The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/marc.201800650. ChemistryBefore moving to the recent advances within the last 5 years in the diverse applications of sulfur chemistry in polymer and Sulfur-Containing PolymersSulfur and its functional groups are major players in an area of exciting research taking place in modern polymer and materials science, both in academia and industry. In fact, manifold sulfur-based reactions that are both exceptionally versatile as well as tremendously useful have been implemented, and further utilized for the design and preparation of polymeric materials that lead to a plethora of applications ranging from medicine to optics and nanotechnology to separation science. Hence, within this review, an overview of strategies and developments used over the last 5 years to reinforce the importance of the sulfur functional group in modern polymer and materials science is presented. In particular, many important references in the primary literature of sulfur chemistry are referred to, including thiol-ene, thiol-yne, thiol-Michael addition, disulfide cross-linking, and thiol-disulfide exchange, among others, by explaining and illustrating the important principles. Last but not least, the grand aim to underpin the importance of sulfur in modern polymer and materials science is achieved by presenting selected examples in diverse fields and postulating the respective potential for real-world applications. he is now a full professor at KIT.sulfur atoms, and tetraphenylethene-bearing di(alkyl bromide) (Scheme 3). The yield of the polymerization was dependent on the di(alkyl bromide) monomer; the longer spacer between the aromatic moiety and the reactive bromide end groups Scheme 1. The discussion henceforth focuses on the synthesis of polymers possessing the depicted sulfur functional groups. Scheme 2.Representative examples of polythioethers prepared via A) the nucleophilic substitution reaction between an electrophilic dihalide with nucleophilic derivatives of dithiols under alkaline conditions; B) the thiol-ene/yne addition reaction between AA and BB type monomers (i.e., dithiols and dienes/diynes); and C) radical or ionic ring-opening of sulfurcontaining strained rings.Scheme 3. The thiol-bromo polymerization of conformationally fixed monomers to provide multifunctional polymers. [19] Macromol. Rapid Commun. 2019, 40, 1800650 Scheme 4. The regioselective selective nucleophilic aromatic substitution between thiol and fluorinated aromatic compounds, the para-fluorothiol reaction (PFTR).Scheme 5. Synthesis of a linear polymer via PFTR-reaction. [21]

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Synthetic polypeptide-based macroporous cryogels with inherent antimicrobial properties were prepared for potential water purification applications. Gels were chemically cross-linked through the amine residue of a polycationic polylysine-b-polyvaline block copolymer with glutaraldehyde as cross-linker under cryogenic conditions. These cryogels exhibited excellent water swelling and highly compressible mechanical properties owing to their macroporous structure. The antibacterial performance was evaluated based on E. coli viability, with cryogels exhibiting up to 95.6% reduction in viable E. coli after a brief 1 h incubation. In comparison to the hydrogel control, the presence of macropores is shown to be vital to the antimicrobial effect of the gels. The confined environment and increased antimicrobial surface area of the macropores is believed to result in a "trap and kill" mechanism. Mechanical strength and pore integrity of cryogels were also found to be determinants for antibacterial activity. Along with the lack of toxic leaching, these cryogels with inherent antimicrobial properties pose as potential candidates for use in biological and environmentally friendly water purification applications.

A series of ionic poly(acrylamide) (PAAm) gels was prepared by free-radical crosslinking copolymerization of acrylamide and N,NЈ-methylenebisacrylamide in aqueous solutions. The gels were prepared both below and above the bulk freezing temperature of the polymerization solvent water, which are called as the cryogels and the hydrogels, respectively. The deswelling behavior of swollen gels in acetone as well as the reswelling behavior of the collapsed gels in water were investigated. It was shown that the cryogels respond against the external stimuli much faster than the hydrogels. The interior morphology of the cryogel networks exhibits a discontinuity and a two-phase structure, compared to the continuous morphology of the hydrogel networks. Introduction of the ionic units in the network chains further increased the response rate of the cryogels. In contrast to these advantages of cryogels, they exhibit lower swelling capacities than the conventional hydrogels.

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Novel poly(dimethylsiloxane) based macroporous gels (cryogels) were prepared via a simple and rapid photo-induced thiol-ene click reaction at low temperatures. The cryogels formed were able to float on a water surface and selectively remove oils or organic solvents with excellent recyclability.

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