Elemental sulfur is an abundant and inexpensive material obtained as a by-product of natural-gas and petroleum refining operations. Recently, the need for the development of new energy-storage systems brought into light the potential of sulfur as a high-capacity cathode material in secondary batteries. Sulfur-containing materials were also shown to have useful IR optical properties. These developments coupled with growing environmental concerns related to the global production of excess elemental sulfur have led to a keen interest in its utilization as a feedstock in materials applications. This Minireview focuses on the recent developments on physical and chemical methods for directly processing elemental sulfur to produce functional composites and polymers.

Well-defined nanostructures composed of conjugated polymers have attracted significant attention due to their intriguing electronic and optical properties. However, precise control of the size and uniformity of these semiconducting nanostructures is still rare and challenging, despite recent advances in strategies to obtain self-assembled nanostructures with narrow dispersions. Herein, we demonstrate the preparation of fluorescent conjugated block copolymers by one-shot polymerization and rapid formation of nanofibers in a few minutes via light-induced crystallization-driven self-assembly, driven by facile cis-to- trans photoisomerization of its poly( p-phenylenevinylene) blocks. Furthermore, living self-assembly was possible, allowing not only nanofibers with excellent length control and narrow size distribution but also ABA triblock comicelles and gradient comicelles, to be produced by seeded growth. Lastly, the seeded growth could be activated and deactivated repeatedly by switching the light on and off, analogous to light-induced living radical polymerization.

High refractive index polymers (HRIPs) have recently emerged as an important class of materials for use in a variety of optoelectronic devices including image sensors, lithography, and light-emitting diodes. However, achieving polymers having refractive index exceeding 1.8 while maintaining full transparency in the visible range still remains formidably challenging. Here, we present a unique one-step vapor-phase process, termed sulfur chemical vapor deposition, to generate highly stable, ultrahigh refractive index (n > 1.9) polymers directly from elemental sulfur. The deposition process involved vapor-phase radical polymerization between elemental sulfur and vinyl monomers to provide polymer films with controlled thickness and sulfur content, along with the refractive index as high as 1.91. Notably, the HRIP thin film showed unprecedented optical transparency throughout the visible range, attributed to the absence of long polysulfide segments within the polymer, which will serve as a key component in a wide range of optical devices.

Cytokinins are plant hormones with crucial roles in growth and development. Although cytokinin signaling is well characterized in the model dicot Arabidopsis, we are only beginning to understand its role in monocots, such as rice (Oryza sativa) and other cereals of agronomic importance. Here, we used primarily a CRISPR/Cas9 gene-editing approach to characterize the roles of a key family of transcription factors, the type-B response regulators (RRs), in cytokinin signaling in rice. Results from the analysis of single rr mutants as well as higherorder rr21/22/23 mutant lines revealed functional overlap as well as subfunctionalization within members of the gene family. Mutant phenotypes associated with decreased activity of rice type-B RRs included effects on leaf and root growth, inflorescence architecture, flower development and fertilization, trichome formation and cytokinin sensitivity. Development of the stigma brush involved in pollen capture was compromised in the rr21/22/23 mutant, whereas anther development was compromised in the rr24 mutant. Novel as well as conserved roles for type-B RRs in the growth and development of a monocot compared with dicots were identified.

High-refractive-index sulfur-rich polymers with significantly improved thermal properties are prepared using divinylbenzene (DVB) as a comonomer in a modified, lowtemperature inverse vulcanization with elemental sulfur. Differential scanning calorimetry and Fourier transform infrared studies reveal that under the modified inverse vulcanization conditions, homopolymerized DVB segments form, leading to high glass-transition temperatures (T g > 100 °C) and thermal stability previously unattainable from the inverse vulcanization of bifunctional olefin comonomers. On the basis of the modified procedures, a three-step molding process of the inverse vulcanization product of DVB, poly(S-r-DVB), involving (1) prepolymer formation, (2) hot-press compression molding of the soft prepolymer, and (3) thermal annealing of the molded product is demonstrated. The molded high-sulfur-content poly(S-r-DVB) exhibits a high refractive index (n > 1.85), along with high midwave infrared transmittance. Combined with a high T g , these properties render poly(S-r-DVB) with properties highly desirable in applications involving infrared optics.

Fluorescent nanoparticles composed of poly(p-phenylenevinylene) block copolymers were prepared by the facile one-step process and exhibited discriminative detection of neutral explosives against charged molecules.

We present structural analysis of spherical diblock copolymer micelles where core blocks have bottlebrush architecture. The dependence of the core radius (R core) and the corona thickness (L corona) on the core block length (N core) is investigated using small-angle X-ray scattering (SAXS) and discussed in terms of the stiffness of a core-forming polymer posed by its long fluoroalkyl side chains. The conformation of the core block is strongly stretched, and the measured exponents α and β from power-law correlations, R core ∼ N core α and L corona ∼ N core β, respectively, are greater than those from any scaling predictions for block copolymer micelles with a flexible, linear core-block. Such deviations are attributed to the appreciable chain stiffness of the bottlebrush core block, and a simple model is suggested to understand how the core block stiffness influences both the dimensions of core and corona.

High refractive index (RI) thin films are of critical importance for advanced optical devices, and the high refractive index polymers (HRIPs) constitute an interesting class of materials for high RI thin films due to low cost, good processability, light weight, and high flexibility. However, HRIPs have yet to realize their full potential in high RI thin film applications due to their relatively low RI, strong absorption in the blue light region, and limited film formation methods such as rapid vitrification. Herein, we report a development of a new HRIP thin film generated through a one-step vapor-phase process, termed sulfur chemical vapor deposition (sCVD), using elemental sulfur and divinyl benzene. The developed poly­(sulfur-co-divinyl benzene) (pSDVB-sCVD) film exhibited RI (measured at 632.8 nm) exceeding 1.97, one of the highest RIs among polymers without metallic elements reported to date. Because the sCVD utilized vaporized sulfur with a unique sulfur-cracking step, formation of long polysulfide chains was suppressed efficiently, while high sulfur content as high as 85 wt % could be achieved with no apparent phase separation. Unlike most of inorganic high RI materials, pSDVB-sCVD was highly transparent in the entire visible range and showed extremely low birefringence of 10 × 10–4. The HRIP thin film with unprecedentedly high RI, together with outstanding transparency and low birefringence, will serve as a key component in a wide range of high-end optical device applications.