Organocatalyzed Atom Transfer Radical Polymerization Research Articles

Antibacterial Zirconia Surfaces from Organocatalyzed Atom-Transfer Radical Polymerization.

Antibacterial coatings are becoming increasingly attractive for application in the field of biomaterials. In this framework, we developed polymer coating zirconia with antibacterial activity using the "grafting from" methodology. First, 1-(4-vinylbenzyl)-3-butylimidazolium chloride monomer was synthesized. Then, the surface modification of zirconia substrates was performed with this monomer via surface-initiated photo atom transfer radical polymerization for antibacterial activity. X-ray photoelectron spectroscopy, ellipsometry, static contact angle measurements, and an atomic force microscope were used to characterize the films for each step of the surface modification. The results revealed that cationic polymers could be successfully deposited on the zirconia surfaces, and the thickness of the grafted layer steadily increased with polymerization time. Finally, the antibacterial adhesion test was used to evaluate the antibacterial activity of the modified zirconia substrates, and we successfully showed the antibacterial activity against Staphylococcus aureus and Pseudomonas aeruginosa strains.

Self-Templating Copolymerization to Produce Robust Conductive Nanocoatings Based on Conjugated Polymer Brushes with Implementable Memristive Characteristics.

An effective synthesis of conductive polymer brushes, i.e., self-templating surface-initiated copolymerization (ST-SICP), is developed. It proceeds through copolymerization of pendant thiophene groups in the precursor multimonomer poly(3-methylthienyl methacrylate) (PMTM) brushes with free 3-methylthiophene (3MT) monomers leading to PMTM-co-P3MT brushes. This approach leads to improved conformational freedom of generated conjugated poly(thiophene)-based chains and their higher share in the brushes with respect to conjugation of pendant thiophene groups only. As a result, best performing conjugated PMTM-co-P3MT brushes demonstrate high ohmic conductivity in both out-of-plane and in-plane direction. Furthermore, thanks to the covalent anchoring as well as intra- and intermolecular connections, highly stable and mechanically robust nanocoatings are produced which can survive mechanical cleaning and long-term storage under ambient conditions. Grafting of ionic poly(sodium 4-styrenesulfonate) (PSSNa) in between PMTM-co-P3MT chains brings new properties to such binary mixed brushes that can operate as thin-film memristive coating with switchable conductance. It is worth mentioning that the crucial synthetic steps, i.e., grafting of precursor PMTM brushes by surface-initiated organocatalyzed atom transfer radical polymerization (SI-O-ATRP) and PSSNa chains by surface-initiated photoiniferter-mediated polymerization (SI-PIMP) are conducted under ambient conditions using only microliter volumes of reagents providing methodology that can be considered for use beyond the laboratory scale.

Versatile poly(N-vinylcaprolactam)-grafted-hydroxypropyl cellulose polymers with tailored thermo- and pH-responsive properties via sustainable organocatalyzed atom transfer radical polymerization

This study explores the synthesis of dual pH- and thermo-responsive poly(N-vinylcaprolactam)-grafted-hydroxypropyl cellulose (PNVCL-g-HPC) polymers via visible-light-driven, metal-free organocatalyzed atom transfer radical polymerization (O-ATRP).

Impact of Alkyl Core Substitution Kinetics in Diaryl Dihydrophenazine Photoredox Catalysts on Properties and Performance in O-ATRP.

Organocatalyzed atom transfer radical polymerization (O-ATRP) is a controlled radical polymerization method mediated by organic photoredox catalysts (PCs) for producing polymers with well-defined structures. While N,N-diaryl dihydrophenazine PCs have successfully produced polymers with low dispersity (Đ < 1.3) in O-ATRP, low initiator efficiencies (I* ~ 60-80%) indicate an inability to achieve targeted molecular weights and have been attributed to the addition of radicals to the PC core. In this work, we measure the rates of alkyl core substitution (AkCS) to gain insight into why PCs differing in N-aryl group connectivity exhibit differences in polymerization control. Additionally, we evaluate how PC properties evolve during O-ATRP when a non-core-substituted PC is used. PC 1 with 1-naphthyl groups in the N-aryl position resulted in faster AkCS (k 1 = 1.21 ± 0.16 × 10-3 s-1, k 2 = 2.04 ± 0.11 × 10-3 s-1) and better polymerization control at early reaction times as indicated by plots of molecular weight (number average molecular weight = M n) vs conversion compared to PC 2 with 2-naphthyl groups (k 1 = 6.28 ± 0.38 × 10-4 s-1, k 2 = 1.15 ± 0.07 × 10-3 s-1). The differences in rates indicate that N-aryl connectivity can influence polymerization control by changing the rate of AkCS PC formation. The rate of AkCS increased from the initial to the second substitution, suggesting that PC properties are modified by AkCS. Increased PC radical cation (PC•+) oxidation potentials (E 1/2 = 0.26-0.27 V vs SCE) or longer triplet excited-state lifetimes (τ T1 = 1.4-33 μs) for AkCS PCs 1b and 2b compared to parent PCs 1 and 2 (E 1/2 = 0.21-0.22 V vs SCE, τ T1 = 0.61-3.3 μs) were observed and may explain changes to PC performance with AkCS. Insight from evaluation of the formation, properties, and performance of AkCS PCs will facilitate their use in O-ATRP and in other PC-driven organic transformations.

Photomediated core modification of diaryl dihydrophenzines through three-component alkylarylation of alkenes toward organocatalyzed ATRP

The design and synthesis of a novel organic photocatalyst (OPC) have attracted broad interest from both the organic chemistry and polymer community. Herein, we presented a visible-light-induced alkylarylation of alkenes strategy for core modification of 5,10-diaryl-5,10-dihydrophenazines (DADHPs) under metal- and additive-free conditions, with the aim to develop powerful photocatalyst for organocatalyzed atom transfer radical polymerization (O-ATRP). Good tolerance for a wide variety of functional groups and affording the corresponding tetrasubstituted products in moderate to good yields were achieved in the batch and flow reactor. The experimental and computational mechanistic study confirmed that DADHPs’ radical cations and π-π stacking interactions played important roles in the alkylarylation of alkenes. A series of the tetrasubstituted DADHPs were directly synthesized from the corresponding noncore-modified phenazines, which were demonstrated to be effective organic photoredox catalysts for O-ATRP. Light responsive nature, controlled polymerization manner, and well-defined poly (methyl methacrylate) were achieved via tetrasubstituted DADHPs mediated O-ATRP.

Specific Active Sites of Organo-Photocatalysts for Photo-Atom Transfer Radical Polymerization: A Combined Experimental and Theoretical Study of N-Unsubstituted Diketopyrrolopyrrole

Organocatalyzed atom transfer radical polymerization (O-ATRP) with light, acting as photoredox catalysis, is growing to be one of the emerging fields of photocatalysis and chemical transformations due to the mild, environment-friendly, and light-control manners. To screen much more effective metal-free photocatalysts and the exact functions of different fragments in organic molecular photocatalysts, this report selected N-unsubstituted diketopyrrolopyrrole (DPP) analogues and figured out the structure–properties relationship and the catalytic mechanism. The results revealed the key role of the N-unsubstituted DPP core in the charge transfer, singlet/triplet formation, and intermediate formation. Furthermore, the DPP core acted as the function of reductive reaction initiators with reductive potentials, while the adjacent groups tuned oxidative potentials and stability of the radical cations and simultaneously controlled the oxidative quenching deactivation process through the bromide (−Br) intermediates of doublet complexes. The systematic inspection of the atomic active sites of photoredox catalysts has so far not been taken into consideration regarding both the experimental and theoretical examination. The findings about these novel DPP photoredox catalysts will aid in the rational search for much more effective organo-photoredox metal-free compounds for use in controlled radical polymerization and other organic transformations.

Improving chitosan performance in the simultaneous adsorption of multiple polycyclic aromatic hydrocarbons by oligo(β-pinene) incorporation

The occurrence of persistent organic pollutants in aquatic bodies, namely polycyclic aromatic hydrocarbons (PAHs), has been increasingly detected. The presence of such contaminants represents a serious threat to human health due to their toxicity. Therefore, aiming to provide a novel and efficient alternative for PAHs' removal from water, the present study assesses the effect of oligo(β-pinene) blended with chitosan for the adsorption of these pollutants. Oligo(β-pinene) with phenyl end-groups was synthesized by organocatalyzed atom transfer radical polymerization (O-ATRP) and incorporated in different concentrations (6, 12, and 18 %) to chitosan films. The oligo(β-pinene) loading in the chitosan matrix impressively improved this polysaccharide adsorption capacity. The formulation containing 12 % of oligomer demonstrated a contaminant removal performance three times higher (298.82 %) than pure chitosan during only 1 h of the decontamination process. Adsorption isotherms showed an improved uptake of PAHs with the increase of the contaminants' concentration in the aqueous media due to the formation of a higher concentration gradient. Additionally, a comprehensive characterization of oligo(β-pinene)/chitosan formulation was performed to provide a better understanding of the interactions between the components of the blends. Overall, it was concluded that oligo(β-pinene)/chitosan blends can be used as a high-performance and sustainable alternative for PAHs removal.

Removal of photoredox catalysts from polymers synthesized by organocatalyzed atom transfer radical polymerization.

Organocatalyzed atom transfer radical polymerization (O-ATRP) is a method of producing polymers with precise structures under mild conditions using organic photoredox catalysts (PCs). Due to the unknown toxicity of PCs and their propensity to introduce color in polymers synthesized by this method, removal of the PC from the polymer product can be important for certain applications of polymers produced using O-ATRP. Current purification methods largely rely on precipitation to remove the PC from the polymer, but a more effective and efficient purification method is needed. In this work, an alternative purification method relying on oxidation of the PC to PC · + followed by filtration through a plug to remove PC · + from the polymer and removal of the volatiles was developed. A range of chemical oxidants and stationary phases were tested for their ability to remove PCs from polymers, revealing chemical oxidation by N-bromosuccinimide followed by a filtration through a silica plug can remove up to 99% of the PC from poly(methyl methacrylate). Characterization of the polymer before and after purification demonstrated that polymer molecular weight, dispersity, and chain-end fidelity are not signficantly impacted by this purification method. Finally, this purification method was tested on a range of dihydrophenazine, phenoxazine, dihydroacridines, and phenothiazine PCs, revealing the strength of the chemical oxidant must match the oxidation potential of the PC for effective purification.

Effects of the Chalcogenide Identity in N-Aryl Phenochalcogenazine Photoredox Catalysts.

Phenochalcogenazines such as phenoxazines and phenothiazines have been widely employed as photoredox catalysts (PCs) in small molecule and polymer synthesis. However, the effect of the chalcogenide in these catalysts has not been fully investigated. In this work, a series of four phenochalcogenazines is synthesized to understand how the chalcogenide impacts catalyst properties and performance. Increasing the size of the chalcogenide is found to distort the PC structure, ultimately impacting the properties of each PC. For example, larger chalcogenides destabilize the PC radical cation, possibly resulting in catalyst degradation. In addition, PCs with larger chalcogenides experience increased reorganization during electron transfer, leading to slower electron transfer. Ultimately, catalyst performance is evaluated in organocatalyzed atom transfer radical polymerization and a photooxidation reaction for C(sp2)−N coupling. Results from these experiments highlight that a balance of PC properties is most beneficial for catalysis, including a long‐lived excited state, a stable radical cation, and a low reorganization energy.

Donor modification of thermally activated delayed fluorescence photosensitizers for organocatalyzed atom transfer radical polymerization

TADF donor-acceptor conjugates were applied as photosensitizers for organocatalyzed organic atom transfer radical polymerization. A donor-modification strategy was found to dramatically improve the control over the polymerization.

Photoinduced Organocatalyzed Atom Transfer Radical Polymerization (O-ATRP): Precision Polymer Synthesis Using Organic Photoredox Catalysis.

The development of photoinduced organocatalyzed atom transfer radical polymerization (O-ATRP) has received considerable attention since its introduction in 2014. Expanding on many of the advantages of traditional ATRP, O-ATRP allows well-defined polymers to be produced under mild reaction conditions using organic photoredox catalysts. As a result, O-ATRP has opened access to a range of sensitive applications where the use of a metal catalyst could be of concern, such as electronics, certain biological applications, and the polymerization of coordinating monomers. However, key limitations of this method remain and necessitate further investigation to continue the development of this field. As such, this review details the achievements made to-date as well as future research directions that will continue to expand the capabilities and application landscape of O-ATRP.

O-ATRP synthesized poly(β-pinene) blended with chitosan for antimicrobial and antioxidant bio-based films production

Antioxidant and antimicrobial activities are important characteristics of active film packaging designed to extend food preservation. In this study, functional bio-based films were produced using different concentrations of antioxidant poly(β-pinene) bio-oligomer synthesized via organocatalyzed atom transfer radical polymerization (O-ATRP) and blended with chitosan of different molecular weights. The structural, mechanical, thermal, solubility, antioxidant, and antimicrobial properties of the films were investigated. The poly(β-pinene)-chitosan blends presented significant pores and irregularities with the increase of poly(β-pinene) concentration over 30%. Chitosan molecular weight did not show any important influence in the physical properties of the blends. Poly(β-pinene) load decreased the materials' tensile strength and melting temperature, exhibiting a plasticizing effect on chitosan chains. The antioxidant and antimicrobial activities of the films were improved by poly(β-pinene) incorporation and mainly depended on its concentration. Therefore, the incorporation of poly(β-pinene) in chitosan films can be an alternative for active packaging production.

Visible-Light Amine Thioxanthone Derivatives as Photoredox Catalysts for Photopolymerization Processes

Herein, mono- and disubstituted thioxanthones have been synthesized and introduced as photosensitizers of iodonium salt for cationic and free-radical photopolymerization of epoxy and an acrylate monomer, respectively. Photoinitiation activity of these molecules was verified during photopolymerization processes performed upon exposure to visible LEDs of 420, 455, and 470 nm. The kinetics of the photopolymerization processes was followed using FT-IR spectroscopy. Moreover, the developed compounds were proposed as strongly reducing metal-free photoredox catalysts in organocatalyzed atom transfer radical polymerization (ATRP). Thioxanthone derivatives (with alkyl halide) efficiently activate the ATRP of methyl methacrylate using a visible LED as an irradiation source. The formed polymers in the ATRP process were characterized by SEC. Apart from studying the photopolymerization processes with the participation of obtained thioxanthones, absorption, fluorescence, as well as electrochemical properties of thioxanthone derivatives were investigated. Furthermore, the performance of studied compounds in 3D printing applications was also examined. The most important result of this study is the design and possible application of photosensitizers/photocatalysts for photopolymerization processes.

Structure-Dependent Electron Transfer Rates for Dihydrophenazine, Phenoxazine, and Phenothiazine Photoredox Catalysts Employed in Atom Transfer Radical Polymerization.

Organic photocatalysts (PCs) are gaining popularity in applications of photoredox catalysis, but few studies have explored their modus operandi. We report a detailed mechanistic investigation of the electron transfer activation step of organocatalyzed atom transfer radical polymerization (O-ATRP) involving electronically excited organic PCs and a radical initiator, methyl 2-bromopropionate (MBP). This study compares nine N-aryl modified PCs possessing dihydrophenazine, phenoxazine, or phenothiazine core chromophores. Transient electronic and vibrational absorption spectroscopies over subpicosecond to nanosecond and microsecond time intervals, respectively, track spectroscopic signatures of both the reactants and products of photoinduced electron transfer in N,N-dimethylformamide, dichloromethane, and toluene solutions. The rate coefficients for electron transfer exhibit a range of values up to ∼1010 M-1 s-1 influenced systematically by the PC structures. These rate coefficients are an order of magnitude smaller for catalysts with charge transfer character in their first excited singlet (S1) or triplet (T1) states than for photocatalysts with locally excited character. The latter species show nearly diffusion-limited rate coefficients for the electron transfer to MBP. The derived kinetic parameters are used to model the contributions to electron transfer from the S1 state of each PC for different concentrations of MBP. Comparisons of singlet and triplet reactivity for one of the phenoxazine PCs reveal that the rate coefficient kET(T1) = (2.7 ± 0.3) × 107 M-1 s-1 for electron transfer from the T1 state is 2 orders of magnitude lower than that from the S1 state, kET(S1) = (2.6 ± 0.4) × 109 M-1 s-1. The trends in bimolecular electron transfer rate coefficients are accounted for using a modified Marcus theory for dissociative electron transfer.

Metal-Free Organocatalyzed Atom Transfer Radical Polymerization: Synthesis, Applications, and Future Perspectives.

Reversible deactivation radical polymerization (RDRP) is a class of powerful techniques capable of synthesizing polymers with a well-defined structure, properties, and functionalities. Among the available RDRPs, ATRP is the most investigated. However, the necessity of a metal catalyst represents a drawback and limits its use for some applications. O-ATRP emerged as an alternative to traditional ATRP that uses organic compounds that catalyze polymerization under light irradiation instead of metal. The friendly nature and the robustness of O-ATRP allow its use in the synthesis of tailorable advanced materials with unique properties. In this review, the fundamental aspects of the reductive and oxidative quenching mechanism of O-ATRP are provided, as well as insights into each component and its role in the reaction. Besides, the breakthrough recent studies that applied O-ATRP for the synthesis of functional materials are presented, which illustrate the significant potential and impact of this technique across diverse fields.

Radical Addition to N,N-Diaryl Dihydrophenazine Photoredox Catalysts and Implications in Photoinduced Organocatalyzed Atom Transfer Radical Polymerization.

Photoinduced organocatalyzed atom transfer radical polymerization (O-ATRP) is a controlled radical polymerization methodology catalyzed by organic photoredox catalysts (PCs). In an efficient O-ATRP system, good control over molecular weight with an initiator efficiency (I* = M n,theo/M n,exp × 100%) near unity is achieved, and the synthesized polymers possess a low dispersity (Đ). N,N-Diaryl dihydrophenazine catalysts typically produce polymers with low dispersity (Đ < 1.3) but with less than unity molecular weight control (I* ~ 60-80%). This work explores the termination reactions that lead to decreased control over polymer molecular weight and identifies a reaction leading to radical addition to the phenazine core. This reaction can occur with radicals generated through reduction of the ATRP initiator or the polymer chain end. In addition to causing a decrease in I*, this reactivity modifies the properties of the PC, ultimately impacting polymerization control in O-ATRP. With this insight in mind, a new family of core-substituted N,N-diaryl dihydrophenazines is synthesized from commercially available ATRP initiators and employed in O-ATRP. These new core-substituted PCs improve both I* and Đ in the O-ATRP of MMA, while minimizing undesired side reactions during the polymerization. Further, the ability of one core-substituted PC to operate at low catalyst loadings is demonstrated, with minimal loss of polymerization control down to 100 ppm (weight average molecular weight [M w] = 10.8 kDa, Đ = 1.17, I* = 104% vs M w = 8.26, Đ = 1.10, I* = 107% at 1000 ppm) and signs of a controlled polymerization down to 10 ppm of the catalyst (M w = 12.1 kDa, Đ = 1.36, I* = 107%).

Radical Cations of Phenoxazine and Dihydrophenazine Photoredox Catalysts and Their Role as Deactivators in Organocatalyzed Atom Transfer Radical Polymerization.

Radical cations of photoredox catalysts used in organocatalyzed atom transfer radical polymerization (O-ATRP) have been synthesized and investigated to gain insight into deactivation in O-ATRP. The stability and reactivity of these compounds were studied in two solvents, N,N-dimethylacetamide and ethyl acetate, to identify possible side reactions in O-ATRP and to investigate the ability of these radical cations to deactivate alkyl radicals. A number of other factors that could influence deactivation in O-ATRP were also probed, such as ion pairing with the radical cations, radical cation oxidation potential, and halide oxidation potential. Ultimately, these studies enabled radical cations to be employed as reagents during O-ATRP to demonstrate improvements in polymerization control with increasing radical cation concentrations. In the polymerization of acrylates, this approach enabled superior molecular weight control, a decrease in polymer dispersity from 1.90 to 1.44, and an increase in initiator efficiency from 78 to 102%. This work highlights the importance of understanding the mechanism and side reactions of O-ATRP, as well as the importance of catalyst radical cations for successful O-ATRP.

Synthesis, Characterization, and Reactivity of N-Alkyl Phenoxazines in Organocatalyzed Atom Transfer Radical Polymerization.

Core-modified N-alkyl phenoxazines were synthesized and evaluated as photoredox catalysts (PCs) in organocatalyzed atom transfer radical polymerization (O-ATRP). Each PC was characterized and found to strongly absorb UVA and visible light, undergo reversible oxidation to radical cation species, and exhibit high quantum yields of fluorescence (Φf > 77%). PCs found to exhibit intramolecular charge transfer in their excited state were capable of the controlled synthesis of poly(methyl methacrylate) with good molecular weight control (I* ~ 100%) and moderately low dispersity (Đ < 1.30).

Singlet and Triplet Contributions to the Excited-State Activities of Dihydrophenazine, Phenoxazine, and Phenothiazine Organocatalysts Used in Atom Transfer Radical Polymerization.

The photochemical dynamics of three classes of organic photoredox catalysts employed in organocatalyzed atom-transfer radical polymerization (O-ATRP) are studied using time-resolved optical transient absorption and fluorescence spectroscopy. The nine catalysts selected for study are examples of N-aryl and core-substituted dihydrophenazine, phenoxazine and phenothiazine compounds with varying propensities for control of polymerization outcomes. Excited singlet-state lifetimes extracted from the spectroscopic measurements are reported in N,N-dimethylformamide (DMF), dichloromethane (DCM), and toluene. Ultrafast (<200 fs to 3 ps) electronic relaxation of the photocatalysts after photoexcitation at near-UV wavelengths (318-390 nm) populates the first singlet excited state (S1). The S1-state lifetimes range from 130 ps to 40 ns with a considerable dependence on the photocatalyst structure and the solvent. The competition between ground electronic state recovery and intersystem crossing controls triplet state populations and is a minor pathway in the dihydrophenazine derivatives but is of greater importance for phenoxazine and phenothiazine catalysts. A comparison of our results with previously reported O-ATRP performances of the various photoredox catalysts shows that high triplet-state quantum yields are not a prerequisite for controlling polymer dispersity. For example, the photocatalyst 5,10-bis(4-cyanophenyl)-5,10-dihydrophenazine, shown previously to exert good polymerization control, possesses the shortest S1-state lifetime (135 ps in DMF and 180 ps in N,N-dimethylacetamide) among the nine examples reported here and a negligible triplet-state quantum yield. The results call for a re-evaluation of the excited-state properties of most significance in governing the photocatalytic behavior of organic photoredox catalysts in O-ATRP reactions.

Structure–property relationships of core-substituted diaryl dihydrophenazine organic photoredox catalysts and their application in O-ATRP

Photoinduced organocatalyzed atom-transfer radical polymerization (O-ATRP) is a controlled radical polymerization technique that can be driven using low-energy, visible light and makes use of organic photocatalysts.