Aqueous Metal-Free Atom Transfer Radical Polymerization: Experiments and Model-Based Approach for Mechanistic Understanding

Bian, Chao; Zhou, Yin‐Ning; Guo, Jinsong; Luo, Zheng‐Hong

doi:10.1021/acs.macromol.8b00348

Cited by 70 publications

(73 citation statements)

References 69 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Bian et al. ′s mechanistic study revealed the importance of the sacrificial electron donor in the reductive quenching mechanism [72] . It was found that the rate of polymerization increases with an increase in the concentrations of electron donors, which results in a higher concentration of the alkyl radicals (P n °), which initiate the polymerization.…”

Section: Organic Photocatalystsmentioning

confidence: 99%

Developments in the Components of Metal‐Free Photoinitiated Organocatalyzed‐Atom Transfer Radical Polymerization (O‐ATRP)

Aklujkar

Rao

2020

ChemistrySelect

View full text Add to dashboard Cite

The evolution of the atomic transfer radical polymerization (ATRP) has instigated an increased demand for designing versatile and tailored polymeric structures. However, the use of metal catalysts in traditional ATRP limits the use of polymers in many niche applications. The recent advancement in ATRP has engendered the substitution of metal‐catalysts by a more user‐friendly class of organic photoredox catalysts, which offer enhanced control over the polymerization reaction as these compounds can be easily activated and deactivated with just a source of light. These new photocatalysts have transformed the traditional ATRP to a metal‐free photoinitiated organocatalyzed – ATRP (O‐ATRP), which has potential applications in the medical and electronic sectors. This review covers the reductive and oxidative quenching mechanism of the metal‐free photoinduced O‐ATRP reaction and the function of each component to establish a successfully controlled polymerization reaction. The scope for each component has been encompassed in the study, which paves the way for future developments in the field.

show abstract

Section: Organic Photocatalystsmentioning

confidence: 99%

Developments in the Components of Metal‐Free Photoinitiated Organocatalyzed‐Atom Transfer Radical Polymerization (O‐ATRP)

Aklujkar

Rao

2020

ChemistrySelect

View full text Add to dashboard Cite

show abstract

“…In addition, metal-free ATRP is a very recent technique, with only a few simulation studies that can be cited. [33,41] To the best of our knowledge, no research has Table 1. Reaction mechanism with the fundamental reactions of the metal-free ATRP process.…”

Section: Determination Of Kinetic Parametersmentioning

confidence: 99%

An Experimental and Computational Approach on Controlled Radical Photopolymerization of Limonene

Silva

Vieira

2020

Macro Chemistry & Physics

View full text Add to dashboard Cite

Limonene is a potential candidate for the synthesis of polymers from renewable and non-toxic sources. The synthesis of poly(limonene) via controlled photopolymerization is studied for the first time, both at an experimental and computational level. A kinetic modeling is developed and all unknown parameters are estimated by adjusting them to the experimental data (conversion, molar mass, and dispersity). The reasonable model fit indicates that the proposed mechanism can be considered valid for this process simulation. In that fashion, different reagent ratios are evaluated, as well as simulations for long polymerization times. The experiments provide less than 10% monomer conversion at 40 °C, and short times. However, it is possible to identify a reasonable polymerization control (dispersities <1.5). In a complementary way, the simulations allowed to identify a threshold of reagent ratios in order to maintain the polymerization control for conversions around 20%, and at the same time enable monomer conversions at the same level as traditional thermally-initiated radical polymerizations at high temperatures. Therefore, this new route can be a promising alternative for the synthesis of limonene-based polymers.

show abstract

“…Light-driven reactions are vital for all life. [26] To the best of our knowledge,p hotoATRP as as trategy to achievea mplified detection of biomolecules has been rarely reported. [14][15][16][17][18] Recently,p hotoredox catalysts has been widely investigated due to the strongo xidation and reductiono fi ts exciteds tate and poor oxidation and reduction in the grounds tate.…”

Section: Introductionmentioning

confidence: 99%

“…Metal‐free photoATRP possesses two photoredox catalytic cycles by means of single electron transfer, oxidative quenching pathway and reductive quenching pathway . Compared with oxidative quenching pathway, the formation of excited states of photoredox catalysts need lower energy in the reductive quenching pathway . To the best of our knowledge, photoATRP as a strategy to achieve amplified detection of biomolecules has been rarely reported…”

Section: Introductionmentioning

confidence: 99%

Metal‐Free Photoinduced Atom Transfer Radical Polymerization for Highly Sensitive Detection of Lung Cancer DNA

Liu

Jian

Liu

et al. 2020

Chemistry A European J

View full text Add to dashboard Cite

Convenient and sensitive detection of biomolecules is of great significance to disease diagnosis. In this work, am etal-free photoinduced atom transfer radicalp olymerization (photoATRP) by ar eductive quenching pathway as an ovel strategy is appliedt oa chieve lung cancerD NA detection. Thiolated PNA is exploited to specifically recognize target DNA, and the initiator of photoATRP is linked to the electrode surface via phosphate-Zr 4 + -carboxylate. Under the excitation of blue light, the reductive quenching path-way is activatedw ith eosin Y( EY) as photoredox catalyst and N,N,N',N'',N'-pentamethyldiethylenetriamine (PMDETA) as electron donor,a nd numerous polymeric chains are formed. Under optimal conditions, the linear range of this strategy is from 0.1 pm to 10 nm (R 2 = 0.989)w ith al imit of detection (LOD) of 1.4 fm (14 zmol in 10 mL). Thev ariety of possible light sourcesf or photoATRP and simple operation endowt his biosensorw ith great potential for practical applications.[a] Dr.Supporting information and the ORCID identification number(s) for the author(s) of this articlecan be found under: https://doi.

show abstract

Aqueous Metal-Free Atom Transfer Radical Polymerization: Experiments and Model-Based Approach for Mechanistic Understanding

Cited by 70 publications

References 69 publications

Developments in the Components of Metal‐Free Photoinitiated Organocatalyzed‐Atom Transfer Radical Polymerization (O‐ATRP)

Developments in the Components of Metal‐Free Photoinitiated Organocatalyzed‐Atom Transfer Radical Polymerization (O‐ATRP)

An Experimental and Computational Approach on Controlled Radical Photopolymerization of Limonene

Metal‐Free Photoinduced Atom Transfer Radical Polymerization for Highly Sensitive Detection of Lung Cancer DNA

Contact Info

Product

Resources

About