Versatile Method for Preparing Two-Dimensional Metal Dihalides.

Ever since the ground-breaking isolation of graphene, numerous two-dimensional (2D) materials have emerged with 2D metal dihalides gaining significant attention due to their intriguing electrical and magnetic properties. In this study, we introduce an innovative approach via anhydrous solvent-induced recrystallization of bulk powders to obtain crystals of metal dihalides (MX2, with M = Cu, Ni, Co and X = Br, Cl, I), which can be exfoliated to 2D flakes. We demonstrate the effectiveness of our method using CuBr2 as an example, which forms large layered crystals. We investigate the structural properties of both the bulk and 2D CuBr2 using X-ray diffraction, along with Raman scattering and optical spectroscopy, revealing its quasi-1D chain structure, which translates to distinct emission and scattering characteristics. Furthermore, microultraviolet photoemission spectroscopy and electronic transport reveal the electronic properties of CuBr2 flakes, including their valence band structure. We extend our methodology to other metal halides and assess the stability of the metal halide flakes in controlled environments. We show that optical contrast can be used to characterize the flake thicknesses for these materials. Our findings demonstrate the versatility and potential applications of the proposed methodology for preparing and studying 2D metal halide flakes.

Fabrication of angstrom-scale two-dimensional channels for mass transport.

Fluidic channels at atomic scales regulate cellular trafficking and molecular filtration across membranes, and thus play crucial roles in the functioning of living systems. However, constructing synthetic channels experimentally at these scales has been a significant challenge due to the limitations in nanofabrication techniques and the surface roughness of the commonly used materials. Angstrom (Å)-scale slit-like channels overcome such challenges as these are made with precise control over their dimensions and can be used to study the fluidic properties of gases, ions and water at unprecedented scales. Here we provide a detailed fabrication method of the two-dimensional Å-scale channel devices that can be assembled to contain a desired number of channels, a single channel or up to hundreds of channels, made with atomic-scale precision using layered crystals. The procedure includes the fabrication of the substrate, flake, spacer layer, flake transfers, van der Waals assembly and postprocessing. We further explain how to perform molecular transport measurements with the Å-channels to directly probe the intriguing and anomalous phenomena that help shed light on the physics governing ultra-confined transport. The procedure requires a total of 1-2 weeks for the fabrication of the two-dimensional channel device and is suitable for users with prior experience in clean room working environments and nanofabrication.

Casein Kinase 1δ Phosphorylates TDP-43 and Suppresses Its Function in Tau mRNA Processing.

BACKGROUND: Neurofibrillary tangle aggregated from anomalous hyperphosphorylated tau is a hallmark of Alzheimer's disease (AD). Trans-active response DNA-binding protein of 43 kDa (TDP-43) enhances the instability and exon (E) 10 inclusion of tau mRNA. Cytoplasmic inclusion of hyperphosphorylated TDP-43 in the neurons constitutes the third most prevalent proteinopathy of AD. Casein kinase 1δ (CK1δ) is elevated in AD brain and phosphorylates TDP-43 in vitro. OBJECTIVE: To determine the roles of CK1δ in phosphorylation, aggregation, and function of TDP-43 in the processing of tau mRNA. METHODS: The interaction and colocalization of TDP-43 and CK1δ were analyzed by co-immunoprecipitation and immunofluorescence staining. TDP-43 phosphorylation by CK1δ was determined in vitro and in cultured cells. RIPA-insoluble TDP-43 aggregates obtained by ultracentrifugation were analyzed by immunoblots. The instability and E10 splicing of tau mRNA were studied by using a reporter of green fluorescence protein tailed with 3'-untranslational region of tau mRNA and a mini-tau gene and analyzed by real-time quantitative PCR and reverse transcriptional PCR. RESULTS: We found that CK1δ interacted and co-localized with TDP-43. TDP-43 was phosphorylated by CK1δ at Ser379, Ser403/404, and Ser409/410 in vitro and in cultured cells, which was mutually enhanced. CK1δ overexpression promoted the aggregation of TDP-43 and suppressed its activity in enhancing the instability and E10 inclusion of tau mRNA. CONCLUSION: CK1δ phosphorylates TDP-43, promotes its aggregation, and inhibits its activity in promoting the instability of tau mRNA and inclusion of tau E10. Elevated CK1δ in AD brain may contribute to TDP-43 and tau pathologies directly or indirectly.

Selective Electrosynthesis of 2,5-Diformylfuran in a Continuous-Flow System.

The gram-scale selective oxidation of biomass-based chemicals, in particular 5-hydroxymethylfurfural (HMF), into value-added 2,5-diformylfuran (DFF) has a high application potential but suffers from high cost, low selectivity, and harsh reaction conditions. Besides, the electrooxidation strategy requires the usage of expensive electrodes and struggles with low selectivity and efficiency, which restricts its further scaled-up application. In this regard, a continuous-flow system was developed through redox mediator I- /I2 for the efficient synthesis of DFF, which could accelerate the mass transfer of I- (I2 ) to aqueous (organic) phase and avoid over-oxidation to achieve high selectivity. After the solvent system, iodine concentration, and reaction time were optimized, highly efficient DFF synthesis (selectivity >99 %) could be achieved in the electrochemical flow system using inexpensive graphite felt (GF) as electrode. Moreover, selective HMF oxidation was paired with the hydrogen evolution reaction with increased efficiency after using in-situ-loaded GF-CoS2 /CoS and GF-Pt electrodes. As a result, the required energy to achieve the gram-scale synthesis of DFF was significantly reduced, demonstrating outstanding potential for large-scale production of the target product.

Chemical Coupled PEDOT:PSS/Si Electrode: Suppressed Electrolyte Consumption Enables Long-Term Stability.

Huge volume changes of Si during lithiation/delithiation lead to regeneration of solid-electrolyte interphase (SEI) and consume electrolyte. In this article, γ-glycidoxypropyl trimethoxysilane (GOPS) was incorporated in Si/PEDOT:PSS electrodes to construct a flexible and conductive artificial SEI, effectively suppressing the consumption of electrolyte. The optimized electrode can maintain 1000 mAh g-1 for nearly 800 cycles under limited electrolyte compared with 40 cycles of the electrodes without GOPS. Also, the optimized electrode exhibits excellent rate capability. The use of GOPS greatly improves the interface compatibility between Si and PEDOT:PSS. XPS Ar+ etching depth analysis proved that the addition of GOPS is conducive to forming a more stable SEI. A full battery assembled with NCM 523 cathode delivers a high energy density of 520 Wh kg-1, offering good stability.

Hydrocarbon contamination in angström-scale channels.

Nonspecific molecular adsorption such as airborne contamination occurs on most surfaces including those of 2D materials and alters their properties. While surface contamination is studied using a plethora of techniques, the effect of contamination on confined systems such as nanochannels/pores leading to their clogging is still lacking. We report a systematic investigation of hydrocarbon adsorption in angstrom (Å) slit channels of varying heights. Hexane is chosen to mimic the hydrocarbon contamination and the clogging of the Å-channels is evaluated via a helium gas flow measurement. The level of hexane adsorption, in other words, the degree of clogging depends on the size difference between the channels and hexane. A dynamic transition of the clogging and revival process is shown in sub-2 nm thin channels. Long-term storage and stability of our Å-channels are demonstrated here for up to three years, alleviating the contamination and unclogging the channels using thermal treatment. This study highlights the importance of the nanochannels' stability and demonstrates the self-cleansing nature of sub-2 nm thin channels enabling a robust platform for molecular transport and separation studies. We provide a method to assess the cleanliness of nanoporous membranes, which is vital for the practical applications of nanofluidics in various fields such as molecular sensing, separation and power generation.

Ion-Cross-Linking-Promoted High-Performance Si/PEDOT:PSS Electrodes: The Importance of Cations' Ionic Potential and Softness Parameters.

PEDOT: PSS has been studied as a silicon-based binder due to its inherent superior electricity and electrochemical stability. However, it cannot effectively alleviate the huge volume changes of silicon during lithiation/delithiation due to its linear structure, resulting in poor cycling stability. Ion-cross-linking is a usual method to cross-link linear polymers into 3D structures. In this paper, multivalent cations of the 5th period and Group 2 cross-linked PEDOT:PSS were applied as silicon anode binders and studied systematically. It was found that the variation trend of viscosity and conductivity of PEDOT:PSS after cross-linking was consistent with that of ionic potential and softness parameters of multivalent cations. The mesostructure of a binder after cross-linking is influenced by the solubility product constant of sulfites or hydroxides of cations and the growth characteristics of crystals. An Sn4+-cross-linked binder displayed increased viscosity and electrical conductivity and higher reduced modulus and hardness due to its positive softness parameter and higher ion potential. The Si electrode with the Sn4+-cross-linked binder showed improved cycling stability (1876.4 mAh g-1 compared with 1068.4 mAh g-1 of the electrode with the pure PEDOT:PSS binder after 100 cycles) and superior rate capability (∼800 mAh g-1 at an ultrahigh current density of 8.0 A g-1).

Glycerol-crosslinked PEDOT:PSS as bifunctional binder for Si anodes: Improved interfacial compatibility and conductivity.

Developing conductive polymer binders is a new way to enhance the electric connectivity and mechanical contact of Si based anode material. While the linear structure of commercial PEDOT:PSS cannot effectively alleviate the volume expansion of Si. Herein, glycerol was introduced as a cross-linker to PEDOT:PSS binder for Si anodes, which can further improve the interfacial compatibility between silicon and PEDOT:PSS. After crosslinking, the peel force increased 2 times. As a result, the Si nanoparticles anode with the glycerol-crosslinked binder exhibited a high reversible capacity of 1951.5 mAh g-1 after 200 cycles at 0.5 A g-1 and superior rate capability (804 mAh g-1 at a high current of 8.0 A g-1) for the inherent superior conductivity of PEDOT:PSS.

Capacitive humidity sensors based on mesoporous silica and poly(3,4-ethylenedioxythiophene) composites.

Owing to the outstanding dielectric properties derived from the conjugated π-electron systems, conjugated polymers have been explored and developed in capacitive humidity sensors for a few decades. In this work, a series of composites - mesoporous silica and semiconducting polymers - MCM-41 (MCM, Mesoporous Crystalline Material)/PEDOT (poly(3,4-ethylenedioxythiophene)) were chemically obtained by in-situ polymerization at 0 °C, while the amounts of PEDOT were adjusted by different evaporation times of EDOT (3,4-ethylenedioxythiophene) in the porous MCM-41 film. Additionally, it was able to modulate both the dielectricity and porosity of the composites via this convenient approach. The obtained capacitive humidity sensors based on MCM-41/PEDOT composites exhibit much better sensing performance than their bulk counterparts, with wider humidity sensing range, higher sensitivity and much faster response speed.

Flower-like SnS2 composite with 3D pyrolyzed bacterial cellulose as the anode for lithium-ion batteries with ultralong cycle life and superior rate capability.

The enormous volume expansion during cycling and poor electron conductivity of SnS2 limit its cycling stability and high rate capability. Herein, flower-like SnS2 anchored on 3D carbon nanofiber structures were designed and synthesized by a simple hydrothermal method. Pyrolyzed bacterial cellulose as 3D carbon nanofibers can not only offer a continuous pathway of Li+ and electrons, but can also migrate the serious volume change of SnS2 during charging and discharging. The obtained composite shows a specific capacity of 408.8 mA h g-1 even after 1500 cycles at 10 A g-1, and almost no specific capacity decay after 20 cycles with a retention of 97.5%.

Curcumin-Loaded Solid Lipid Nanoparticles Enhanced Anticancer Efficiency in Breast Cancer.

Curcumin (Cur) has been widely used in medicine, due to its antibacterial, anti-inflammatory, antioxidant, and antitumor effects. However, its clinic application is limited by its instability and poor solubility. In the present wok, curcumin was loaded into solid lipid nanoparticles (SLNs), in order to improve the therapeutic efficacy for breast cancer. The results measured using transmission electron microscopy (TEM) indicated that Cur-SLNs have a well-defined spherical shape; the size was about 40 nm with a negative surface charge. The drug loading and encapsulation efficiency in SLNs reached 23.38% and 72.47%, respectively. The Cur-SLNs showed a stronger cytotoxicity against SKBR3 cells. In vitro cellular uptake study demonstrated a high uptake efficiency of the Cur-SLNs by SKBR3 cells. Moreover, Cur-SLNs induced higher apoptosis in SKBR3 cells, compared to cells treated by free drug. In addition, Western blot analysis revealed that Cur-SLNs could promote the ratio of Bax/Bcl-2, but decreased the expression of cyclin D1 and CDK4. These results suggested that Cur-SLNs could be a potential useful chemotherapeutic formulation for breast cancer therapy.

Drawn on Paper: A Reproducible Humidity Sensitive Device by Handwriting.

This article describes the development of a kind of full carbon-based humidity sensor fabricated on the paper substrate by handwriting. The electrodes were written by commercial pencils, and the sensitive layer was drawn with an oxidized multiwalled carbon nanotubes (o-MWCNTs) ink marker. The resultant devices exhibit good reproducibility and stability during the dynamic measurement. The response of the optimized paper-based sensor exhibits about five times higher than sensors fabricated on the ceramic substrate, which is owing to the hydrophilic property of the paper substrate. The structure of the sensitive layer formed by dispersing sensitive materials in the porous surface of paper substrates alleviates the inner stress in the process of bending. The response of printing paper-based sensors only shows the 6.7% decay even under an extremely high bending degree.

3D Hierarchical Co-Al Layered Double Hydroxides with Long-Term Stabilities and High Rate Performances in Supercapacitors.

Three-dimensional (3D) flower-like Co-Al layered double hydroxide (Co-Al-LDH) architectures composed of atomically thin nanosheets were successfully synthesized via a hydrothermal method in a mixed solvent of water and butyl alcohol. Owing to the unique hierarchical structure and modification by butyl alcohol, the electrochemical stability and the charge/mass transport of the Co-Al-LDHs was improved. When used in supercapacitors, the obtained Co-Al-LDHs deliver a high specific capacitance of 838 F g-1 at a current density of 1 A g-1 and excellent rate performance (753 F g-1 at 30 A g-1 and 677 F g-1 at 100 A g-1), as well as excellent cycling stability with 95% retention of the initial capacitance even after 20,000 cycles at a current density of 5 A g-1. This work provides a promising alternative strategy to enhance the electrochemical properties of supercapacitors.

Silica Wastes to High-Performance Lithium Storage Materials: A Rational Designed Al2 O3 Coating Assisted Magnesiothermic Process.

Si/C yolk-shell structures have been developed to deal with the major issues associated with Si anodes: the huge volume changes and the low electrical conductivity. However, the fabrication process often involves expensive starting materials and/or simultaneously generates insulated SiC, which is harmful for Si anodes. Here, silica wastes from the optical fibers industry are used as starting materials to prepare high performance Si/C materials with Si@void@C yolk-shell structure via a rational designed Al2 O3 coating assisted magnesiothermic process. The obtained yolk-shell Si@void@C materials have a capacity of more than 1450 mA h g-1 after 100 cycles at 0.4 A g-1 . Thanks to the easily coated and removed Al2 O3 layer, the general formation of SiC can be avoided which is beneficial for improving the rate performances, and a capacity of ≈800 mA h g-1 is still kept after 200 cycles at a high rate of 10 A g-1 with a low capacity loss of 0.08% per cycle.