Thermal Chiroptical Switch Based on an Ultra-High Temperature-Initiated Macrocycle Gel Platform.

Responsive chiral optical materials have gained considerable interests from the fields of sensing, display and optical devices. Materials that are capable of changing chiral optics under harsh conditions such as strong basic/acidic or ultra-high temperature provides thoughts for the design of materials working at special environments, which however, are still underdeveloped. Here, we report a proof-of-concept design of organogel that acts as matrices for thermal chiroptical switch with critical working temperature above 100 °C. The reversible solution-to-gel transition of the specific ß-cyclodextrin/dimethyl formide/LiCl system was initialized at about 130 °C, when the luminophores with aggregation-induced-emission property shall be lighted up with transferred chirality from inherent chiral ß-cyclodextrin. It allows for the controlled emergence of circularly polarized luminescence. This delicate design enables successful fabrication of ultra-high temperature thermal chiroptical switch. This article is protected by copyright. All rights reserved.

Multiple-State Control over Supramolecular Chirality through Dynamic Chemistry Mediated Molecular Engineering.

Dynamic chemistry utilizing both covalent and noncovalent bonds provides valid protocols in manipulating properties of self-assemblies and functions. Here we employ dynamic chemistry to realize multiple-route control over supramolecular chirality up to five states. N-protected fluorinated phenylalanine in the carboxylate state self-assembled into achiral nanoparticles ascribed to the amphiphilicity. Protonation promoted one-dimensional growth into helices with shrunk hydrophilicity, which in the presence of disulfide pyridine undergo chirality inversion promoted by the hydrogen bonding-directed coassembly. Further interacting with the water-soluble reductant cleavages the disulfide bond to initiate the rearrangement of coassemblies with a chirality inversion as well. Finally, by tuning the pH environments, aromatic nucleophilic substitution reaction between reduced products and perfluorinated phenylalanine occurs, giving distinct chiral nanoarchitectures with emerged luminescence and circularly polarized luminescence. We thus realized a particular five-state control by combining dynamic chemistry at one chiral compound, which greatly enriches the toolbox in fabricating responsive chiroptical materials.

Pnictogen bonding in imide derivatives for chiral folding and self-assembly.

Pnictogen bonding (PnB) is an attraction interaction that originates from the anisotropic distribution of electron density of pnictogen elements, which however has been rarely found in nitrogen atoms. In this work, for the first time, we unveil the general presence of N-involved PnB in aromatic or aliphatic imide groups and reveal its implications in chiral self-assembly of folding. This long-neglected interaction was consolidated by Cambridge structural database (CSD) searching as well as subsequent computational studies. Though the presence of PnB has limited effects on spectroscopic properties in the solution phase, conformation locking effects are sufficiently expressed in the chiral folding and self-assembly behavior. PnB anchors the chiral conformation to control the emergence and inversion of chiroptical signals, while intramolecular PnB induces the formation of supramolecular tilt chirality. It also enables the chiral folding of imide-containing amino acid or peptide derivatives, which induces the formation of unique secondary structural sequences such as ß-sheets. Finally, the effects of PnB in directing folded helical structures were revealed. Examples of cysteine and cystine derivatives containing multiple N⋯O and N⋯S PnBs constitute an α-helix like secondary structure with characteristic circular dichroism. This work discloses the comprehensive existence of imide-involved PnB, illustrates its important role in folding and self-assembly, and sheds light on the rational fabrication of conformation-locked compounds and polymers with controllable chiroptical activities.

Strain-Induced Phase Separation and Mechanomodulation of Ionic Conduction in Anisotropic Nanocomposite Ionogels.

Ionogels have great potential for the development of tissue-like, soft, and stretchable ionotronics. However, conventional isotropic ionogels suffer from poor mechanical properties, low efficient force transmission, and tardy mechanoelectric response, hindering their practical utility. Here, we propose a simple one-step method to fabricate bioinspired anisotropic nanocomposite ionogels based on a combination of strain-induced phase separation and mechanomodulation of ionic conduction in the presence of attapulgite nanorods. These ionogels show high stretchability (747.1% strain), tensile strength (6.42 MPa), Young's modulus (83.49 MPa), and toughness (18.08 MJ/m3). Importantly, the liquid crystalline domain alignment-induced microphase separation and ionic conductivity enhancement during stretching endow these ionogels with an unusual mechanoelectric response and dual-programmable shape-memory properties. Moreover, the anisotropic structure, good elasticity, and unique resistance-strain responsiveness give the ionogel-based strain sensors high sensitivity, rapid response time, excellent fatigue resistance, and unique waveform-discernible strain sensing, which can be applied to real-time monitoring of human motions. The findings offer a promising way to develop bioinspired anisotropic ionogels to modulate the microstructure and properties for practical applications in advanced ionotronics.

Incorporation of Diketopyrrolopyrrole into Polythiophene for the Preparation of Organic Polymer Transistors.

Polythiophene, as a class of potential electron donor units, is widely used in organic electronics such as transistors. In this work, a novel polymeric material, PDPPTT-FT, was prepared by incorporating the electron acceptor unit into the polythiophene system. The incorporation of the DPP molecule assists in improving the solubility of the material and provides a convenient method for the preparation of field effect transistors via subsequent solution processing. The introduction of fluorine atoms forms a good intramolecular conformational lock, and theoretical calculations show that the structure displays excellent co-planarity and regularity. Grazing incidence wide-angle X-ray (GIWAXS) results indicate that the PDPPTT-FT is highly crystalline, which facilitates carrier migration within and between polymer chains. The hole mobility of this π-conjugated material is as high as 0.30 cm2 V-1 s-1 in organic transistor measurements, demonstrating the great potential of this polymer material in the field of optoelectronics.

Organic Transistors Based on Highly Crystalline Donor-Acceptor π-Conjugated Polymer of Pentathiophene and Diketopyrrolopyrrole.

Oligomers and polymers consisting of multiple thiophenes are widely used in organic electronics such as organic transistors and sensors because of their strong electron-donating ability. In this study, a solution to the problem of the poor solubility of polythiophene systems was developed. A novel π-conjugated polymer material, PDPP-5Th, was synthesized by adding the electron acceptor unit, DPP, to the polythiophene system with a long alkyl side chain, which facilitated the solution processing of the material for the preparation of devices. Meanwhile, the presence of the multicarbonyl groups within the DPP molecule facilitated donor-acceptor interactions in the internal chain, which further improved the hole-transport properties of the polythiophene-based material. The weak forces present within the molecules that promoted structural coplanarity were analyzed using theoretical simulations. Furthermore, the grazing incidence wide-angle X-ray scanning (GIWAXS) results indicated that PDPP-5Th features high crystallinity, which is favorable for efficient carrier migration within and between polymer chains. The material showed hole transport properties as high as 0.44 cm2 V-1 s-1 in conductivity testing. Our investigations demonstrate the great potential of this polymer material in the field of optoelectronics.

Donor-Acceptor-Based Organic Polymer Semiconductor Materials to Achieve High Hole Mobility in Organic Field-Effect Transistors.

Organic polymer semiconductor materials are conveniently tuned to energy levels because of their good chemically modifiable properties, thus enhancing their carrier transport capabilities. Here, we have designed and prepared a polymer with a donor-acceptor structure and tested its potential as a p-type material for organic field-effect transistor (OFET) applications using a solution-processing method. The conjugated polymers, obtained via the polymerization of the two monomers relying on the Stille coupling reaction, possess extremely high molecular weights and thermodynamic stability. Theoretical-based calculations show that PDPP-2S-Se has superior planarity, which is favorable for carrier transport within the main chain. Photophysical and electrochemical measurements systematically investigated the properties of the material and the energy levels with respect to the theoretical values. The maximum hole mobility of the PDPP-2S-Se-based OFET device is 0.59 cm2 V-1 s-1, which makes it a useful material for potential organic electronics applications.

Rational Design of Novel Conjugated Terpolymers Based on Diketopyrrolopyrrole and Their Applications to Organic Thin-Film Transistors.

Organic polymer semiconductor materials, due to their good chemical modifiability, can be easily tuned by rational molecular structure design to modulate their material properties, which, in turn, affects the device performance. Here, we designed and synthesized a series of materials based on terpolymer structures and applied them to organic thin-film transistor (OTFT) device applications. The four polymers, obtained by polymerization of three monomers relying on the Stille coupling reaction, shared comparable molecular weights, with the main structural difference being the ratio of the thiazole component to the fluorinated thiophene (Tz/FS). The conjugated polymers exhibited similar energy levels and thermal stability; however, their photochemical and crystalline properties were distinctly different, leading to significantly varied mobility behavior. Materials with a Tz/FS ratio of 50:50 showed the highest electron mobility, up to 0.69 cm2 V-1 s-1. Our investigation reveals the fundamental relationship between the structure and properties of materials and provides a basis for the design of semiconductor materials with higher carrier mobility.

Non-coding RNAs are key players and promising therapeutic targets in atherosclerosis.

Cardiovascular disease (CVD) is the primary cause of death in humans. Atherosclerosis (AS) is the most common CVD and a major cause of many CVD-related fatalities. AS has numerous risk factors and complex pathogenesis, and while it has long been a research focus, most mechanisms underlying its progression remain unknown. Noncoding RNAs (ncRNAs) represent an important focus in epigenetics studies and are critical biological regulators that form a complex network of gene regulation. Abnormal ncRNA expression disrupts the normal function of tissues or cells, leading to disease development. A large body of evidence suggests that ncRNAs are involved in all stages of atherosclerosis, from initiation to progression, and that some are significantly differentially expressed during AS development, suggesting that they may be powerful markers for screening AS or potential treatment targets. Here, we review the role of ncRNAs in AS development and recent developments in the use of ncRNAs for AS-targeted therapy, providing evidence for ncRNAs as diagnostic markers and therapeutic targets.

Synergistic Use of All-Acceptor Strategies for the Preparation of an Organic Semiconductor and the Realization of High Electron Transport Properties in Organic Field-Effect Transistors.

The development of n-type organic semiconductor materials for transporting electrons as part of logic circuits is equally important to the development of p-type materials for transporting holes. Currently, progress in research on n-type materials is relatively backward, and the number of polymers with high electron mobility is limited. As the core component of the organic field-effect transistor (OFET), the rational design and judicious selection of the structure of organic semiconductor materials are crucial to enhance the performance of devices. A novel conjugated copolymer with an all-acceptor structure was synthesized based on an effective chemical structure modification and design strategy. PDPPTT-2Tz was obtained by the Stille coupling of the DPPTT monomer with 2Tz-SnMe3, which features high molecular weight and thermal stability. The low-lying lowest unoccupied molecular orbital (LUMO) energy level of the copolymer was attributed to the introduction of electron-deficient bithiazole. DFT calculations revealed that this material is highly planar. The effect of modulation from a donor-acceptor to acceptor-acceptor structure on the improvement of electron mobility was significant, which showed a maximum value of 1.29 cm2 V-1 s-1 and an average value of 0.81 cm2 V-1 s-1 for electron mobility in BGBC-based OFET devices. Our results demonstrate that DPP-based polymers can be used not only as excellent p-type materials but also as promising n-type materials.

Halogen Interaction Effects on Chiral Self-Assemblies on Cyclodipeptide Scaffolds Across Hierarchy.

How halogenation affects protein or peptide folding and self-assembly hierarchically? This study tries to answer this question by using the halogen bonding mediated self-assemblies on cyclodipeptide scaffolds. Single-functionalized cyclodipeptides (Cyclo-GX) based on para-halogenated phenylalanine in the solid state form homochiral helical nanotubes via consecutive X···O bonds (X = Cl, Br, and I) independent of halogen kinds. In contrast, double-functionalized cyclodipeptides (Cyclo-XX) feature versatile self-assembly architectures depending on the para-substituents (X = H, F, Cl, Br, and I), affording nanotubular, lamellar, and triple helical nanotubular architectures. Cyclo-BrBr exclusively adopts intramolecular Type-IV X···X interaction that alters the molecular folding and packing, which also gives rise to opposite chirality at molecular folding (secondary structure), stacking (tertiary structure), and self-assembled nanohelices (quarternary structure) at macroscopic scale. It unveils how halogenation impacts on the self-assembly and chirality at hierarchical levels in specific peptides. Clusteroluminescence is found for the cyclodipeptides, achieving high quantum yield up to 71%, whereby circularly polarized luminescence is realized with tunable handedness by controlling halogen substituents.

The natural product, echinatin, protects mice from methicillin-resistant Staphylococcus aureus pneumonia by inhibition of alpha-hemolysin expression.

Antimicrobial resistance (AMR) is a global, multifaceted crisis that poses significant challenges to the successful eradication of devastating pathogens, particularly methicillin-resistant Staphylococcus aureus (MRSA), a persistent superbug that causes devastating infections. The scarcity of new antibacterial drugs is obvious, and antivirulence strategies that reduce the pathogenicity of bacteria by weakening their virulence have become the subject of intense investigation. Alpha-hemolysin (Hla), a cytolytic pore-forming toxin, has a pivotal role in S. aureus pathogenesis. Here, we demonstrated that echinatin, a natural compound isolated from licorice, effectively inhibited the hemolytic activity of MRSA at 32 µg/mL. In addition, echinatin did not interfere with bacterial growth and had no significant cytotoxicity at the inhibitory concentration of S. aureus hemolysis. Heptamer formation tightly correlated with Hla-mediated cell invasion, whereas echinatin did not affect deoxycholic acid-induced oligomerization of Hla. Echinatin affected hemolytic activity through indirect binding to Hla as confirmed by the neutralization assay and cellular thermal shift assay (CETSA). Furthermore, qRT-PCR and western blot analyses revealed that echinatin suppressed Hla expression at both the mRNA and protein levels as well as the transcript levels of Agr quorum-sensing system-related genes. Additionally, when echinatin was added to a coculture system of A549 cells and S. aureus, it significantly reduced cell damage. Importantly, echinatin exhibited a significant therapeutic effect in an MRSA-induced mouse pneumonia model. In conclusion, the present findings demonstrated that echinatin significantly inhibits the hemolysin effect and may be a potential candidate compound for combating drug-resistant MRSA infections.

Charge-Transfer Complex Doped Photothermal Hydrogels for Discriminating Circularly Polarized Near-Infrared Light.

Hydrogels behave as potential candidates to investigate circularly polarized light (CP)-matter interaction, which however suffer from small sensitivity towards circular polarization. Here we report a general protocol to build hydrogels from π-conjugated amino acids with coassembled charge-transfer (CT) complexes, covering a wide scope of donors and acceptors, which were incorporated into stable hydrogel matrices. CT complexes formed block coassemblies with gelators, induced the emergence of macroscopic chiral helices, where efficient chirality transfer occurs to realize tunable Cotton effects from visible light to NIR-I region depending on the structures of CT pairs. The hybrid hydrogels showed tunable photothermal performances with excellent heating-cooling cycling durability. Circularly polarized NIR light selectively triggered gel-solution phase transition at different timescales. Left- and right-CP illumination generates up to 2.5 folds difference in gel collapse time that allows for direct discrimination by naked eyes.

Preparation of Dye Semiconductors via Coupling Polymerization Catalyzed by Two Catalysts and Application to Transistor.

Organic dye semiconductors have received increasing attention as the next generation of semiconductors, and one of their potential applications is as a core component of organic transistors. In this study, two novel diketopyrrolopyrrole (DPP) dye core-based materials were designed and separately prepared using Stille coupling reactions under different palladium catalyst conditions. The molecular weights and elemental compositions were tested to demonstrate that both catalysts could be used to successfully prepare materials of this structure, with the main differences being the weight-average molecular weight and the dispersion index. PDPP-2Py-2Tz I with a longer conjugation length exhibited better thermodynamic stability than the counterpart polymer PDPP-2Py-2Tz II. The intrinsic optical properties of the polymers were relatively similar, while the electrochemical tests showed small differences in their energy levels. The polymers obtained with different catalysts displayed similar and moderate electron mobility in transistor devices, while PDPP-2Py-2Tz I possessed a higher switching ratio. Our study provides a comparison of such dye materials under different catalytic conditions and also demonstrates the great potential of dye materials for optoelectronic applications.

Multicomponent Reaction of Isocyanide, Ditelluride, and Mn(III) Carboxylate: Synthesis of N-Acyl Tellurocarbamate.

A multicomponent reaction of isocyanides, ditellurides and manganese(III) carboxylates under mild reaction conditions leads to the synthesis of various N-acyl tellurocarbamates. This method demonstrates good functional tolerance and broad substrate scope and, as a result, is especially suitable for the postfunctionalization of complicated molecules such as drugs. The given method can be further extended to the synthesis of selenocarbamates.

Porous tantalum shell and augment for acetabular defect reconstruction in revision total hip arthroplasty: a mid-term follow-up study.

AIM: The use of porous tantalum trabecular metal (TM) shell and augment to reconstruct acetabular defects in revision total hip arthroplasty (THA) is a reliable technique. We evaluated the mid-term implant survival, clinical, and radiological outcomes of our first 48 revisions using this technique. PATIENTS AND METHODS: A total of 45 patients (48 hips) who had acetabular revision of THA between 2011 and 2017 using TM shell and augment with possible mid-term follow-up were included. Twenty-two patients were men (49%) and 23 were women (51%), mean age was 62.5 years (34 to 85) and mean follow-up was 75 months (54 to 125). Twenty-four hips (50%) had a Paprosky IIIA defect, 14 (29.2%) had a type IIIB defect, six (12.5%) had a type IIC defect, and four hips (8.3%) had a type IIB defect. None of the patients had pelvic discontinuity (PD). RESULTS: At a mean 6.25 years follow-up, all hips remained well-fixed and implant survival of 100% with the need of re-revision as the end point. Screw fixation was used for all shells; augments and the shell-augment interface was cemented. Excellent pain relief (mean WOMAC score pain 90.5, (38.3 to 100)), and functional outcomes (mean WOMAC function 88.3 (31.9 to 100), mean OHS 89.2 (31.8 to 100)) were noted. Patient satisfaction scores were excellent. CONCLUSION: This study demonstrated satisfactory mid-term clinical and radiological outcomes of using TM shell and augment for reconstructing major acetabular defects without PD in revision THA.

Transpositional Circularly Polarized Luminescence from Transient Charge-Transfer Coassembly.

Charge-transfer (CT) complexation between electron-rich and deficient aromatics has been widely applied in functional optical and photovoltaic materials. The selective complexation and spontaneous disassociation behavior of a dynamic charge-transfer coassembly possess potential in designing smart and dynamic luminescent materials, which however have not been addressed so far. In this work, the transient charge-transfer driven coassembly between π-conjugated amino acids and tetracyanobenzene, showing dynamic luminescent transition and circularly polarized luminescence (CPL) evolution property, is illustrated. Transient coassembly behaviors are independent to the diverse binding sites covering fluorene, naphthalene, and anthracene, attributed to the intramolecular CH…π interaction. Incorporation of fluorescent dyes enables a transient light harvesting process with hyperchromic CPL properties. Spontaneous green-to-red CPL transition hydrogels are also fabricated by embedding a competitive CT donor. Using a polymeric matrix treated by organic solvents, charge-transfer coassembly is immobilized with diverse circularly polarized luminescence. Such sensitive complexation shows applications in moisture-responsive luminescent materials and multiple luminescent color evolutions are realized.

Multi-Modal Chiral Superstructures in Self-Assembled Anthracene-Terminal Amino Acids with Predictable and Adjustable Chiroptical Activities and Color Evolution.

Deep understanding of structure-property relationship between packing of chiral building units and their chiroptical behaviors would significantly facilitate the rational design and fabrication of the emerging chiroptical materials such as circularly polarized luminescence (CPL) emissive materials. In this paper, we unveil the universal existence of supramolecular tilt helical superstructures in self-assembled π-conjugated amino acid derivatives. A series of coded amino acid methyl esters were conjugated to anthracene segments at N-terminus, which afforded 21 and 31 symmetry supramolecular tilt chirality in solid-states. Helical assemblies enabled diversified Cotton effects and CPL performances, which were in accordance with the tilted chirality between anthracene segments. Such correlation shows fine universality, whereby the chiroptical prediction could be realized. Furthermore, on top of charge-transfer complexation, manipulation of CPL emission colors and handedness were realized.

Modular Molecular Self-Assembly for Diversified Chiroptical Systems.

Bottom-up multicomponent molecular self-assembly is an efficient approach to fabricate and manipulate chiral nanostructures and their chiroptical activities such as the Cotton effect and circular polarized luminescence (CPL). However, the integrated coassembly suffers from spontaneous and inherent systematic pathway complexity with low yield and poor fidelity. Consequently, a rational design of chiral self-assembled systems with more than two components remains a significant challenge. Herein, a modularized, ternary molecular self-assembly strategy that generates chiroptically active materials at diverse hierarchical levels is reported. N-terminated aromatic amino acids appended with binding sites for charge transfer and multiple hydrogen bonds undergo the evolution of supramolecular chirality with unique handedness and luminescent color, generating abundant CPL emission with high luminescence dissymmetry factor values in precisely controlled modalities. Ternary coassembly facilitates high-water-content hydrogel formation constituted by super-helical nanostructures, demonstrating a helix to toroid topological transition. This discovery would shed light on developing complicated multicomponent systems in mimicking biological coassembly events.