Controlling the Nematic Liquid Crystallinity of Cellulose Nanocrystals with an Alcohol Ethoxy Sulfonate Surfactant.

Cellulose nanocrystals (CNCs) are biobased colloidal nanorods that have unlocked new opportunities in the area of sustainable functional nanomaterials including structural films and coatings, biomedical devices, energy, sensing, and composite materials. While selective light reflection and sensing develop from the typical chiral nematic (cholesteric, Nem*) liquid crystallinity exhibited by CNCs, a wealth of technologies would benefit from a nematic liquid crystal (LC) with CNC uniaxial alignment. Therefore, this study answers the central question of whether surfactant complexation suppresses CNC chirality in favor of nematic lyotropic and thermotropic liquid crystallinity. Therein, we use a common surfactant having both nonionic and anionic blocks, namely, oligo(ethylene glycol) alkyl-3-sulfopropyl diether potassium salt (an alcohol ethoxy sulfonate (AES)). AES forms complexes with CNCs in toluene (a representative for nonpolar organic solvent) via hydrogen bonding with an AES' oligo(ethylene glycol) block. A sufficiently high AES weight fraction endows the dispersibility of CNC in toluene. Lyotropic liquid crystallinity with Schlieren textures containing two- and four-point brush defects is observed in polarized optical microscopy (POM), along with the suppression of the cholesteric fingerprint textures. The results suggest a nematic (Nem) phase in toluene. Moreover, thermotropic liquid crystallinity is observed by incorporating an excess of AES, in the absence of an additional solvent and upon mild heating. The Schlieren textures suggest a nematic system that undergoes uniaxial alignment under mild shear. Importantly, replacing AES with a corresponding nonionic surfactant does not lead to liquid crystalline properties, suggesting electrostatic structural control of the charged end group of AES. Overall, we introduce a new avenue to suppress CNC chirality to achieve nematic structures, which resolves the long-sought uniaxial alignment of CNCs in filaments, composite materials, and optical devices.

Self-assembled highly ordered acid layers in precisely sulfonated polyethylene produce efficient proton transport.

Recent advances in polymer synthesis have allowed remarkable control over chain microstructure and conformation. Capitalizing on such developments, here we create well-controlled chain folding in sulfonated polyethylene, leading to highly uniform hydrated acid layers of subnanometre thickness with high proton conductivity. The linear polyethylene contains sulfonic acid groups pendant to precisely every twenty-first carbon atom that induce tight chain folds to form the hydrated layers, while the methylene segments crystallize. The proton conductivity is on par with Nafion 117, the benchmark for fuel cell membranes. We demonstrate that well-controlled hairpin chain folding can be utilized for proton conductivity within a crystalline polymer structure, and we project that this structure could be adapted for ion transport. This layered polyethylene-based structure is an innovative and versatile design paradigm for functional polymer membranes, opening doors to efficient and selective transport of other ions and small molecules on appropriate selection of functional groups.

Exploring Redox States, Doping and Ordering of Electroactive Star-Shaped Oligo(aniline)s.

We have prepared a simple star-shaped oligo(aniline) (TDPB) and characterised it in detail by MALDI-TOF MS, UV/Vis/NIR spectroscopy, time-dependent DFT, cyclic voltammetry and EPR spectroscopy. TDPB is part of an underdeveloped class of π-conjugated molecules with great potential for organic electronics, display and sensor applications. It is redox active and reacts with acids to form radical cations. Acid-doped TDPB shows behaviour similar to discotic liquid crystals, with X-ray scattering investigations revealing columnar self-assembled arrays. The combination of unpaired electrons and supramolecular stacking suggests that star-shaped oligo(aniline)s like TDPB have the potential to form conducting nanowires and organic magnetic materials.

Heating-Induced Switching to Hierarchical Liquid Crystallinity Combining Colloidal and Molecular Order in Zwitterionic Molecules.

Hierarchical self-assemblies of soft matter involving triggerable or switchable structures at different length scales have been pursued toward multifunctional behaviors and complexity inspired by biological matter. They require several and balanced competing attractive and repulsive interactions, which provide a grand challenge in particular in the "bulk" state, i.e., in the absence of plasticizing solvents. Here, we disclose that zwitterionic bis-n-tetradecylphosphobetaine, as a model compound, shows a complex thermally switchable hierarchical self-assembly in the solvent-free state. It shows polymorphism and heating-induced reversible switching from low-temperature molecular-level assemblies to high-temperature hierarchical self-assemblies, unexpectedly combining colloidal and molecular self-assemblies, as inferred by synchrotron small-angle X-ray scattering (SAXS). The high-temperature phase sustains birefringent flow, indicating a new type of hierarchical thermotropic liquid crystallinity. The high-temperature colloidal-level SAXS reflections suggest indexation as a 2D oblique pattern and their well-defined layer separation in the perpendicular direction. We suggest that the colloidal self-assembled motifs are 2D nanoplatelets formed by the lateral packing of the molecules, where the molecular packing frustration between the tightly packed zwitterionic moieties and the coiled alkyl chains demanding more space limits the lateral platelet growth controlled by the alkyl stretching entropy. An indirect proof is provided by the addition of plasticizing ionic liquids, which relieve the ionic dense packings of zwitterions, thus allowing purely smectic liquid crystallinity without the colloidal level order. Thus, molecules with a simple chemical structure can lead to structural hierarchy and tunable complexity in the solvent-free state by balancing the competing long-range electrostatics and short-range nanosegregations.

Double smectic self-assembly in block copolypeptide complexes.

We show double smectic-like self-assemblies in the solid state involving alternating layers of different polypeptide α-helices. We employed rod-coil poly(γ-benzyl l-glutamate)-block-poly(l-lysine) (PBLG-b-PLL) as the polymeric scaffold, where the PLL amino residues were ionically complexed to di-n-butyl phosphate (diC4P), di(2-ethylhexyl) phosphate (diC2/6P), di(2-octyldodecyl) phosphate (diC8/12P), or di-n-dodecyl phosphate (diC12P), forming PBLG-b-PLL(diC4P), PBLG-b-PLL(diC2/6P), PBLG-b-PLL(diC8/12P), and PBLG-b-PLL(diC12P) complexes, respectively. The complexes contain PBLG α-helices of fixed diameter and PLL-surfactant complexes adopting either α-helices of tunable diameters or ß-sheets. For PBLG-b-PLL(diC4P), that is, using a surfactant with short n-butyl tails, both blocks were α-helical, of roughly equal diameter and thus with minor packing frustrations, leading to alternating PBLG and PLL(diC4P) smectic layers of approximately perpendicular alignment of both types of α-helices. Surfactants with longer and branched alkyl tails lead to an increased diameter of the PLL-surfactant α-helices. Smectic alternating PBLG and PLL(diC2/6P) layers involve larger packing frustration, which leads to poor overall order and suggests an arrangement of tilted PBLG α-helices. In PBLG-b-PLL(diC8/12P), the PLL(diC8/12P) α-helices are even larger and the overall structure is poor. Using a surfactant with two linear n-dodecyl tails leads to well-ordered ß-sheet domains of PLL(diC12P), consisting of alternating PLL and alkyl chain layers. This dominates the whole assembly, and at the block copolypeptide length scale, the PBLG α-helices do not show internal order and have poor organization. Packing frustration becomes an important aspect to design block copolypeptide assemblies, even if frustration could be relieved by conformational imperfections. The results suggest pathways to control hierarchical liquid-crystalline assemblies by competing interactions and by controlling molecular packing frustrations.

Unidirectional Perpendicularly Aligned Lamella-Structured Oligosaccharide (A) ABA Triblock Elastomer (B) Thin Films Utilizing Triazolium+/TFSI- Ionic Nanochannels.

We designed and synthesized high χ-low N-maltoheptaose-(triazolium+/N(SO2CF3)2-)-polyisoprene-(triazolium+/N(SO2CF3)2-)-maltoheptaose ABA triblock elastomers featuring triazolium+/N(SO2CF3)2- (TFSI-) counteranion ionic interfaces separating their constituting polymeric sub-blocks. Spin-coated and solvent-vapor-annealed (SVA) MH1.2k-(T+/TFSI-)-PI4.3k-(T+/TFSI-)-MH1.2k thin films demonstrate interface-induced charge cohesion through ca. 1 nm "thick" ionic nanochannels which facilitate the self-assembly of a perpendicularly aligned lamellar structure. Atomic force microscopy (AFM) and (grazing-incidence) small-angle X-ray scattering ((GI)SAXS) characterizations of MH1.2k-(T+/TFSI-)-PI4.3k-(T+/TFSI-)-MH1.2k and pristine triBCP analogous thin films revealed sub-10 nm block copolymer (BCP) self-assembly and unidirectionally aligned nanostructures developed over several µm2 areas. Solvated TFSI- counterions enhance the oligosaccharide sub-block packing during SVA. The overall BCP phase behavior was mapped through SAXS characterizations comparing di- vs triblock polymeric architectures, a middle PI sub-block with two different molecular masses, and TFSI- or I- counteranion effects. This work highlights the benefits of inducing single-point electrostatic interactions within chemical structures of block copolymers to master the long-range self-assembly of prescribed morphologies.

Delineating poly(aniline) redox chemistry by using tailored oligo(aryleneamine)s: towards oligo(aniline)-based organic semiconductors with tunable optoelectronic properties.

The simple and elegant Buchwald-Hartwig cross-coupling reaction has been used to synthesise a designed range of new aniline-based tetramers in one step, and without the need for protecting groups. Variation of the central aromatic ring has provided the opportunity to carefully tune the optoelectronic properties in this series, thus enabling a structure-activity relationship study by using a range of photophysical and electrochemical techniques. As a result, the long-proposed sequences of electron-electron (EE) and electron-chemical (EC) processes that support the complex redox and proton-transfer reactions involved in the well-known switching of redox states of poly- and oligo(aniline)s are revealed here for the first time. We also present the initial results from time-dependent DFT calculations to clarify the optoelectronic behaviour of these oligomers. The dc-conductivity measurements of conducting thin films of this series, doped with the prototypical poly(aniline) protonating agent D,L-camphor-10-sulfonic acid (CSA), externally plasticised with triphenyl phosphate (TPP), and processed from m-cresol (MC) solutions, are also presented.

Organic Liquid Crystals as Single-Ion Li+ Conductors.

The development of new materials for tomorrow's electrochemical energy storage technologies, based on thoroughly designed molecular architectures is at the forefront of materials research. In this line, we report herein the development of a new class of organic lithium-ion battery electrolytes, thermotropic liquid crystalline single-ion conductors, for which the single-ion charge transport is decoupled from the molecular dynamics (i. e., obeys Arrhenius-type conductivity) just like in inorganic (single-)ion conductors. Focusing on an in-depth understanding of the structure-to-transport interplay and the demonstration of the proof-of-concept, we provide also strategies for their further development, as illustrated by the introduction of additional ionic groups to increase the charge carrier density, which results in a substantially enhanced ionic conductivity especially at lower temperatures.

Grafted Nanoparticle Surface Wetting during Phase Separation in Polymer Nanocomposite Films.

Wetting of polymer-grafted nanoparticles (NPs) in a polymer nanocomposite (PNC) film is driven by a difference in surface energy between components as well as bulk thermodynamics, namely, the value of the interaction parameter, χ. The interplay between these contributions is investigated in a PNC containing 25 wt % polymethyl methacrylate (PMMA)-grafted silica NPs (PMMA-NPs) in poly(styrene-ran-acrylonitrile) (SAN) upon annealing above the lower critical solution temperature (LCST, 160 °C). Atomic force microscopy (AFM) studies show that the areal density of particles increases rapidly and then approaches 80% of that expected for random close-packed hard spheres. A slightly greater areal density is observed at 190 °C compared to 170 °C. The PMMA-NPs are also shown to prevent dewetting of PNC films under conditions where the analogous polymer blend is unstable. Transmission electron microscopy (TEM) imaging shows that PMMA-NPs symmetrically wet both interfaces and form columns that span the free surface and substrate interface. Using grazing-incidence Rutherford backscattering spectrometry (GI-RBS), the PMMA-NP surface excess (Z*) initially increases rapidly with time and then approaches a constant value at longer times. Consistent with the areal density, Z* is slightly greater at deeper quench depths, which is attributed to the more unfavorable interactions between the PMMA brush and SAN segments. The Z* values at early times are used to determine the PMMA-NP diffusion coefficients, which are significantly larger than theoretical predictions. These studies provide insights into the interplay between wetting and phase separation in PNCs and can be utilized in nanotechnology applications where surface-dependent properties, such as wettability, durability, and friction, are important.

Ionically self-assembled terephthalylidene-bis-4-n-alkylanilines/n-decanesulfonic acid supramolecules: synthesis, mesomorphic behaviour and optical properties.

This paper describes the preparation, mesomorphic and photophysical studies of a two type of calamitic molecules derived from azomethines, N,N'-(1,4-phenylenebis(methan-1-yl-1-ylidene)bis(4-pentylbenzenamine) (LCBAZ1) and N,N'-(1,4-phenylenebis(methan-1-yl-1-ylidene)bis(4-decylbenzenamine) (LCBAZ2) before and after protonation with the n-decyl sulfonic acid (DSA). The lengths of the outer spacers are four or nine methylene units connected with the imine group by phenyl ring in the para position. Liquid crystal properties of the undoped and doped azomethines are studied by differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). Wide-angle X-ray diffraction (WAXD) technique is used to probe the structural properties of the azomethines as well as its complexes. The lengths of the outer flexible spacers have an effect on the mesomorphic properties of the azomethines. The compound LCBAZ2 with nine methylene units exhibit smectic phases (Sm C and Sm X), while the LCBAZ1 with four methylene units exhibit nematic and smectic phases (N and Sm C). The effects of protonation on the phase transitions of the azomethines are investigated. The structure formation of (LCBAZx)(1)(DSA)(2) complexes are discussed on the basis of FTIR spectroscopy. Additionally, the azomethines before and after protonation with DSA are investigated by UV-vis and photoluminescence (PL) spectroscopy. With the exception of LCBAZ1 in its undoped state, the chloroform solution of the doped or undoped azomethines exhibit greenish fluorescence when the solutions are subjected to 400 nm excitation wavelength. It are concluded that the combination of the molecular and supramolecular engineering concepts stabilized the smectic phase.

Lyotropic liquid crystals and linear supramolecular polymers of end-functionalized oligosaccharides.

We synthesized permethylated maltoheptaose oligosaccharides, whose both ends, untrivially, have been functionalized with supramolecular binders 2-ureido-4[1H]-pyrimidinones (UPy) after single ring-opening of ß-cyclodextrin counterpart. In 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), they show lyotropic liquid crystallinity. In the dried state they allow linear saccharide-based supramolecular polymers by UPy-dimerization.

Alignment of Nanoplates in Lamellar Diblock Copolymer Domains and the Effect of Particle Volume Fraction on Phase Behavior.

Polymer nanocomposites (PNCs) that employ diblock copolymers (BCPs) to organize and align anisotropic nanoparticles (NPs) have the potential to facilitate self-assembling hierarchical structures. However, limited studies have been completed to understand the parameters that guide the assembly of nonspherical NPs in BCPs. In this work, we establish a well-defined nanoplate system to investigate the alignment of two-dimensional materials in a lamellar-forming poly(styrene-b-methyl methacrylate) (PS-b-PMMA) BCP with domains oriented parallel to the substrate. Monodisperse gadolinium trifluoride rhombic nanoplates doped with ytterbium and erbium [GdF3:Yb/Er (20/2 mol %)] are synthesized and grafted with phosphoric acid functionalized polyethylene glycol (PEG-PO3H2). Designed with chemical specificity to one block, the nanoplates align in the PMMA domain at low volume fractions (ϕ = 0.0083 and ϕ = 0.017). At these low NP loadings, the BCP lamellae are ordered and induce preferential alignment of the GdF3:Yb/Er nanoplates. However, at high volume fractions (ϕ = 0.050 and ϕ = 0.064), the BCP lamellae are disordered with isotropically dispersed nanoplates. The transition from an ordered BCP system with aligned nanoplates to a disordered BCP with unaligned nanoplates coincides with the calculated overlap volume fraction, ϕ* = 0.051, where the pervaded space of the NPs begins to overlap. Two phenomena are observed in the results: the effect of lamellar formation on nanoplate orientation and the overall phase behavior of the PNCs. The presented research not only expands our knowledge of PNC phase behavior but also introduces a framework to further study the parameters that affect nanoplate alignment in BCP nanocomposites. Our ability to control anisotropic NP orientation in PNCs through self-assembling techniques lends itself to creating multifunctional materials with unique properties for various applications such as photovoltaic cells and barrier coatings.

A synthetic redox biofilm made from metalloprotein-prion domain chimera nanowires.

Engineering bioelectronic components and set-ups that mimic natural systems is extremely challenging. Here we report the design of a protein-only redox film inspired by the architecture of bacterial electroactive biofilms. The nanowire scaffold is formed using a chimeric protein that results from the attachment of a prion domain to a rubredoxin (Rd) that acts as an electron carrier. The prion domain self-assembles into stable fibres and provides a suitable arrangement of redox metal centres in Rd to permit electron transport. This results in highly organized films, able to transport electrons over several micrometres through a network of bionanowires. We demonstrate that our bionanowires can be used as electron-transfer mediators to build a bioelectrode for the electrocatalytic oxygen reduction by laccase. This approach opens opportunities for the engineering of protein-only electron mediators (with tunable redox potentials and optimized interactions with enzymes) and applications in the field of protein-only bioelectrodes.

The influence of polymer purification on photovoltaic device performance of a series of indacenodithiophene donor polymers.

A series of low bandgap indacenodithiophene polymers is purified by recycling SEC in order to isolate narrow polydispersity fractions. This additional purification step is found to have a significant beneficial influence on the solar cell performance and the reasons for this performance increase are investigated.

Influence of polymorphism on charge transport properties in isomers of fluorenone-based liquid crystalline semiconductors.

We measured the charge carrier mobilities for two isomers of fluorenone-based liquid crystalline organic semiconductors from their isotropic down to crystalline states through one or two mesophases. Improved charge transport properties of melt-processed crystalline films were obtained for the isomer exhibiting a highly ordered mesophase below its disordered smectic phase.

Star-shaped azomethines based on tris(2-aminoethyl)amine. Characterization, thermal and optical study.

The synthesis and detailed (physico)-chemical ((1)H/(13)C NMR, FTIR, UV-vis and elemental analysis) characterizations of new star-shaped compounds based on tris(2-aminoethyl)amine, including in their structure an azomethine function (HCN-) and alkoxysemiperfluorinated (-O-(CH(2))(3)-(CF(2))(7)-CF(3)), octadecyloxy aliphatic (-O-(CH(2))(17)-CH(3)) chain or two phenyl rings (-Ph-Ph-) as a terminal group, were reported. The mesomorphic behavior was investigated by means of differential scanning calorimetry (DSC), polarized optical microscopy (POM) and additionally by FTIR(T) and UV-vis(T) spectroscopy. Wide-angle X-ray diffraction (WAXD) technique was used to probe the structural properties of the azomethines. Moreover, the azomethine A1 was electro-spun to prepare fibers with poly(methyl methacrylate) (PMMA) and investigated by DSC and POM. Additionally, a film of the A1 with PMMA was cast from chloroform and the thermal properties of the film were compared with the thermal properties of the fiber and powder. It was showed that terminal groups dramatically influence the thermal and optical properties of the star-shaped azomethines.

UV-vis absorption properties of polyazomethine in base and protonated with 1,2-(di-2-ethylhexyl)ester of 4-sulfophthalic acid form.

The UV-vis absorption properties of undoped and doped 1,4-phenylenemethylidynenitrilo-1,4-phenylenenitrilomethylidyne (PAZ) in various temperatures are reported. It is demonstrated that the absorption spectra can be modified not only by changing the temperature from 193K to 413K, but also via acid-base doping involving the protonation of nitrogen atom in imine group. The use of special protonating agent, i.e. 1,2-(di-2-ethylhexyl)ester of 4-sulfophthalic acid (PSA) lead to the modification of the absorption spectrum of the PAZ. The imine band in UV-vis spectrum of the doped with the PSA polyazomethine is 85 nm red shifts in comparison with unprotonated one. The thermochromism of PAZ included the conformational changes in the conjugating backbone structure of the undoped and doped polyazomethine.

Probing the electronic properties of self-organized poly(3-dodecylthiophene) monolayers by two-dimensional scanning tunneling spectroscopy imaging at the single chain scale.

Regioregular poly(3-dodecylthiophene) films self-organized on highly oriented pyrolytic graphite have been investigated by scanning tunneling microscopy and two-dimensional scanning tunneling spectroscopy (STS). Simulated spectra in very good agreement with the experimental data have been obtained by a method combining ab initio and semiempirical approaches, which allows a careful discussion of the polymer electronic states. From the experimental data, with the support of modeling, it is shown that the STS spectra give a direct access to the polymer semiconducting band gap without noticeable charge-transfer effects from the substrate. Spectroscopic images are achieved at the single chain scale, which allows scrutinizing the electronic consequences of chain folds and pi-stacking effects through spectroscopic contrasts. While chain folds do not locally increase the polymer band gap more than a few tens of millielectonvolt, a striking widening of the STS conductance gap is observed in the case of electronic tunneling through two interacting polymer layers. Scenarios based on nonplanar configuration of thiophene cycles within the second layer or variations of the charge screening effects are proposed to explain this phenomenon.

Counter-ions dynamics in highly plastic and conducting compounds of poly(aniline). A quasi-elastic neutron scattering study.

Proton dynamics in films of poly(aniline) "plastdoped" with di-esters of sulfophthalic (or sulfosuccinic) acids have been investigated by using quasi-elastic neutron scattering techniques. A broad time range (10(-13)-10(-9) s) has been explored by using four different spectrometers. In this time range, the dynamics is exclusively due to protons attached to the flexible tails of the counter-ions. A model of limited diffusion in spheres whose radii are distributed in size gives a realistic view of the geometry of molecular motions. However, it is found that the characteristic times of these motions are widely distributed over several orders of magnitude. The time decay of the intermediate scattering function is well described by a time power law. This behaviour is qualitatively discussed in connection with the structure of the systems and by comparison with other so-called complex systems.