Emerging Trends in Polymerization-Induced Self-Assembly

ACS Macro Letters, Год журнала: 2019, Номер 8(8), С. 1029 - 1054

Опубликована: Авг. 7, 2019

In this Perspective, we summarize recent progress in polymerization-induced self-assembly (PISA) for the rational synthesis of block copolymer nanoparticles with various morphologies. Much PISA literature has been based on thermally initiated reversible addition-fragmentation chain transfer (RAFT) polymerization. Herein, pay particular attention to alternative protocols, which allow preparation improved control over morphology and functionality. For example, initiation visible light, redox chemistry, or enzymes enables incorporation sensitive monomers fragile biomolecules into nanoparticles. Furthermore, syntheses postfunctionalization resulting (e.g., cross-linking) can be conducted sequentially without intermediate purification by using external stimuli. Finally, formulations have optimized via high-throughput polymerization recently evaluated within flow reactors facile scale-up syntheses.

Язык: Английский

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Applications of Halogen-Atom Transfer (XAT) for the Generation of Carbon Radicals in Synthetic Photochemistry and Photocatalysis

Chemical Reviews, Год журнала: 2021, Номер 122(2), С. 2292 - 2352

Опубликована: Дек. 9, 2021

The halogen-atom transfer (XAT) is one of the most important and applied processes for generation carbon radicals in synthetic chemistry. In this review, we summarize highlight aspects associated with XAT impact it has had on photochemistry photocatalysis. organization material starts analysis mechanistic then follows a subdivision based nature reagents used halogen abstraction. This review aims to provide general overview fundamental concepts main agents involved objective offering tool understand facilitate development new radical strategies.

Язык: Английский

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

Chemical Reviews, Год журнала: 2021, Номер 122(2), С. 1830 - 1874

Опубликована: Ноя. 29, 2021

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

Язык: Английский

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Recent Trends in Catalytic Polymerizations

ACS Catalysis, Год журнала: 2019, Номер 9(12), С. 11153 - 11188

Опубликована: Ноя. 8, 2019

Polymers have become one of the largest and most important materials we use in daily life. Their popularity has stemmed from their wide range material properties combined with low cost production. Both these attractive traits part been enabled by development catalytic polymerizations, which provide both high levels control while also delivering productivity. In this Perspective, highlight recent trends achievements made growing field polymerizations.

Язык: Английский

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Role of External Field in Polymerization: Mechanism and Kinetics

Chemical Reviews, Год журнала: 2020, Номер 120(5), С. 2950 - 3048

Опубликована: Фев. 21, 2020

The past decades have witnessed an increasing interest in developing advanced polymerization techniques subjected to external fields. Various physical modulations, such as temperature, light, electricity, magnetic field, ultrasound, and microwave irradiation, are noninvasive means, having superb but distinct abilities regulate polymerizations terms of process intensification spatial temporal controls. Gas emerging regulator plays a distinctive role controlling resembles some cases. This review provides systematic overview seven types external-field-regulated polymerizations, ranging from chain-growth step-growth polymerization. A detailed account the relevant mechanism kinetics is provided better understand each field In addition, given crucial modeling simulation mechanisms investigation, model construction typical numerical methods used this well highlights interaction between experiment toward existing systems given. At end, limitations future perspectives for critically discussed. state-of-the-art research progress not only fundamental principles underlying also stimulates new development methods.

Язык: Английский

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Preparation of biomolecule-polymer conjugates by grafting-from using ATRP, RAFT, or ROMP

Progress in Polymer Science, Год журнала: 2019, Номер 100, С. 101186 - 101186

Опубликована: Ноя. 18, 2019

Язык: Английский

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Making ATRP More Practical: Oxygen Tolerance

Accounts of Chemical Research, Год журнала: 2021, Номер 54(7), С. 1779 - 1790

Опубликована: Март 22, 2021

Atom-transfer radical polymerization (ATRP) is a well-known technique for the controlled of vinyl monomers under mild conditions. However, as with any other polymerization, ATRP typically requires rigorous oxygen exclusion, making it time-consuming and challenging to use by nonexperts. In this Account, we discuss various approaches achieving tolerance in ATRP, presenting overall progress field.Copper-mediated which first discovered late 1990s, uses CuI/L activator that reversibly reacts dormant C(sp3)-X polymer chain end, forming X-CuII/L deactivator propagating radical. Oxygen interferes activation propagation quenching radicals oxidizing activator. At equilibrium, present at much higher concentration than radicals. Thus, oxidation dominant inhibition pathway. conventional reaction irreversible, so must be strictly excluded achieve good results.Over last two decades, our group has developed several techniques based on concept regenerating When oxidized continuously converted back its active reduced form, then catalytic system itself can act an scavenger. Regeneration accomplished reducing agents photo-, electro-, mechanochemical stimuli. This family methods offers degree tolerance, but most them tolerate only limited amount do not allow open vessel.More recently, enzymes used auxiliary systems directly deoxygenate medium protect process. We method glucose oxidase (GOx), glucose, sodium pyruvate very effectively scavenge enable open-vessel ATRP. By adding second enzyme, horseradish peroxidase (HPR), managed extend role enzymatic generating carbon-based changed from oxygen-sensitive oxygen-fueled reaction.While performing control experiments methods, noticed using UV irradiation triggers without presence GOx. serendipitous discovery allowed us develop oxygen-proof, small-molecule-based, photoinduced system. It similar exhibits superior compatibility both aqueous media organic solvents, avoids problems associated purifying polymers enzymes. The was able rapidly polymerize N-isopropylacrylamide, monomer, high control.These contributions have substantially simplified more practical accessible everyone.

Язык: Английский

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Beyond C₃N₄ π-conjugated metal-free polymeric semiconductors for photocatalytic chemical transformations

Chemical Society Reviews, Год журнала: 2020, Номер 50(3), С. 2147 - 2172

Опубликована: Дек. 17, 2020

Photocatalysis with stable, efficient and inexpensive metal-free catalysts is one of the most promising options for non-polluting energy production. This review article covers state-of-the-art development various effective polymeric photocatalysts large π-conjugated units chemical transformations including water splitting, CO2 N2 reduction, organic synthesis monomer polymerisation. The starts catalytic mechanisms photocatalysts. Then a particular focus on rational manipulation π-conjugation enlargement, charge separation, electronic structures band in design Following principles, selection construction functional are discussed, as well connecting bonds dimensions Finally hot emerging applications photocatalytic summarized. strategies provide potential avenues to address challenges catalyst activity, selectivity stability further highly

Язык: Английский

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Emerging Organic Photoredox Catalysts for Organic Transformations

European Journal of Organic Chemistry, Год журнала: 2020, Номер 2020(38), С. 6028 - 6043

Опубликована: Июль 28, 2020

A lot of efforts have been made for the development novel organic photoredox catalysts (PCs) due to their gratifying replacement conventional transition metal‐based PCs in catalysis. In this minireview, we summarized and classified recently reported into several categories based on functional groups (e.g. cyanoarene, phenazine, xanthene, others) with applications various transformations including polymerization reactions. The strategies used design then also introduced. emerging trends discovery are systematic approaches which include computer‐aided mechanism‐based design. We anticipate that minireview will provide not only characteristics PCs, but an insight desired applications.

Язык: Английский

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Precision polymer synthesis by controlled radical polymerization: Fusing the progress from polymer chemistry and reaction engineering

Progress in Polymer Science, Год журнала: 2022, Номер 130, С. 101555 - 101555

Опубликована: Май 7, 2022

Язык: Английский

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