Helical polymers for dissymmetric circularly polarized light imaging.

Control of the spin angular momentum (SAM) carried in a photon provides a technologically attractive element for next-generation quantum networks and spintronics1-5. However, the weak optical activity and inhomogeneity of thin films from chiral molecular crystals result in high noise and uncertainty in SAM detection. Brittleness of thin molecular crystals represents a further problem for device integration and practical realization of chiroptical quantum devices6-10. Despite considerable successes with highly dissymmetric optical materials based on chiral nanostructures11-13, the problem of integration of nanochiral materials with optical device platforms remains acute14-16. Here we report a simple yet powerful method to fabricate chiroptical flexible layers via supramolecular helical ordering of conjugated polymer chains. Their multiscale chirality and optical activity can be varied across the broad spectral range by chiral templating with volatile enantiomers. After template removal, chromophores remain stacked in one-dimensional helical nanofibrils producing a homogeneous chiroptical layer with drastically enhanced polarization-dependent absorbance, leading to well-resolved detection and visualization of SAM. This study provides a direct path to scalable realization of on-chip detection of the spin degree of freedom of photons necessary for encoded quantum information processing and high-resolution polarization imaging.

Spectrally Resolved Exciton Polarizability for Understanding Charge Generation in Organic Bulk Hetero-Junction Diodes.

Despite decades of research, the dominant charge generation mechanism in organic bulk heterojunction (BHJ) devices is not completely understood. While the local dielectric environments of the photoexcited molecules are important for exciton dissociation, conventional characterizations cannot separately measure the polarizability of electron-donor and electron-acceptor, respectively, in their blends, making it difficult to decipher the spectrally different charge generation efficiencies in organic BHJ devices. Here, by spectrally resolved electroabsorption spectroscopy, we report extraction of the excited state polarizability for individual donors and acceptors in a series of organic blend films. Regardless of the donor and acceptor, we discovered that larger exciton polarizability is linked to larger π-π coherence length and faster charge transfer across the heterojunction, which fundamentally explains the origin of the higher charge generation efficiency near 100% in the BHJ photodiodes. We also show that the molecular packing of the donor and acceptor influence each other, resulting in a synergetic enhancement in the exciton polarizability.

Macroscopic Monograin Nano-Gyroid Thin Films in 4-inch Scale Through Shear-Rolling and Subsequent Solvent Annealing.

The gyroid structure from self-assembly is highly attractive for optical applications such as photonic crystals and metamaterials. However, due to the direction-dependent nature of these applications, achieving a monograin-level structure over a large area has remained challenging. In this study, the fabrication of unidirectionally oriented anisotropic nanocylinders of polystyrene-block-polydimethylsiloxane (PS-b-PDMS) is reported block copolymer thin films up to a 4-inch scale via a shear-rolling process, followed by solvent annealing to induce phase transition to nearly monograin gyroid structures. Grazing-incidence small-angle X-ray scattering (GISAXS) analysis and cross-sectional scanning electron microscope (SEM) images in the direction parallel to the shear-rolling direction reveal the preferential orientation with the (111) plane onto the YZ axis of the film, while only the (110) plane on the YZ axis of the film is observed in the perpendicular direction, with grain sizes approaching single-grain levels. For metamaterial applications, the PDMS domain is selectively removed, and gold is electroplated to produce monograin gold gyroid films.

Suppression of Thermally Induced Surface Traps in Colloidal Quantum Dot Solids via Ultrafast Pulsed Light.

Thermal annealing (TA) of colloidal quantum dot (CQD) films is considered an important process for recent high-performing CQD solar cells (SCs) due to its beneficial effects on CQD solids, including enhanced electrical conductivity, denser packing of CQD films, and the removal of organic residues and solvents. However, the conventional TA for CQDs, which requires several  minutes, leads to hydroxylation and oxidation on the CQD surface, resulting in the formation of trap states and a subsequent decline in SC performance. To address these challenges, this study introduces a flashlight annealing (FLA) technique that significantly reduces the annealing time to the millisecond scale. Through the FLA approach, it successfully suppressed hydroxylation and oxidation, resulting in decreased trap states within the CQD solids while simultaneously preserving their charge transport properties. As a result, CQD SCs treated with FLA exhibited a notable improvement, achieving an open-circuit voltage of 0.66 V compared to 0.63 V in TA-treated devices, leading to an increase in power conversion efficiency from 12.71% to 13.50%.

Enhancing P2/O3 Biphasic Cathode Performance for Sodium-Ion Batteries: A Metaheuristic Approach to Multi-Element Doping Design.

Sodium-ion batteries (SIBs) have emerged as a compelling alternative to lithium-ion batteries (LIBs), exhibiting comparable electrochemical performance while capitalizing on the abundant availability of sodium resources. In SIBs, P2/O3 biphasic cathodes, despite their high energy, require furthur improvements in stability to meet current energy demands. This study introduces a systematic methodology that leverages the meta-heuristically assisted NSGA-II algorithm to optimize multi-element doping in electrode materials, aiming to transcend conventional trial-and-error methods and enhance cathode capacity by the synergistic integration of P2 and O3 phases. A comprehensive phase analysis of the meta-heuristically designed cathode material Na0.76Ni0.20Mn0.42Fe0.30Mg0.04Ti0.015Zr0.025O2 (D-NFMO) is presented, showcasing its remarkable initial reversible capacity of 175.5 mAh g-1 and exceptional long-term cyclic stability in sodium cells. The investigation of structural composition and the stabilizing mechanisms is performed through the integration of multiple characterization techniques. Remarkably, the irreversible phase transition of P2→OP4 in D-NFMO is observed to be dramatically suppressed, leading to a substantial enhancement in cycling stability. The comparison with the pristine cathode (P-NFMO) offers profound insights into the long-term electrochemical stability of D-NFMO, highlighting its potential as a high-voltage cathode material utilizing abundant earth elements in SIBs. This study opens up new possibilities for future advancements in sodium-ion battery technology.

Hole Mobility Enhancement in Benzo[1,2-b:4,5-b']Dithiophene-Based Conjugated Polymer Transistors through Directional Alignment, Perovskite Functionalization and Solid-State Electrolyte Gating.

Tunability in electronic and optical properties has been intensively explored for developing conjugated polymers and their applications in organic and perovskite-based electronics. Particularly, the charge carrier mobility of conjugated polymer semiconductors has been deemed to be a vital figure-of-merit for achieving high-performance organic field-effect transistors (OFETs). In this study, the systematic hole carrier mobility improvement of benzo[1,2-b:4,5-b']dithiophene-based conjugated polymer in perovskite-functionalized organic transistors is demonstrated. In conventional OFETs with a poly(methyl methacrylate) (PMMA) gate dielectric, improvements in hole mobility of 0.019 cm2 V-1 s-1 are measured using an off-center spin-coating technique, which exceeds those of on-center counterparts (0.22 ± 0.07 × 10-2 cm2 V-1 s-1). Furthermore, the mobility drastically increases by adopting solid-state electrolyte gating, corresponding to 2.99 ± 1.03 cm2 V-1 s-1 for the control, and the best hole mobility is 8.03 cm2 V-1 s-1 (average ≈ 6.94 ± 0.59 cm2 V-1 s-1) for perovskite-functionalized OFETs with a high current on/off ratio of >106. The achieved device performance would be attributed to the enhanced film crystallinity and charge carrier density in the hybrid perovskite-functionalized organic transistor channel, resulting from the high-capacitance electrolyte dielectric.

Thermal Management Enables Stable Perovskite Nanocrystal Light-Emitting Diodes with Novel Hole Transport Material.

The severely insufficient operational lifetime of perovskite light-emitting diodes (LEDs) is incompatible with the rapidly increasing external quantum efficiency, even as it approaches the theoretical limit, thereby significantly impeding the commercialization of perovskite LEDs. In addition, Joule heating induces ion migration and surface defects, degrades the photoluminescence quantum yield and other optoelectronic properties of perovskite films, and induces the crystallization of charge transport layers with low glass transition temperatures, resulting in LED degradation under continuous operation. Here, a novel thermally crosslinked hole transport material, poly(FCA60 -co-BFCA20 -co-VFCA20 ) (poly-FBV), with temperature-dependent hole mobility is designed, which is advantageous for balancing the charge injection of the LEDs and limiting the generation of Joule heating. The optimised CsPbI3 perovskite nanocrystal LEDs with poly-FBV realise approximately a 2-fold external quantum efficiency increase over the LED with commercial hole transport layer poly(4-butyl-phenyl-diphenyl-amine) (poly-TPD), owing to the balanced carrier injection and suppressed exciton quenching. Moreover, because of the Joule heating control provided by the novel crosslinked hole transport material, the LED utilising crosslinked poly-FBV has a 150-fold longer operating lifetime (490 min) than that utilizing poly-TPD (3.3 min). The study opens a new avenue for the use of PNC LEDs in commercial semiconductor optoelectronic devices.

The Influence of Regiochemistry on the Performance of Organic Mixed Ionic and Electronic Conductors.

Thiophenes functionalised in the 3-position are ubiquitous building blocks for the design and synthesis of organic semiconductors. Their non-centrosymmetric nature has long been used as a powerful synthetic design tool exemplified by the vastly different properties of regiorandom and regioregular poly(3-hexylthiophene) owing to the repulsive head-to-head interactions between neighbouring side chains in the regiorandom polymer. The renewed interest in highly electron-rich 3-alkoxythiophene based polymers for bioelectronic applications opens up new considerations around the regiochemistry of these systems as both the head-to-tail and head-to-head couplings adopt near-planar conformations due to attractive intramolecular S-O interactions. To understand how this increased flexibility in the molecular design can be used advantageously, we explore in detail the geometrical and electronic effects that influence the optical, electrochemical, structural, and electrical properties of a series of six polythiophene derivatives with varying regiochemistry and comonomer composition. We show how the interplay between conformational disorder, backbone coplanarity and polaron distribution affects the mixed ionic-electronic conduction. Ultimately, we use these findings to identify a new conformationally restricted polythiophene derivative for p-type accumulation-mode organic electrochemical transistor applications with performance on par with state-of-the-art mixed conductors evidenced by a µC* product of 267 F V-1 cm-1 s-1 .

Recyclable Periodic Nanostructure Formed by Sublimable Liquid Crystals for Robust Cell Alignment.

We demonstrate a facile method to fabricate a recyclable cell-alignment scaffold using nanogrooves based on sublimable liquid crystal (LC) material. Randomly and uniaxially arranged smectic LC structures are obtained, followed by sublimation and recondensation processes, which directly produce periodic nanogrooves with dimensions of a couple of hundreds of nanometers. After treatment with osmium tetroxide (OsO4), the nanogroove can serve as a scaffold to efficiently induce directed cell growth without causing cytotoxicity, and it can be used repeatedly. Together, various cell types are applied to the nanogroove, proving the scaffold's broad applicability. Depending on the nanotopography of the LC structures, cells exhibit different morphologies and gene expression patterns, compared to cells on standard glass substrates, according to microscopic observation and qPCR. Furthermore, cell sheets can be formed, which consist of oriented cells that can be repeatedly formed and transferred to other substrates, while maintaining its organization. We believe that our cell-aligning scaffold may pave the way for the soft material field to bioengineering, which can involve fundamentals in cell behavior and function, as well as applications for regenerative medicine.

Effect of Bulky Atom Substitution on Backbone Coplanarity and Electrical Properties of Cyclopentadithiophene-Based Semiconducting Polymers.

The effect of atomic substitution on the optoelectronic properties of a coplanar donor-acceptor (D-A) semiconducting polymer (SPs), prepared using cyclopentadithiophene (CDT) and 2,1,3-benzothiadiazole (BT) moieties, is investigated. By substituting a carbon atom in the BT unit with CF or C-Cl, two random D-A SPs are prepared, and their optoelectronic properties are thoroughly investigated. Density functional theory calculations demonstrate that the fluorinated polymer has a slightly smaller dihedral angle (Ï´ = 0.6°) than the pristine polymer (Ï´ = 1.9°) in its lowest-energy conformation, implying efficient charge transport through the coplanar backbone of the fluorinated polymer. However, the chlorinated polymer shows the lowest energy at a relatively larger dihedral angle (Ï´ = 139°) due to the steric hindrance induced by bulky chlorine atoms in the backbone, thereby leading to thin-film morphology, which is unfavorable for charge transport. Consequently, the fluorinated polymer yields the highest field-effect mobility (µ) of 0.57 cm2 V-1 s-1 , slightly higher than that of the pristine polymer (µ = 0.33 cm2 V-1 s-1 ), and the extended device lifetime of organic field-effect transistors over 12 d without any encapsulation layers. The results of this study provide design guidelines for air-stable D-A SPs.

Mesoscale Frank-Kasper Crystal Structures from Dendron Assembly by Controlling Core Apex Interactions.

Single-component polymeric materials open up a great potential for self-assembly into mesoscale complex crystal structures that are known as Frank-Kasper (FK) phases. Predicting the packing structures of the soft-matter spheres, however, remains a challenge even when the molecular design is precisely known. Here, we investigate the role of the molecules' enthalpic interaction in determining the low-symmetry crystal structures. To this end, we synthesize architecturally asymmetric dendrons by varying their apex functionalities and examine the packing structures of the second-generation (G2) dendritic wedges. Our work shows that weakening the hydrogen bonding of the dendron apex makes the particles softer and smaller, and leads to the formation of various FK structures at lower temperatures, including the new observation of a FK C14 phase in the cone-shaped dendron systems. As a consequence of the free energy balance between the particle's interfacial tension and the chain's stretching, various packing structures are mainly tuned by designing the hydrogen bonding interaction.

Directing Polymorphism in the Helical Nanofilament Phase.

Herein, it is reported that the polymorphism in the helical nanofilament (HNF, B4 ) liquid-crystalline phase depends on the fabrication methods, that is, UV-driven formation and template-assisted self-assembly in the nanoconfined geometry. As a result, uniaxially oriented HNFs with different helical structures were obtained, in which generation of the twisted-ribbon and cylindrical-ribbon polymorphs showed that even the molecular lattice has a different orientation. The detailed structures were directly observed by SEM and grazing-incidence X-ray diffraction with synchrotron radiation. The resultant polymorphs could be used in chiro-optical applications due to the capability for fine control of the helical structures.

Stretchable and Self-Healable Poly(styrene-co-acrylonitrile) Elastomer with Metal-Ligand Coordination Complexes.

Recently, soft electronics have attracted significant attention for various applications such as flexible devices, artificial electronic skins, and wearable devices. For practical applications, the key requirements are an appropriate electrical conductivity and excellent elastic properties. Herein, using the cyano-silver complexes resulting from coordination bonds between the nitrile group of poly(styrene-co-acrylonitrile) (SAN) and Ag ions, a self-healing elastomer demonstrating electrical conductivity is obtained. Because of these coordination complexes, the Ag-SAN elastomer possesses elasticity, compared with pristine SAN. The fracture strain of the Ag-SAN elastomers increased with the amount of added Ag ions, reaching up to 1000%. Additionally, owing to the presence of reversible coordination bonds, the elastomer exhibits self-healing properties at room temperature and electrical conductivity, thereby improving the possibility of its utilization in novel applications wherein elastic materials are generally exposed to external stimuli.

Formicolides A and B, Antioxidative and Antiangiogenic 20-Membered Macrolides from a Wood Ant Gut Bacterium.

Two new macrolides, formicolides A (1) and B (2), were isolated from Streptomyces sp. BA01, a gut bacterial strain of the wood ant (Formica yessensis). Their 20-membered macrocyclic lactone structures were established using NMR and mass spectrometric data. The relative configurations of the formicolides were determined by J-based configuration analysis utilizing ROESY, HETLOC, and HECADE NMR spectroscopic data. Genomic and bioinformatics analysis of the bacterial strain enabled us to identify the type-I polyketide synthase pathway employing a trans-acyltransferase system. The absolute configurations of 1 and 2 are proposed based on detailed analysis of the sequences of the ketoreductases in the modular gene cluster and statistical comparative analysis of the experimental NMR chemical shifts and quantum mechanical calculations. Formicolides A and B (1 and 2) induced quinone reductase activity in murine Hepa-1c1c7 cells and antiangiogenic activity by suppression of tube formation in human umbilical vein endothelial cells.

Manipulation of Supramolecular Columnar Structures of H-Bonded Donor-Acceptor Units through Geometrical Nanoconfinement.

Ambipolar organic semiconductors are considered promising for organic electronics because of their interesting electric properties. Many hurdles remain yet to be overcome before they can be used for practical applications, especially because their orientation is hard to control. We demonstrate a method to control the orientation of columnar structures based on a hydrogen (H)-bonded donor-acceptor complex between a star-shaped tris(triazolyl)triazine and triphenylene-containing benzoic acid, using physicochemical nanoconfinement. The molecular configuration and supramolecular columnar assemblies in a one-dimensional porous anodic aluminium oxide (AAO) film were dramatically modulated by controlling the pore-size and by chemical modification of the inner surface of the porous AAO film. In situ experiments using grazing-incidence X-ray diffraction (GIXRD) were carried out to investigate the structural evolution produced at the nanometer scale by varying physicochemical conditions. The resulting highly ordered nanostructures may open a new pathway to effectively control the alignment of liquid crystal ambipolar semiconductors.

Frank-Kasper Phases Identified in PDMS-b-PTFEA Copolymers with High Conformational Asymmetry.

In the search for the formation of Frank-Kasper phases from diblock copolymer self-assembly, a series of compositionally asymmetric poly(dimethylsiloxane)-b-poly(2,2,2-triflouroethyl acrylate)s (PDMS-b-PTFEAs) are synthesized to produce PDMS-rich phases with PDMS volume fractions (fPDMS ) ranging from 0.746 to 0.869. As determined by small-angle X-ray scattering analysis, the Frank-Kasper σ and C14 phases are identified at fPDMS = 0.796 and 0.851, respectively, plausibly due to high conformational asymmetry (ε ≈ 2.20) between the two blocks. Intriguingly, the σ phase develops during heating from a short-range liquid-like packing (LLP) state, whereas the C14 phase is achieved at room temperature, which are both followed by a disordering at higher temperatures. Based on thermal experiments from a super cooled disordered state, the findings further provide compelling evidence of an LLP-hexagonally packed cylinder-σ transition and a direct pathway to the C14 phase during heating from an LLP state.

Acid-Assisted Ligand Exchange Enhances Coupling in Colloidal Quantum Dot Solids.

Colloidal quantum dots (CQDs) are promising solution-processed infrared-absorbing materials for optoelectronics. In these applications, it is crucial to replace the electrically insulating ligands used in synthesis to form strongly coupled quantum dot solids. Recently, solution-phase ligand-exchange strategies have been reported that minimize the density of defects and the polydispersity of CQDs; however, we find herein that the new ligands exhibit insufficient chemical reactivity to remove original oleic acid ligands completely. This leads to low CQD packing and correspondingly low electronic performance. Here we report an acid-assisted solution-phase ligand-exchange strategy that, by enabling efficient removal of the original ligands, enables the synthesis of densified CQD arrays. Our use of hydroiodic acid simultaneously facilitates high CQD packing via proton donation and CQD passivation through iodine. We demonstrate highly packed CQD films with a 2.5 times increased carrier mobility compared with prior exchanges. The resulting devices achieve the highest infrared photon-to-electron conversion efficiencies (>50%) reported in the spectral range of 0.8 to 1.1 eV.

Perpendicular Orientation of Diblock Copolymers Induced by Confinement between Graphene Oxide Sheets.

We have studied an orientation structure of self-assembled block copolymers (dPS-b-PMMA) of deuterated polystyrene (dPS) and poly(methyl methacrylate) (PMMA) confined between graphene oxide (GO) surfaces. The results of combination techniques, such as neutron reflectivity, time-of-flight secondary-ion mass spectrometry, grazing-incidence small-angle X-ray scattering, and scanning electron microscopy, show that self-assembled domains of the block copolymers in thin films near the GO sheets are oriented perpendicular to the surface of the GO monolayers, in contrast to the horizontal lamellar structure of the copolymer thin film in the absence of the GO monolayers. This is due to the amphiphilic nature of the GO, which leads to a nonpreferential interaction of both dPS and PMMA blocks. Double-sided confinement with the GO monolayers further extends the ordering behavior of the dPS-b-PMMA thin films. Continuous vertical orientation of the block copolymer thin films is also obtained in the presence of alternating GO layers within thick copolymer films.

One-Dimensional Supramolecular Nanoplatforms for Theranostics Based on Co-Assembly of Peptide Amphiphiles.

We report a simple and facile strategy for the preparation of multifunctional nanoparticles with programmable properties using self-assembly of precisely designed block amphiphiles in an aqueous solution-state. Versatile, supramolecular nanoplatform for personalized needs, particularly-theranostics, was fabricated by coassembly of peptide amphiphiles (PAs) in aqueous solution, replacing time-consuming and inaccessible chemical synthesis. Fibrils, driven by the assembly of hydrophobic ß-sheet-forming peptide block, were utilized as a nanotemplate for drug loading within their robust core. PAs were tagged with octreotide [somatostatin (SST) analogue] for tumor-targeting or were conjugated with paramagnetic metal ion (Gd3+)-chelating 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) for magnetic resonance (MR) imaging. The two PA types were coassembled to integrate each PA function into original fibrillar nanotemplates. The adoption of a bulky target-specific cyclic octreotide and ß-sheet-forming peptide with enhanced hydrophobicity led to a morphological transition from conventional fibrils to helical fibrils. The resulting one-dimensional nanoaggregates allowed the successful intracellular delivery of doxorubicin (DOX) to MCF-7 cancer cells overexpressing SST receptor (SSTR) and MR imaging by enabling high longitudinal (T1) relaxivity of water protons. Correlation between the structural nature of fibrils formed by PA coassembly and contrast efficacy was elucidated. The coassembly of PAs with desirable functions may thus be a useful strategy for the generation of tailor-made biocompatible nanomaterials.

Linkage-length dependent structuring behaviour of bent-core molecules in helical nanostructures.

We studied the correlation between the molecular structure and the formation of helical nanofilaments (HNFs) of bent-core dimeric molecules with varying linkage lengths. To obtain precise structural data, a single domain of HNFs was prepared under physical confinement using porous 1D nanochannels, made up of anodic aluminium oxide films. Electron microscopy and grazing incidence X-ray diffraction were used to elucidate the linkage length-dependent formation of HNFs.