Fabricating multi-scale controllable PEDOT:PSS arrays via templated freezing assembly.

The fabrication of conducting polymer poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) into controllable hierarchical arrays is gaining increasing interest for various applications, e.g., bioelectronics, and regenerative medicine. Currently, solution-based print processing is the main methodology for fabricating PEDOT:PSS arrays. However, its constraints on crystallinity and polymer chain orientation often necessitate intricate post-processing procedures to enhance their material properties. Here, we report the precise control in the assembly of PEDOT:PSS to have customized arrays via a templated freezing assembly strategy (TFA). We can prepare centimeter-scale PEDOT:PSS patterns with tunable micro-morphology, nanofiber width, crystallinity, and polymer chain orientation. Importantly, the refined micro-morphologies endow good stretchability to the obtained arrays, and regulated crystallinity and polymer chain orientation directly lead to adjustable conductivity, ranging from 10-3 S cm-1 to 100 S cm-1. This strategy provides a novel avenue for fabricating conductive polymers into tailored electric devices, suggesting potential applications in flexible electronic devices and beyond.

Correction: Fabricating multi-scale controllable PEDOT:PSS arrays via templated freezing assembly.

Correction for 'Fabricating multi-scale controllable PEDOT:PSS arrays via templated freezing assembly' by Yang Lin et al., Soft Matter, 2024, 20, 2394-2399, https://doi.org/10.1039/D3SM01651J.

Preparation of Ultrasmall AIE Nanoparticles with Tunable Molecular Packing via Freeze Assembly.

Advances in the development of aggregation-induced emission luminogens (AIEgens) depend on understanding how the molecular packing affects their luminescent properties and on making nanoparticles (NPs) with desired sizes. Although reported strategies have advanced the field, rational control of molecular packing and efficient fabrication of AIEgen NPs sub-5.5 nm in diameter remain pressing issues. Here we report a "freeze assembly" strategy, in which the diameter of AIEgen NPs can be precisely tuned from ∼3 nm to hundreds of nanometers, and a molecular packing in kinetically trapped states that are not easily captured by conventional assembly methods can be obtained, leading to tunable fluorescence emissions. Therefore, this study provides a significant tool to fabricate organic luminescent nanomaterials with diameters smaller than 5 nm, which is of critical importance for biomedical applications; meanwhile, tuning molecular packing in nanoparticles displaying different fluorescence may help to shed new light on the mechanism of AIEgens.

Strong Hydration Ability of Silk Fibroin Suppresses Formation and Recrystallization of Ice Crystals During Cryopreservation.

The cryopreservation (CP) of cell/tissue is indispensable in medical science. However, the formation of ice during cooling and ice recrystallization/growth in time of thawing present significant risk of cell/tissue damage upon analysis of CP process. Herein, the natural and biocompatible silk fibroin (SF) with regular hydrophobic and hydrophilic domains, were first employed as a cryoprotectant (CPA), to the CP of human bone-derived mesenchymal stem cells (hBMSCs), which has been routinely cyropreserved for cell-based therapies. Addtion of SF can regulate the formation of ice crystals during cooling process because of its strong hydration ability in the comparation to the cryopreservation medium (CM) without SF. Moreover, the devitrification-induced recrystallization/growth of ice during the thawing process is suppressed. Most importantly, the addition of 10 mg mL-1 SF can achieve 81.28% cell viability of cryopreserved hBMSCs as similar as those with the addition of 180 mg mL-1 Ficoll 70 (commercial CPA), and the functions of the cryopreserved hBMSCs are maintained as good as that of the fresh ones. This work is not only significant for meeting the ever-increasing demand of cell therapy, but also trailblazing for designing materials in controlling ice formation and growth during the CP of other cells and tissues.

Unraveling Molecular Mechanism on Dilute Surfactant Solution Controlled Ice Recrystallization.

Ice recrystallization (IR) is ubiquitous, playing an important role in many areas of science, such as cryobiology, food science, and atmospheric physics. However, controllable ice recrystallization remains a challenging task largely due to an incomplete understanding of the physical mechanism associated with ice recrystallization. Herein, we explore the molecular mechanism underlying the controlling of ice recrystallization by using different small amphiphilic molecules (surfactants) through joint experimental measurements and molecular dynamics simulation. Our experiment shows that in nonionic/zwitterionic surfactant solutions, the mean size of the recrystallized ice grains increases monotonically with the concentration of surfactants, whereas in the ionic surfactant solutions, the mean size of the recrystallized ice grains tends to increase first and then decrease with increasing the concentration, yielding a peak typically at ∼5 µM. Further sequential ice affinity purification experiments and molecular dynamics simulations show that the surfactants actually do not bind to ice directly. Rather, the different spatial distributions of counter ions and molecular surfactants in the interfacial regions (ice-water interface and water-air interface) and bulk region can markedly affect the mean size of the recrystallized ice grain.

Precise Control Over Kinetics of Molecular Assembly: Production of Particles with Tunable Sizes and Crystalline Forms.

It has been long-pursued but remains a challenge to precisely manipulate the molecular assembly process to obtain desired functional structures. Reported here is the control over the assembly of solute molecules, by a programmed recrystallization of solvent crystal grains, to form micro/nanoparticles with tunable sizes and crystalline forms. A quantitative correlation between the protocol of recrystallization temperature and the assembly kinetics results in precise control over the size of assembled particles, ranging from single-atom catalysts, pure drug nanoparticles, to sub-millimeter organic-semiconductor single crystals. The extensive regulation of the assembly rates leads to the unique and powerful capability of tuning the stacking of molecules, involving the formation of single crystals of notoriously crystallization-resistant molecules and amorphous structures of molecules with a very high propensity to crystallize, which endows it with wide-ranging applications.

Dicyclohepta[ijkl,uvwx]rubicene with Two Pentagons and Two Heptagons as a Stable and Planar Non-benzenoid Nanographene.

Polycyclic aromatic hydrocarbons with hexagons/pentagons or hexagons/heptagons have been intensively investigated in recent years, but those with simultaneous presence of hexagons, pentagons and heptagons remain rare. In this paper, we report dicyclohepta[ijkl,uvwx]rubicene (DHR), a non-benzenoid isomer of dibenzo[bc,kl]coronene with two pentagons and two heptagons. We developed an efficient and scalable synthetic method for DHR by using Scholl reaction and dehydrogenation. Crystal structure of DHR shows that the benzenoid rings, two pentagons and two heptagons are coplanar. The bond lengths analysis and the ICSS(1)zz and LOL-π calculations indicate that the incorporation of two formal azulene moieties has an effect on the conjugated structure. The π-electrons of benzenoid and pentagon rings are more delocalized. Cyclic voltammetry studies indicate that DHR shows multiple oxidation and reduction potentials. Interestingly, DHR exhibits unusual S0 to S2 absorption and abnormal anti-Kasha S2 to S0 emission. Moreover, crystals of DHR exhibit semiconducting behaviour with hole mobility up to 0.082 cm2 V-1 s-1 .

Air-Stable n-Type Thermoelectric Materials Enabled by Organic Diradicaloids.

Air-stable n-type thermoelectric materials are recognized as an important and challenging topic in organic thermoelectrics (OTEs) because conventional n-type OTE materials prepared by chemical doping are highly volatile upon exposure to air. Besides, doping efficiency and microstructure are hard to control with the incorporation of external dopants. We report herein the design and synthesis of unconventional n-type OTE materials based on the diradicaloids 2DQQT-S and 2DQQT-Se, which are proved to be neutral single-component organic conductors that exhibit an unprecedented air stability. Without external n-doping, a pristine film of 2DQQT-Se shows an electrical conductivity as high as 0.29 S cm-1 delivering a power factor of 1.4 µW m-1 K-2 . Under ambient conditions, no decay in electrical conductivity is observed for over 260 hours. This work demonstrates that diradicaloids are promising candidates for air-stable and high-performance OTE materials.

Highly Efficient and Robust Oil/Water Separation Materials Based on Wire Mesh Coated by Reduced Graphene Oxide.

We develop a simple approach for the preparation of oil/water separation material based on the reduced graphene oxide. First, the graphene oxide (GO) is coated on the commercially available wire mesh. The treatment of O2 plasma is exploited to open the pores from the back side using the wire mesh as a ready-made mask, and the GO-coated mesh is subjected to the thermal annealing at 200 °C for 2 h to form stable superhydrophobic reduced graphene oxide (RGO) coating. The as-prepared mesh has excellent stability and reusability and the separation selectivity is above 98% for a variety of mixtures of oil and water. Meanwhile, the as-prepared RGO@mesh-300 shows stable and robust superhydrophobic properties including the stability of long-term storage, the resistance to high temperatures, high humidities, and mechanical abrasion. It is expected that this method of fabricating superhydrophobic materials can find more practical applications, especially in the oil/water separation.

Methane saline suppresses ferroptosis via the Nrf2/HO-1 signaling pathway to ameliorate intestinal ischemia-reperfusion injury.

OBJECTIVES: Intestinal ischemia-reperfusion (I/R) injury is a multifactorial and complex clinical pathophysiological process. Current research indicates that the pathogenesis of intestinal I/R injury involves various mechanisms, including ferroptosis. Methane saline (MS) has been demonstrated to primarily exert anti-inflammatory and antioxidant effects in I/R injury. In this study, we mainly investigated the effect of MS on ferroptosis in intestinal I/R injury and determined its potential mechanism. METHODS: In vivo and in vitro intestinal I/R injury models were established to validate the relationship between ferroptosis and intestinal I/R injury. MS treatment was applied to assess its impact on intestinal epithelial cell damage, intestinal barrier disruption, and ferroptosis. RESULTS: MS treatment led to a reduction in I/R-induced intestinal epithelial cell damage and intestinal barrier disruption. Moreover, similar to treatment with ferroptosis inhibitors, MS treatment reduced ferroptosis in I/R, as indicated by a decrease in the levels of intracellular pro-ferroptosis factors, an increase in the levels of anti-ferroptosis factors, and alleviation of mitochondrial damage. Additionally, the expression of Nrf2/HO-1 was significantly increased after MS treatment. However, the intestinal protective and ferroptosis inhibitory effects of MS were diminished after the use of M385 to inhibit Nrf2 in mice or si-Nrf2 in Caco-2 cells. DISCUSSION: We proved that intestinal I/R injury was mitigated by MS and that the underlying mechanism involved modulating the Nrf2/HO-1 signaling pathway to decrease ferroptosis. MS could be a promising treatment for intestinal I/R injury.

Bioinspired in situ repeatable self-recovery of superhydrophobicity by self-reconstructing the hierarchical surface structure.

Inspired by the biological self-recovery mechanism of superhydrophobicity, a new class of waxgel material with sustainable hierarchical surface micro-structures has been reported. After being damaged or removed, the waxgel material can self-reconstruct its surface layer both chemically and structurally, as well as successfully recovers its superhydrophobicity. In addition, it shows non-fluorinated composition, durability to severe mechanical challenges, and self-recoverable surface structures without external input of any kind such as; heat, UV, plasma etc., which distinguishes waxgel from any previous self-healing superhydrophobic systems. This strategy will open a new path for improving the long-term functionality of different interfacial materials.

Recrystallized ice-templated electroless plating for fabricating flexible transparent copper meshes.

Flexible transparent conductors as a replacement for indium tin oxide (ITO) have been urgently pursued due to the inherent drawbacks of ITO films. Here, we report the fabrication of flexible transparent copper meshes with recrystallized ice-crystal templates. Completely different to conventional approaches, this novel method needs neither the fabrication of mesh patterns via micro/nanofabrication technologies nor the deposition of copper through evaporation or sputtering. The linewidth and mesh size of the prepared copper meshes can be regulated, as the ice recrystallization process is controllable. Therefore, the formed copper meshes have tailorable conductivity and transparency, which are critical for optoelectronic devices. Remarkably, the electrical performance of the copper meshes is maintained even after storing for 60 days in ambient conditions or bending for 1000 cycles. This strategy is modular and can also be employed to prepare other metal meshes, such as silver meshes, offering versatile substitutes for ITO in electronic devices.

Flexible Graphene Nanocomposites with Simultaneous Highly Anisotropic Thermal and Electrical Conductivities Prepared by Engineered Graphene with Flat Morphology.

Achieving nanocomposites with simultaneous highly anisotropic thermal and electrical conductivities using carbon materials remains challenging as carbon material tends to form random networks in nanocomposites. Here, highly anisotropic and flexible graphene@naphthalenesulfonate (NS)/poly(vinyl alcohol) (GN/PVA) nanocomposites were fabricated using a layer-by-layer scraping method with flat graphene as the starting functional filler. NS acted as a bond bridge for linking the graphene (π-π interaction) and PVA (hydrogen bond). The results showed well-dispersed graphene in the nanocomposites while maintaining flat morphology with uniform in-plane orientation. The as-fabricated nanocomposites exhibited highly anisotropic thermal and electrical conductivities. The in-plane and out-of-plane thermal conductivities of the nanocomposite prepared with 10.0 wt % graphene reached 13.8 and 0.6 W m-1 K-1, and in-plane and out-of-plane electrical conductivities were 10-1 and 10-10 S cm-1, respectively. This indicated highly anisotropic thermal and electrical conductivities. Furthermore, the nanocomposites showed elevated flexibility and tensile strength from 42.0 MPa for pure PVA to 110.0 MPa for GN-5.0 wt %/PVA. In sum, the proposed strategy is effective for the preparation of nanocomposites with high flexibility, as well as superior anisotropic thermal and electrical conductivities.

Hydroxyl Groups on the Graphene Surfaces Facilitate Ice Nucleation.

Although it is crucial to the formation of cirrus clouds and consequently the climate on Earth, the unambiguous effect of carbonaceous materials (CM) on ice nucleation remains to be unveiled as the chemical variation on the surface of CM is always complicated by the change in morphology. Here, we separately investigate the effects of the surface chemistry and morphology of CM on ice nucleation by studying ice nucleation on highly oriented pyrolytic graphite surfaces treated with different types of plasmas. We discover unambiguously that increasing the density of hydroxyl groups leads to an increased activity of ice nucleation on the surface of graphene, while no observable effects are found when carboxylic groups are introduced. Analysis based on the classical nucleation theory reveals that the increase in the density of hydroxyl groups on the graphene surface results in an increased binding energy between the ice nucleus and the graphene surface, which consequently facilitates the formation of the critical ice nucleus.

Durable Anti-Icing Coatings Based on Self-Sustainable Lubricating Layer.

A versatile, convenient, and cost-effective method that can be used for grafting anti-icing materials onto different surfaces is highly desirable. Based on mussel-inspired chemistry, the anti-icing coating with extremely low ice adhesion is enabled by constructing a self-sustainable lubricating layer, achieved via modifying solid substrates with a highly hydrophilic conjugate of poly(acrylic acid)-dopamine. Both unfreezable and freezable water remain liquidlike at subzero conditions and synergistically fulfill the role of lubrication for reducing the ice adhesion. The anti-icing coatings show excellent stability in harsh environments and durability after the cross-linking. More importantly, this coating can be applied to various substrates and is of great promise for practical applications.

Size Controllable, Transparent, and Flexible 2D Silver Meshes Using Recrystallized Ice Crystals as Templates.

Ice templates have been widely utilized for the preparation of porous materials due to the obvious advantages, such as environmentally benign and applicable to a wide range of materials. However, it remains a challenge to have controlled pore size as well as dimension of the prepared porous materials with the conventional ice template, since it often employs the kinetically not-stable growing ice crystals as the template. For example, there is no report so far for the preparation of 2D metal meshes with tunable pore size based on the ice template, although facile and eco-friendly prepared metal meshes are highly desirable for wearable electronics. Here, we report the preparation of 2D silver meshes with tunable mesh size employing recrystallized ice crystals as templates. Ice recrystallization is a kinetically stable process; therefore, the grain size of recrystallized ice crystals can be easily tuned, e.g., by adding different salts and changing the annealing temperature. Consequently, the size and line width of silver meshes obtained after freeze-drying can be easily adjusted, which in turn varied the conductivity of the obtained 2D silver film. Moreover, the silver meshes are transparent and display stable conductivity after the repeated stretching and bending. It can be envisioned that this approach for the preparation of 2D conducting films is of practical importance for wearable electronics. Moreover, this study provides a generic approach for the fabrication of 2D meshes with a controllable pore size.

Ion-specific ice recrystallization provides a facile approach for the fabrication of porous materials.

Ice recrystallization is of great importance to both fundamental research and practical applications, however understanding and controlling ice recrystallization processes remains challenging. Here, we report the discovery of an ion-specific effect on ice recrystallization. By simply changing the initial type and concentration of ions in an aqueous solution, the size of ice grains after recrystallization can be tuned from 27.4±4.1 to 277.5±30.9 µm. Molecular dynamics simulations show that the ability of the ion to be incorporated into the ice phase plays a key role in the ultimate size of the ice grains after recrystallization. Moreover, by using recrystallized ice crystals as templates, 2D and 3D porous networks with tuneable pore sizes could be prepared from various materials, for example, NaBr, collagen, quantum dots, silver and polystyrene colloids. These porous materials are suitable for a wide range of applications, for example, in organic electronics, catalysis and bioengineering.

Cross-linkage effect of cellulose/laponite hybrids in aqueous dispersions and solid films.

Homogenous cellulose/laponite aqueous dispersions and composite films were respectively prepared from the pre-cooling NaOH/urea aqueous systems. Rheological measurements of aqueous dispersions demonstrated a sol-to-gel transition triggered by loading of laponite, reflecting a cross-linkage effect of cellulose/laponite hybrids. Similarly, based on scanning electron microscopy (SEM), Fourier-transform infrared (FTIR) spectroscopy, and X-ray diffraction (XRD) characterizations, as well as mechanical and thermal measurements, the cross-linkage effect of cellulose/laponite hybrids was also found in solid films, which played an important role in improving the tensile strength (σb) of composite films. For instance, the σb exhibited a largest enhancement up to 75.7% at a critical laponite content of 0.100 wt%, indicating that the property of composite film was closely related with the dispersion and interaction state of laponite, i.e. its content in cellulose matrix. These results were expected to provide significant information for fabrication and utility of cellulose-based materials.

Characterisation of cellulose films regenerated from acetone/water coagulants.

A precooled aqueous solution of 7 wt% NaOH/12 wt% urea was used to dissolve cellulose up to a concentration of 2 wt%, which was then coagulated in an acetone/water mixture to regenerate cellulose film. The volume ratio of acetone to water (φ) had a dominant influence on film dimensional stability, film-forming ability, micromorphology, and mechanical strength. The film regenerated at φ=2.0 showed excellent performance in both dimensional stability and film-forming ability. Compared to that from pure acetone, the cellulose film from the acetone/water mixture with φ=2.0 was more densely interwoven, since the cellulosic fibrils formed during regeneration had pores with smaller average diameter. The alkali capsulated in the film during film formation could be released at quite a slow rate into the surrounding aqueous solution. The regenerated cellulose film with adjustable structure and properties may have potential applications in drug release and ultra filtration.