Polymeric membranes, based on a polysulfone-type aromatic polyether matrix, were successfully developed via the non-solvent induced phase separation (NIPS) method. The polyethersulfone type polymer poly[2-(4-(diphenylsulfonyl)-phenoxy)-6-(4-phenoxy) pyridine] (PDSPP) was used as the membrane matrix, and mixed with its sulfonated derivative (SPDSPP) and a polymeric porogen. The SPDPPP was added to impart hydrophilicity, while at the same time maintaining the interactions with the non-sulfonated aromatic polyether forming the membrane matrix. Different techniques were used for the membranes’ properties characterization. The results revealed that the use of the non-sulfonated and sulfonated polymers of the same polymeric backbone, at certain compositions, can lead to membranes with controllable porosity and hydrophilicity.

Perylene diimide (PDI) is one of the most studied functional dyes due to their structural versatility and fine tuning of the materials properties. Core substituted PDIs are prominent n-type semiconductor materials that could be used as non-fullerene acceptors in organic photovoltaics. Herein, we develop versatile organic building blocks based on PDI by decorating the PDI core with quinoline groups. Styryl and hydroxy phenyl mono and difunctionalized molecules were prepared using mono-nitro and dibromo bay substituted PDIs by Suzuki coupling with the respective boronic acid derivatives. A novel methodology using nitro-PDI under Suzuki coupling conditions as an electrophile partner was successfully tested. Furthermore, the PDI derivatives were used for the synthesis of soluble, electron accepting small molecules combining PDI with weak electron withdrawing quinoline derivatives. The new molecules presented wide absorbance in the visible spectrum from 450 to almost 700 nm while their LUMO levels and their energy levels are in the range of −3.8 to −4.2 eV.

Cotton cationization with low molecular weight or polymeric cationic modifiers allows the effective dyeing of cotton substrates with reactive dyes under salt-free and more environmentally friendly conditions. The current work focuses on the spectroscopic study of the intermolecular interactions, which dictate the physicochemical process associated with fabric dyeing. Water-soluble cationic copolymers of vinyl benzyl chloride (VBC) and vinyl benzyl triethylammonium chloride (VBCTEAM) have been used as cellulose cationic modifiers. Dye uptake was assessed using Remazol Brilliant Blue R and Novacron Ruby S-3B dyes. The study involves ATR-FTIR, UV-Vis, fluorescence, and XPS spectroscopy. The results of binary polymer-rich dye-polymer aqueous solutions or dye-polymer precipitates at stoichiometric charge-ratio revealed that the sulfonate/sulfate anions of the dyes interact with the cationic VBCTEAM units of the polymer via electrostatic interactions. Moreover, the comparative study of dye application on modified and unmodified fabrics suggests that, unlike the latter, where dyes are chemically bound to cellulose, electrostatic forces dominate the interaction of modified fabrics with dye molecules.

Though an important and chronic source of dyes released to the environment, the determination of the release of dyes that occurs during household or industrial washing is usually disregarded. The main scope of this study is to reveal the extent of dye release through washing, and to understand if the modification of cotton fabrics with cationic polymers could reduce it. Modified cotton fabrics, dyed with Acid Blue 281 (AB) or by a mixture of the reactive dyes Novacron Yellow S-3R (NY), Novacron Ruby S-3B (NR) and Novacron Dark Blue S-GL (NDB), underwent a certified washing process. The dyed fabrics were analyzed colorimetrically, while the washing waters were analyzed spectroscopically, via UV/Vis absorption and surface enhanced Raman scattering (SERS). In the modified fabrics dyed with the acid dye, an increased dye uptake was noticed that exhibited a color intensity of K/S~16, compared to K/S~0.45 of the unmodified fabrics. The corresponding normalized dye release (dye concentration/color intensity factor) in the wash water was ~1.6 for the modified fabrics, compared to ~6.5 in the case of the unmodified fabrics, indicating the significance of cotton modification on both the dye uptake and dye release during washing. In the fabrics dyed with a mixture of selected reactive dyes, the color uptake of modified (K/S~10) was also increased compared with unmodified fabrics (K/S~4.5). An important observation, is that in the case of the dyeing of the reactive dyes mixture, a selectivity on the part of the dye uptake was noticed, since the contribution of NY (yellow) is higher compared to that of the blue (positive value of color indicator coordinate (b)); however, this also resulted in an increased NY dye release during washing. The findings of this study could contribute to the dye release problem control due to fabric washing, and to the understanding of any potential selectivity on the part of dye–cotton interactions.

Oligomers of the low-band-gap PCDTBT polymer, based on either 3,6 or 2,7 carbazole units, were modified with vinyl ω-chain end functionalities. The vinyl-functionalized oligomers were used as comonomers in free radical polymerizations with quinoline-based monomers such as 6-vinylphenyl-(2-pyridinyl)-4-phenyl-quinoline (vinyl-QPy), and 6-vinylphenyl-(2-perfluorophenyl)-4-phenyl quinoline (vinyl-5FQ). The co-polymeric materials bearing the vinyl-QPy moiety were developed as potential compatibilizers in polymer electron donor–fullerene acceptor blends for non-covalent interactions with the fullerene part. The co-polymeric materials bearing the vinyl-5FQ moiety were developed for the covalent attachment of carbon nanostructures; specifically, PC₆₁BM. Both copolymers and hybrids, after thorough purification, were characterized in terms of their spectroscopic and optical properties as well as their ability to form nanophased separated films as such, or as additives at various percentages into PCDTBT: PC₇₁BM blends.

In this work, hybrid polymeric bis-tridentate iridium(III) complexes bearing derivatives of terpyridine (tpy) and 2,6-di(phenyl) pyridine as ligands were successfully synthesized and evaluated as red-light emitters. At first, the synthesis of small molecular bis-tridendate Ir(III) complexes bearing alkoxy-, methyl-, or hydroxy-functionalized terpyridines and a dihydroxyphenyl-pyridine moiety was accomplished. Molecular complexes bearing two polymerizable end-hydroxyl groups and methyl- or alkoxy-decorated terpyridines were copolymerized with difluorodiphenyl-sulphone under high temperature polyetherification conditions. Alternatively, the post-polymerization complexation of the terpyridine-iridium(III) monocomplexes onto the biphenyl-pyridine main chain homopolymer was explored. Both cases afforded solution-processable metallocomplex-polymers possessing the advantages of phosphorescent emitters in addition to high molecular weights and excellent film-forming ability via solution casting. The structural, optical, and electrochemical properties of the monomeric and polymeric heteroleptic iridium complexes were thoroughly investigated. The polymeric metallocomplexes were found to emit in the orange–red region (550–600 nm) with appropriate HOMO and LUMO levels to be used in conjunction with blue-emitting hosts. By varying the metal loading on the polymeric backbone, the emitter’s specific emission maxima could be successfully tuned.