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The elasticities of double-stranded (ds) DNA and RNA, which are critical to their biological functions and applications in materials science, can be significantly modulated by solution conditions such as ions and temperature. However, there is still a lack of a comprehensive understanding of the role of solvents in the elasticities of dsRNA and dsDNA in a comparative way. In this work, we explored the effect of ethanol solvent on the elasticities of dsRNA and dsDNA by magnetic tweezers and all-atom molecular dynamics simulations. We found that the bending persistence lengths and contour lengths of dsRNA and dsDNA decrease monotonically with the increase in ethanol concentration. Furthermore, the addition of ethanol weakens the positive twist–stretch coupling of dsRNA, while promotes the negative twist–stretch coupling of dsDNA. Counter-intuitively, the lower dielectric environment of ethanol causes a significant re-distribution of counterions and enhanced ion neutralization, which overwhelms the enhanced repulsion along dsRNA/dsDNA, ultimately leading to the softening in bending for dsRNA and dsDNA. Moreover, for dsRNA, ethanol causes slight ion-clamping across the major groove, which weakens the major groove-mediated twist–stretch coupling, while for dsDNA, ethanol promotes the stretch–radius correlation due to enhanced ion binding and consequently enhances the helical radius-mediated twist–stretch coupling. [ABSTRACT FROM AUTHOR]

Summary: Among various electrocatalysts, high-entropy alloys (HEAs) have gained significant attention for their unique properties and excellent catalytic activity in the hydrogen evolution reaction (HER). However, the precise synthesis of HEA catalysts in small sizes remains challenging, which limits further improvement in their catalytic performance. In this study, boron- and nitrogen-doped HEA porous carbon nanofibers (HE-BN/PCNF) with an in situ–grown dendritic structure were successfully prepared, inspired by the germination and growth of tree branches. Furthermore, the dendritic fibers constrained the growth of HEA particles, leading to the synthesis of quantum dot-sized (1.67 nm) HEA particles, which also provide a pathway for designing HEA quantum dots in the future. This work provides design ideas and guiding suggestions for the preparation of borated HEA fibers with different elemental combinations and for the application of dendritic nanofibers in various fields.

Li metal anodes are enticing for batteries due to high theoretical charge storage capacity, but commercialization is plagued by dendritic Li growth and short circuits when cycled at high currents. Applied pressure has been suggested to improve morphology, and therefore performance. We hypothesized that increasing pressure would suppress dendritic growth at high currents. To test this hypothesis, here, we extensively use cryogenic scanning electron microscopy to show that varying the applied pressure from 0.01 to 1 MPa has little impact on Li morphology after one deposition. We show that pressure improves Li density and preserves Li inventory after 50 cycles. However, contrary to our hypothesis, pressure exacerbates dendritic growth through the separator, promoting short circuits. Therefore, we suspect Li inventory is better preserved in cells cycled at high pressure only because the shorts carry a larger portion of the current, with less being carried by electrochemical reactions that slowly consume Li inventory.

Summary: Benefiting from the high modulation bandwidth (BW), low energy consumption and excellent optical performance, lead halide perovskite has attracted wide attention in visible light communication (VLC). However, the ion migration which results in mobile point defects in perovskite structures is recognized as a crucial key factor inducing the performance degradation. Here, the influence of ion migration in perovskite devices on the performance of VLC was systematically studied. The ion migration process is realized by mixing CsPbBr3 and CsPbI3 quantum dots, during which, the performance of the VLC system is reduced, but it can return to its initial state after stabilization. The on-off keying (OOK) modulation scheme of the perovskite light-emitting diode (LED) device was carried out, achieving a data rate of 90 Mbps.

Industry, agriculture, and a growing population all have a major impact on the scarcity of clean‐water. Desalinating or purifying contaminated water for human use is crucial. The combination of thermal membrane systems can outperform conventional desalination with the help of synergistic management of the water‐energy nexus. High energy requirement for desalination is a key challenge for desalination cost and its commercial feasibility. The solution to these problems requires the intermarriage of multidisciplinary approaches such as electrochemistry, chemical, environmental, polymer, and materials science and engineering. The most feasible method for producing high‐quality freshwater with a reduced carbon footprint is demanding incorporation of industrial low‐grade heat with membrane distillation (MD). More precisely, by using a reverse electrodialysis (RED) setup that is integrated with MD, salinity gradient energy (SGE) may be extracted from highly salinized MD retentate. Integrating MD‐RED can significantly increase energy productivity without raising costs. This review provides a comprehensive summary of the prospects, unresolved issues, and developments in this cutting‐edge field. In addition, we summarize the distinct physicochemical characteristics of the membranes employed in MD and RED, together with the approaches for integrating them to facilitate effective water recovery and energy conversion from salt gradients and freshwater. [ABSTRACT FROM AUTHOR]

All-insulator heterostructures with an emerging metallicity are at the forefront of material science, which typically contain at least one band insulator while it is not necessary to be. Here we show emergent phenomena in a series of all-correlated-insulator heterostructures that composed of insulating CaIrO3 and insulating La0.67Sr0.33MnO3. We observed an intriguing insulator-to-metal transition, that depends delicately on the thickness of the iridate component. The simultaneous enhancements of magnetization, electric conductivity, and magnetoresistance effect indicate a percolation-type nature of the insulator-to-metal transition, with the percolation threshold can be reached at an exceptionally low volume fraction of the iridate. Such a drastic transition is induced by an interfacial charge transfer, which interestingly alters the electronic and crystalline structures of the bulk region rather than the limited ultrathin interface. We further showcased the central role of effective correlation in modulating the insulator-to-metal transition, by demonstrating that the critical thickness of iridate for triggering the metallic state can be systematically reduced down to a single unit-cell layer. Insulator-metal transitions driven by electronic correlations in oxide heterostructures have been widely studied, usually involving a correlated insulator and a band insulator. Here the authors study all-correlated-insulator heterostructures and observe a thickness-dependent insulator-metal transition. [ABSTRACT FROM AUTHOR]

Summary: Rechargeable Mg|O2 batteries (RMOBs) offer several advantages over alkali metal-based battery systems owing to Mg’s ease of transport/storage in ambient environment, low cost originating from its high abundance, as well as the high theoretical specific energy of RMOBs. However, research on RMOBs has been stagnant for the past decade, largely owing to unacceptably poor electrochemical performance. Here, we present a RMOB that employs Mg anode, Mg((CF3SO2)2N)2-MgCl2 in diglyme (G2) electrolyte, and commercial Pt/C on carbon fiber paper (Pt/C@CFP) oxygen cathode. This battery demonstrates unparalleled improvement over existing RMOBs by rendering a discharge capacity over 1.6 mAh cm−2, achieving cycle lives up to 35 cycles with a cumulative energy density of ∼3.2 mWh cm−2 at room temperature. This RMOB system seeks to reignite the pursuit of novel electrochemical systems based on Mg-O2 chemistries.

CF2-containing compounds hold significant potential in drug discovery, organic synthesis, and materials science. However, synthesizing various CF2-containing building blocks from a single compound remains challenging. Here, we present a Cu-catalyzed, switchable defluoroborylation and hydrodefluorination of trifluoromethylated alkynes, yielding four types of CF2-containing compounds. The chemo- and regio-selective sp2/sp3 1,2-diborylation and sp2 monoborylation of 1-(trifluoromethyl)alkynes are controlled by adjusting the solvent and ligand quantity. Additionally, altering the base allows selective generation of gem-difluoroalkenes or difluoromethylalkenes. Notably, our method prevents over-defluorination of the CF3 group on unsaturated C-C bonds during nucleophilic additions, preserving the pharmaceutically valuable CF2 group. Experimental data and density functional theory (DFT) calculations elucidate the regioselectivities of Cu-Bpin addition and the regulatory role of the ligand in selective deborylation processes. Achieving the modular synthesis of various CF2-containing building blocks from a single compound remains a formidable challenge. Herein, the authors present a Cu-catalyzed switchable defluoroborylation and hydrodefluorination of trifluoromethylated alkynes, affording four types of synthetically challenging CF2-containing compounds. [ABSTRACT FROM AUTHOR]

Multifunctional fibers represent a cornerstone of human civilization, playing a pivotal role in numerous aspects of societal development. Natural biomaterials, in contrast to synthetic alternatives, offer environmental sustainability, biocompatibility, and biodegradability. Among these biomaterials, natural silk is favored in biomedical applications and smart fiber technology due to its accessibility, superior mechanical properties, diverse functional groups, controllable structure, and exceptional biocompatibility. This review delves into the intricate structure and properties of natural silk fibers and their extensive applications in biomedicine and smart fiber technology. It highlights the critical significance of silk fibers in the development of multifunctional materials, emphasizing their mechanical strength, biocompatibility, and biodegradability. A detailed analysis of the hierarchical structure of silk fibers elucidates how these structural features contribute to their unique properties. The review also encompasses the biomedical applications of silk fibers, including surgical sutures, tissue engineering, and drug delivery systems, along with recent advancements in smart fiber applications such as sensing, optical technologies, and energy storage. The enhancement of functional properties of silk fibers through chemical or physical modifications is discussed, suggesting broader high-end applications. Additionally, the review addresses current challenges and future directions in the application of silk fibers in biomedicine and smart fiber technologies, underscoring silk's potential in driving contemporary technological innovations. The versatility and sustainability of silk fibers position them as pivotal elements in contemporary materials science and technology, fostering the development of next-generation smart materials. [ABSTRACT FROM AUTHOR]

Nanocellulose is not only a renewable material but also brings functions that are opening new technological opportunities. Here we discuss a special subset of this material, in its fibrillated form, which is produced by aerobic microorganisms, namely, bacterial nanocellulose (BNC). BNC offers distinct advantages over plant-derived counterparts, including high purity and high degree of polymerization as well as crystallinity, strength, and water-holding capacity, among others. More remarkably, beyond classical fermentative protocols, it is possible to grow BNC on non-planar interfaces, opening new possibilities in the assembly of advanced bottom-up structures. In this review, we discuss the recent advances in the area of BNC-based biofabrication of three-dimensional (3D) designs by following solid- and soft-material templating. These methods are shown as suitable platforms to achieve bioadaptive constructs comprising highly interlocked biofilms that can be tailored with precise control over nanoscale morphological features. BNC-based biofabrication opens applications that are not possible by using traditional manufacturing routes, including direct ink writing of hydrogels. This review emphasizes the critical contributions of microbiology, colloid and surface science, as well as additive manufacturing in achieving bioadaptive designs from living matter. The future impact of BNC biofabrication is expected to take advantage of material and energy integration, residue utilization, circularity and social latitudes. Leveraging existing infrastructure, the scaleup of biofabrication routes will contribute to a new generation of advanced materials rooted in exciting synergies that combine biology, chemistry, engineering and material sciences. [ABSTRACT FROM AUTHOR]

Summary: Li metal anodes are enticing for batteries due to high theoretical charge storage capacity, but commercialization is plagued by dendritic Li growth and short circuits when cycled at high currents. Applied pressure has been suggested to improve morphology, and therefore performance. We hypothesized that increasing pressure would suppress dendritic growth at high currents. To test this hypothesis, here, we extensively use cryogenic scanning electron microscopy to show that varying the applied pressure from 0.01 to 1 MPa has little impact on Li morphology after one deposition. We show that pressure improves Li density and preserves Li inventory after 50 cycles. However, contrary to our hypothesis, pressure exacerbates dendritic growth through the separator, promoting short circuits. Therefore, we suspect Li inventory is better preserved in cells cycled at high pressure only because the shorts carry a larger portion of the current, with less being carried by electrochemical reactions that slowly consume Li inventory.

Summary: Sulfonated polyphenylene (SPP)-based ionomers have been developed for electrochemical applications in recent years due to their inherent thermal and chemical stability. However, the difficult synthesis, limited solubility, and rigid backbone obstructs their progress. Herein, a new monomer, 3,3″-dichloro-2′,3′,5′,6′-tetrafluoro-1,1':4′,1″-terphenyl (TP-f) with high polymerization reactivity was designed and polymerized with sulfonated phenylene monomer to prepare SPP-based ionomers (SPP-TP-f) with high ion exchange capacity up to 4.5 mequiv g−1. The resulting flexible membranes were more proton conductive than Nafion (state-of-the-art proton exchange membrane) even at 120°C and 20% RH. Unlike typical SPP ionomers, SPP-TP-f 5.1 was soluble in ethanol and thus, could be reinforced with double expanded polytetrafluorethylene thin layers to obtain SPP-TP-f 5.1/DPTFE membrane. SPP-TP-f 5.1/DPTFE showed superior fuel cell performance to that of Nafion, in particular, at low humidity (30% RH, > 100°C) and reasonable durability under the severe accelerated conditions combining OCV hold and humidity cycling tests.

The controlled preparation of oligopyrroles can be enabling for both chemistry and materials science. In this study, we present a straightforward one-pot synthesis that allows access to a series of α,α′-linked arene-bridged oligopyrrolic dialdehydes. The method relies on the Pd(0)-catalyzed tandem Suzuki cross-coupling of heterocyclic precursors. Access to the present diformyl oligopyrroles enables the construction of new macrocycles as confirmed by NMR spectroscopic and mass spectrometric studies, as well as single crystal X-ray diffraction analyses. [ABSTRACT FROM AUTHOR]

Context: To gain a deeper understanding of zinc-doped boron clusters, theoretical calculations were performed to investigate the size effects and electronic properties of zinc-doped boron clusters. The study of the electronic properties, spectral characteristics, and geometric structures of Zn B n (n = 1–15) is of great significance in the fields of semiconductor materials science, material detection, and improving catalytic efficiency. The results indicate that Zn B n (n = 1–15) clusters predominantly exhibit planar or quasi-planar structures, with the Zn atom positioned in the outer regions of the B n framework. The second stable structure of Zn B 3 is a three-dimensional configuration, indicating that the structures of zinc-doped boron clusters begin to convert from the planar or quasi-planar structures to the 3D configurations. The second low-energy structure of Zn B 15 is a novel configuration. Relative stability analyses show that the Zn B 12 has better chemical stability than other clusters with a HOMO-LUMO gap of 2.79 eV. Electric charge analysis shows that part electrons on zinc atoms are transferred to boron atoms, and electrons prefer to cluster near the B n framework. According to the electron localization function, it gets harder to localize electrons as the equivalent face value drops, and it's challenging to see covalent bond formation between zinc and boron atoms. The spectrograms of Zn B n (n = 1–15) exhibit distinct properties and notable spectral features, which can be used as a theoretical basis for the identification and confirmation of boron clusters doped with single-atom transition metals. Methods: The calculations were performed using the ABCluster global search technique combined with density functional theory (DFT) methods. The selected low-energy structures were subjected to geometric optimization and frequency calculations at the PBE0/6-311 + G(d) level to ensure structural stability and eliminate any imaginary frequencies. To acquire more precise relative energies, we performed single-point energies calculations for the low-lying isomers of Zn B n (n = 1–15) at the CCSD(T)/6-311 + G(d)//PBE0/6-311 + G(d) level of theory. All calculations were performed using Gaussian 09 software. To facilitate analysis, we utilized software tools such as Multiwfn, and VMD. [ABSTRACT FROM AUTHOR]

The derivatization of pillar[n]arenes is a prerequisite for endowing them with functions, as well as enriching the application of pillar[n]arene materials in advanced material science. Herein, we report the self‐assembly of amphiphilic rim‐differentiated pillar[5]arene (H1). One side of the pillar[5]arene is composed of hydrophilic poly(ethylene oxide) chains, benzene and azobenzene groups connected with ether bonds, and the other side is composed of ethoxy groups. In CHCl3 solvent, the amphiphile H1 self‐assembled into spherical micelles, while in H2O/THF mixed solvent H1 self‐assembled into nanorod‐like assemblies. Interestingly, addition of a guest molecule composed of tetraphenylethene and hexanenitrile groups (G1) to the CHCl3 solution of H1 produces large sheet aggregates via the strong π–π stacking of rod segments. The reversible transformation between the nanosheet assemblies of host–guest complexes and nanoparticles is achieved by addition of the guest molecule 1,4‐butylamine (G2) and pillar[5]arene with ethoxy groups as competitive molecules. Notably, worm‐like and nanorod micelles of H1 were constructed in H2O/THF solution triggered by light irradiation, which assemblies can be used as photosensitive erasable writing materials. © 2023 Society of Industrial Chemistry. [ABSTRACT FROM AUTHOR]

We investigate the mechanical properties of amorphous and semi-crystalline semi-aromatic polyamides, polyphthalamides (PPA). Three relaxation processes have been identified by DMTA which is consistent with literature for polyamide. PPA exhibit a brittle-to-ductile transition from a low impact strength to a high impact strength. At room temperature, all the studied PPA are brittle. During both tensile and compression experiments, a strain hardening behavior is observed for all the studied samples and is more pronounced in compression. The testing temperature has an influence on the strain hardening modulus, contrary to the crystallinity. Strain hardening gives properties of stability and resistance to damage.