Correction for 'Elucidating the influence of side chains on the self-assembly of semi-flexible mesogens' by Raluca I. Gearba , , 2025, https://doi.org/10.
View Article and Find Full Text PDFChem Commun (Camb)
December 2024
In the development of functional materials, side chains are traditionally incorporated into the primary chemical structure to induce liquid-crystalline behavior or to enhance solubility for improved processability. However, emerging evidence suggests that side chains play a far more complex role. This study presents a case of a double helical supramolecular structure formed by star-shaped mesogens in the absence of specific interactions.
View Article and Find Full Text PDFMulti-responsive polymeric nanocontainers attract significant attention for their potential applications in biotechnology, drug delivery, catalysis, and other fields. By incorporating a liquid-crystalline (LC) mesogenic ligand with an alkyl tail length ranging from 8-12 carbons, ionically linked to the polymer backbone, we generate vesicles with walls significantly thinner than those of conventional polymersomes, approaching the thickness of a lipid bilayer. These LC vesicles, ranging in size from 50-120 nm, are designed to be mechanically robust due to the alignment of the hydrophilic polymer backbone within the plane of the vesicle wall.
View Article and Find Full Text PDFAnodic aluminum oxide (AAO) membranes were used as templates to control orientation of an ion-channel forming columnar mesophase obtained by self assembly of a wedge-shaped sulfonate molecule. Inside the AAO structure, the director vector of the mesophase is oriented parallel to the pore axis due to the confinement effect. The molecular arrangement induced by the spatial confinement within the pores is extended over several microns into the remnant film on the AAO surface.
View Article and Find Full Text PDFFluorinated proton-exchange membranes (PEMs) based on graft copolymers of dehydrofluorinated polyvinylidene fluoride (D-PVDF), 3-sulfopropyl acrylate (SPA), and 1H, 1H, 2H-perfluoro-1-hexene (PFH) were prepared via free radical copolymerization and characterized for fuel cell application. The membrane morphology and physical properties were studied via small-(SAXS) and wide-angle X-ray scattering (WAXS), SEM, and DSC. It was found that the crystallinity degree is 17% for PEM-RCF (co-polymer with SPA) and 16% for PEM-RCF-2 (copolymer with SPA and PFH).
View Article and Find Full Text PDFThis work presents the synthesis and self-organization of the calamitic fluorinated mesogen, 1,1,2,2-tetrafluoro-2-(1,1,2,2-tetrafluoro-4-iodobutoxy)ethanesulfonic acid, a potential model for perfluorosulfonic acid membranes (PFSA). The compound is derived in three steps from 1,1,2,2-tetrafluoro-2-(1,1,2,2-tetrafluoro-2-iodoethoxy)ethanesulfonyl fluoride, achieving a 78% overall yield. The resulting compound exhibits intricate thermal behavior.
View Article and Find Full Text PDFConjugated small molecules are advanced semiconductor materials with attractive physicochemical and optoelectronic properties enabling the development of next-generation electronic devices. The charge carrier mobility of small molecules strongly influences the efficiency of organic and hybrid electronics based on them. Herein, we report the synthesis of four novel small molecules and their investigation with regard to the impact of molecular structure and thermal treatment of films on charge carriers' mobility.
View Article and Find Full Text PDFFor decades, the endometrium was considered to be a sterile environment. However, now this concept is disputed, and there is growing evidence that microbiota composition might affect endometrial receptivity. Routine clinical management of infertility is still limited to a microbiological assessment of the lower reproductive tract.
View Article and Find Full Text PDFCurrently, the chemistry of self-healing polymers is aimed not only at obtaining materials with high self-healing efficiency, but also at improving their mechanical performance. This paper reports on a successful attempt to obtain self-healing copolymers films of acrylic acid, acrylamide and a new metal-containing complex of cobalt acrylate with a 4'-phenyl-2,2':6',2″-terpyridine ligand. Samples of the formed copolymer films were characterized by ATR/FT-IR and UV-vis spectroscopy, elemental analysis, DSC and TGA, SAXS, WAXS and XRD studies.
View Article and Find Full Text PDFA series of semi-crystalline multi-block thermoplastic polyurethanes (TPU), containing poly(butylene adipate) (PBA), polycaprolactone (PCL) and their equimolar mixture (PBA/PCL) as a soft segment was synthesized. The changes in the physical-mechanical and thermal properties of the materials observed in the course of a 36-month storage at room temperature were related to the corresponding structural evolution. The latter was monitored using Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXS) and mechanical tests (tensile strength test).
View Article and Find Full Text PDFArtificial ion-exchange and other charged membranes, such as biomembranes, are self-organizing nanomaterials built from macromolecules. The interactions of fragments of macromolecules results in phase separation and the formation of ion-conducting channels. The properties conditioned by the structure of charged membranes determine their application in separation processes (water treatment, electrolyte concentration, food industry and others), energy (reverse electrodialysis, fuel cells and others), and chlore-alkali production and others.
View Article and Find Full Text PDFCrystalline and liquid-crystalline conjugated small molecules represent a promising family of semiconductor materials for organic electronics applications. The control of the morphology and optoelectronic properties of small molecules allows tuning their charge transport characteristics and hence, improving the performance of electronic devices. Here, we designed four pentamers based on alternating thiophene and benzothiadiazole moieties and investigated the effect of their structure on the optoelectronic properties, ordering and charge transport characteristics.
View Article and Find Full Text PDFThe influence of the hard segment nature on the crystallization kinetics of multi-block thermoplastic polyurethanes containing poly(butylene adipate) (PBA) as a soft segment was investigated. Using a combination of FTIR spectroscopy, time-domain H nuclear magnetic resonance (TD-NMR), differential scanning calorimetry (DSC), fast-scanning calorimetry (FSC) and wide-angle X-ray diffraction (WAXS), it was shown that aliphatic, cycloaliphatic and aromatic diisocyanates affect the phase separation efficiency of soft and hard segments. The best phase separation efficiency was observed for a sample containing aliphatic diisocyanate due to the development of a hydrogen bond network.
View Article and Find Full Text PDFThe structural evolution of multiblock thermoplastic polyurethane ureas based on two polydiols, poly(1,4-butylene adipate (PBA) and poly-ε-caprolactone (PCL), as soft blocks and two diisocyanites, 2,4-toluylene diisocyanate (TDI) and 1,6-hexamethylene diisocyanate (HMDI), as hard blocks is monitored during in situ deformation by small- and wide-angle X-ray scattering. It was shown that the urethane environment determines the crystal structure of the soft block. Consequently, two populations of crystalline domains of polydiols are formed.
View Article and Find Full Text PDFWe report on formation of a bicontinuous double gyroid phase by a wedge-shaped amphiphilic mesogen, pyridinium 4'-[3″,4″,5″-tris-(octyloxy)benzoyloxy]azobenzene-4-sulfonate. It is found that this compound can self-organize in zeolite-like structures adaptive to environmental conditions (e.g.
View Article and Find Full Text PDFThe mechanisms of orientation of columnar liquid crystals (LCs) on a PTFE-rubbed surface are explored on a homologous series of symmetrically substituted poly(di--alkylsiloxanes) (PDAS). It is shown that by increasing the side-chain length in steps of one CH group, the orientation of PDAS switches back and forth from perpendicular to parallel with respect to PTFE chains. These changes are sensitive to the smallest possible variation of the macromolecular structure (i.
View Article and Find Full Text PDFThe control of structure formation in the active layers of organic solar cells allows for improvement in their processability and enhancement of the efficiency of the final devices. In the present work, in situ studies of film formation from binary toluene solutions of an electron donor, poly(3-hexylthiophene) (P3HT), and an electron acceptor such as [6,6]-phenyl-C-61-butyric acid methyl ester (PCBM) or indene-C60 bisadduct (ICBA) have been conducted. These experiments were carried out using GIWAXS with simultaneous electric current measurements.
View Article and Find Full Text PDFWe report on the phase behaviour of a wedge-shaped mesogen, which can exist in two different states at room temperature, a stable columnar and a metastable cubic gyroid phase. The latter reveals exceptional stability and remarkable water sorption capacity accounted for by the locally-ordered peripheral alkyl chains.
View Article and Find Full Text PDFWe present an all-inorganic photoactive material composed of AgPbI and PbI, which shows unexpectedly good photovoltaic performance in planar junction solar cells delivering external quantum efficiencies of ∼60% and light power conversion efficiencies of ∼3.9%. The revealed characteristics are among the best reported to date for metal halides with nonperovskite crystal structure.
View Article and Find Full Text PDFIn supramolecular assemblies, absorption of water can assist the channel formation, similarly to biological systems and Nafion-like commercial ion-selective membranes. In this work, we investigate humidity-induced formation of water channels in wedge-shaped amphiphilic molecules, namely sodium 4'-[3'',4'',5''-tris(alkyloxy)benzoyloxy]azobenzene-4-sulfonates. The studied molecules contain a polar sulfonate group at the tip and a hydrophobic periphery composed of alkyl chains of two different lengths.
View Article and Find Full Text PDFWe report a careful and systematic study of thermal and photochemical degradation of a series of complex haloplumbates APbX (X = I, Br) with hybrid organic (A = CHNH) and inorganic (A = Cs) cations under anoxic conditions (i.e., without exposure to oxygen and moisture by testing in an inert glovebox environment).
View Article and Find Full Text PDFWe report here all inorganic CsPbI planar junction perovskite solar cells fabricated by thermal coevaporation of CsI and PbI precursors. The best devices delivered power conversion efficiency (PCE) of 9.3 to 10.
View Article and Find Full Text PDFNew multi-blocked thermoplastic polymers containing rigid polyurethane-urea and soft polydiethylene glycol adipate blocks have been synthesized. Basic features of their structure formation have been revealed. Three types of supramolecular organization have been found, which define the behavior of samples under heating and deformation conditions.
View Article and Find Full Text PDFHere we report a systematic study of the Pb substitution in the hybrid iodoplumbate MAPbI with a series of elements affecting optoelectronic, structural, and morphological properties of the system. It has been shown that even partial replacement of lead with Cd, Zn, Fe, Ni, Co, In, Bi, Sn, and Ti results in a significant deterioration of the photovoltaic characteristics. On the contrary, Hg-containing hybrid MAPbHgI salts demonstrated a considerably improved solar cell performance at optimal mercury loading.
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