study for the extended range of layer heights H = 80÷120 mm with an interval of 10 mm showed an increase in the relative average deviation to 4.09 % from the experimental data, but the results are still sufficiently accurate for practical use in the calculation of drying equipment. The obtained dependencies may be used to determine the value of the hydraulic resistance of a stationary layer of material using the filtration drying method and for practical calculations of drying equipment. Together with the results of the kinetic regularities of filtration drying, the obtained experimental data and computer modelling data on the hydrodynamics of the flow of a heat transfer agent through a material layer will allow us to calculate the optimal parameters of filtration drying for beet pulp and to assess the efficiency of filtration drying for drying beet pulp in comparison with other methods of dehydration.

An Innovative Approach for Oxidative Desulfurization Advancement through High Shear Mixing: An Optimization Study on the Application of Benzothiophene.

Alternative fuels are being explored to mitigate the effects of petroleum-based fuels. Pyrolysis oil from waste tires is a promising alternative fuel; however, it contains very high concentrations of benzothiophene (BT) which are beyond the allowable sulfur limits of Taiwan and the Philippines. Mixing-assisted oxidative desulfurization (MAOD) is a method that removes sulfur from fuel oils by utilizing high-shear mixing and oxidants. In this paper, the oxidation of BT in a model fuel was studied to determine optimal process conditions. Crude Fe(VI) prepared from sludge was used as the oxidant. Using the Box-Behnken design under response surface methodology, the significance of the following independent variables was studied: mixing speed (4400-10 800 rpm), phase transfer agent (PTA) amount (100 to 300 mg), Fe(VI) concentration (400-6000 ppm), and mixing temperature (40 to 60 °C). The results from a comprehensive statistical analysis showed the increase of sulfur conversion with high levels of Fe(VI) concentrations and PTA amounts together with low levels of agitation speeds and temperatures. The BT to BT sulfone conversions from experimental runs ranged from 17% to 64%. The optimum sulfur conversion of 88% for the BT model fuel was reached at the maximum levels of Fe(VI) concentration and mixing speed, along with the minimum levels of PTA concentration and temperature. The optimal MAOD variables were applied to a high-sulfur pyrolysis oil sample, which resulted in a sulfur reduction of 55%. The produced fuel oil meets the sulfur requirements of Taiwan and the Philippines for industrial heating oils. Therefore, the findings of the study support the effectiveness of sludge-derived Fe(VI) in the MAOD of BT in the model fuel and pyrolysis oil under mild process conditions.