Themed collection Synthetic Methodologies for Complex Macromolecular Structures

Hatice Mutlu, Filip Du Prez and Remzi Becer present the Polymer Chemistry themed collection on synthetic methodologies for complex macromolecular structures in honour of Prof. Yusuf Yagci's 70^th birthday.

The objective of this mini-review article is to highlight the importance of the chemical design towards the synthesis of polymeric profluorescent nitroxides applicable as self-reporting probes.

A versatile synthetic methodology is presented for the preparation of graft copolymers with mixed graft distributions using reversible addition–fragmentation chain transfer (RAFT) polymerisation.

Several sulfonium salts as unimolecular photoinitiators can efficiently initiate UCNP-assisted direct cationic and radial/cationic photopolymerization under 980 nm NIR light irradiation.

A metal-free visible LED photopolymerization process, initiated by imidazole based charge transfer complexes under mild conditions (room temperature, without an inert atmosphere, monomer purification or stabilizer removal), is reported.

Synthesis of ‘uncontrolled’ commercially-relevant block copolymers by metal- and sulfur-free, bromoform-assisted polymerisation.

A highly sensitive NIR photoinitiating system based on dye/borate associated pairs.

Preventing bacterial infection by using anti-adhesive trehalose polymer is one alternative to antibiotic treatment.

A photolinker for formation of disulfide-crosslinked hydrogels via light-triggered thiol–ene conjugation has been developed. Hydrogels can be patterned via two-photon cleavage of disulfide-linkages in the presence of a two-photon active compound.

Efficient exchange of Br in iron-catalyzed ATRP in anisole provided well-controlled polymers with low dispersity as opposed to the Cl-based initiating system, which resulted in large dispersities due to the slower activation/deactivation with Cl.

A series of acridinium salts with high excited-state oxidative power are employed as photoredox organocatalysts for photomediated cationic RAFT and DT polymerizations under visible light.

Cationic ring-opening polymerization (CROP) is an interesting synthesis technique to obtain well-defined polymers with narrow molar mass distribution (MMD).

Reversible Radical Recombination Polymerization (R3P) using triethylamine (TEA), H₂O₂ and air is a scalable and green method for the synthesis of biodegradable polysulfides.

A rapid, selective and sensitive, novel conducting-polymer sensing platform for the detection and analysis of biothiols.

Responsive double cross-linked hydrogels have proven to be a powerful approach to create smart polymer networks but unfold even greater potential if combined with supramolecular chemistry.

A dibenzylamine derived cyclic dithiocarbonate (1) undergoes ring-opening polymerization due to the greater reactivity of exocyclic sulfur compared to the tertiary amine with methyl triflate.

This manuscript will exhibit the photopolymerization of mevalonic lactone methacrylate, an overlooked monomer, and how functional polymers with lactone pendant units can be synthesized.

Reversible addition–fragmentation chain-transfer (RAFT) polymerization has been exploited to design silica-nanoparticle-incorporated photocurable resins for 3D printing of materials with enhanced mechanical properties and complex structures.

The Suzuki–Miyaura coupling polymerization of PinB-F8T(3)-Br was accompanied by disproportionation, whereas that of PinB-F8T(4)-Br proceeded in a chain-growth polymerization manner to afford a well-defined fluorene-thiophene alternating copolymer.

Block copolymer micelles with a fluorous corona were synthesized via living allene polymerization in fluorous media and a polymerization-induced self-assembly (PISA) process, resulting in excellent superhydrophobic optically transparent coatings.

Macroporous, emulsion-templated, linear poly(urethane urea) elastomers were synthesized from polyols (poly(ε-caprolactone)s or polycarbonates) and a diisocyanate. Growing cells adhered to the walls, spread, and penetrated into the porous structures.

An alternative method to synthesize well-defined cyclic polymers via combination of anionic polymerization high vacuum techniques and Williamson etherification reaction in moderate dilution and up to 1 g scale.

Cationic W alkylidene N-heterocyclic carbene complexes allow for the stereospecific ring-opening metathesis polymerization of norbornenes with high trans-iso- and high cis-syndiospecificity, respectively.

We report a method to efficiently prepare multisegmented polymers via a combination of step-growth (SG) and reversible addition-fragmentation chain transfer (RAFT) polymerization.

Vinylidene fluoride (VDF) emulsion polymerization is conducted in the presence of xanthate-end functionalized poly(ethylene glycol)s leading to stable PVDF latexes.

The cationic ring-opening copolymerization of 2-ethyl-2-oxazoline and 3,4-dimethoxyaryl-substituted 2-oxazolines yields gradient or random copolymers, which can be converted into adhesive copolymers carrying catecholic and cationic groups.

Core cross-linked star shaped polymers possess unique physical properties that can be utilized as drug transporters for biomedical applications.

Polar modifiers strongly affect the statistical anionic copolymerization of biobased β-myrcene with styrene, leading to a variety of morphologies.

Water soluble sequence-defined oligoampholytes with precisely positioned charges were synthesised via an iterative solid-phase synthesis protocol using vinyl sulfonamide and acrylate building blocks.

Core-crosslinked star polymers synthesized via a grafting-through approach using RCMP.

The present work highlights the synthesis and post-modification of silica-based micro-particles containing photo-responsive polymer brushes with photolabile o-nitrobenzyl ester (o-NBE) chromophores.