Upconversion Nanoparticle-Based Cell Membrane-Coated cRGD Peptide Bioorthogonally Labeled Nanoplatform for Glioblastoma Treatment.

Glioblastoma is hard to be eradicated partly because of the obstructive blood-brain barrier (BBB) and the dynamic autophagy activities of glioblastoma. Here, hydroxychloroquine (HDX)-loaded yolk-shell upconversion nanoparticle (UCNP)@Zn0.5Cd0.5S nanoparticle coating with the cyclic Arg-Gly-Asp (cRGD)-grafted glioblastoma cell membrane for near-infrared (NIR)-triggered treatment of glioblastoma is prepared for the first time. UCNPs@Zn0.5Cd0.5S (abbreviated as YSN, yolk-shell nanoparticle) under NIR radiation will generate reactive oxygen species for imposing cytotoxicity. HDX, the only available autophagy inhibitor in clinical studies, can enhance cytotoxicity by preventing damaged organelles from being recycled. The cRGD-decorated cell membrane allowed the HDX-loaded nanoparticles to efficiently bypass the BBB and specifically target glioblastoma cells. Exceptional treatment efficacy of the NIR-triggered chemotherapy and photodynamic therapy was achieved in U87 cells and in the mouse glioblastoma model as well. Our results provided proof-of-concept evidence that HDX@YSN@CCM@cRGD could overcome the delivery barriers and achieve targeted treatment of glioblastoma.

Graphite-Mediated Microwave-Exfoliated Graphene Fluoride as Supercapacitor Electrodes.

A graphite-mediated microwave-based strategy was used for solid-state exfoliation of graphite fluoride in a few seconds, followed by a simple yet efficient separation to obtain exfoliated materials based on the density difference between graphite and graphene fluoride in solvent. The microwave-exfoliated graphene fluoride was a few layers thick and electrically conductive. The electrochemical testing of pouch-cell supercapacitors assembled by using the exfoliated graphene fluoride electrodes and a novel microemulsion-based electrolyte showed reasonable performance with typical electrical double-layer capacitance behavior and good rate capability (gravimetric specific capacitance: 3.2 F g-1 at 500 mA g-1 and 3.1 F g-1 at 5000 mA g-1). The BET specific surface areas of the as-exfoliated graphene fluoride are ~60-80 m2 g-1, which could be increased by activation using this simple yet versatile microwave-based method for further improvements on the electrochemical performance.

Vortex fluidic induced mass transfer across immiscible phases.

Mixing immiscible liquids typically requires the use of auxiliary substances including phase transfer catalysts, microgels, surfactants, complex polymers and nano-particles and/or micromixers. Centrifugally separated immiscible liquids of different densities in a 45° tilted rotating tube offer scope for avoiding their use. Micron to submicron size topological flow regimes in the thin films induce high inter-phase mass transfer depending on the nature of the two liquids. A hemispherical base tube creates a Coriolis force as a 'spinning top' (ST) topological fluid flow in the less dense liquid which penetrates the denser layer of liquid, delivering liquid from the upper layer through the lower layer to the surface of the tube with the thickness of the layers determined using neutron imaging. Similarly, double helical (DH) topological flow in the less dense liquid, arising from Faraday wave eddy currents twisted by Coriolis forces, impact through the less dense liquid onto the surface of the tube. The lateral dimensions of these topological flows have been determined using 'molecular drilling' impacting on a thin layer of polysulfone on the surface of the tube and self-assembly of nanoparticles at the interface of the two liquids. At high rotation speeds, DH flow also occurs in the denser layer, with a critical rotational speed reached resulting in rapid phase demixing of preformed emulsions of two immiscible liquids. ST flow is perturbed relative to double helical flow by changing the shape of the base of the tube while maintaining high mass transfer between phases as demonstrated by circumventing the need for phase transfer catalysts. The findings presented here have implications for overcoming mass transfer limitations at interfaces of liquids, and provide new methods for extractions and separation science, and avoiding the formation of emulsions.

Multifunctional Macroassembled Graphene Nanofilms with High Crystallinity.

A "cooling-contraction" method to separate large-area (up to 4.2 cm in lateral size) graphene oxide (GO)-assembled films (of nanoscale thickness) from substrates is reported. Heat treatment at 3000 °C of such free-standing macroscale films yields highly crystalline "macroassembled graphene nanofilms" (nMAGs) with 16-48 nm thickness. These nMAGs present tensile strength of 5.5-11.3 GPa (with ≈3 µm gauge length), electrical conductivity of 1.8-2.1 MS m-1 , thermal conductivity of 2027-2820 W m-1 K-1 , and carrier relaxation time up to ≈23 ps. As a demonstration application, an nMAG-based sound-generator shows a 30 µs response and sound pressure level of 89 dB at 1 W cm-2 . A THz metasurface fabricated from nMAG has a light response of 8.2% for 0.159 W mm-2 and can detect down to 0.01 ppm of glucose. The approach provides a straightforward way to form highly crystallized graphene nanofilms from low-cost GO sheets.

Sub-micron moulding topological mass transport regimes in angled vortex fluidic flow.

Shear stress in dynamic thin films, as in vortex fluidics, can be harnessed for generating non-equilibrium conditions, but the nature of the fluid flow is not understood. A rapidly rotating inclined tube in the vortex fluidic device (VFD) imparts shear stress (mechanical energy) into a thin film of liquid, depending on the physical characteristics of the liquid and rotational speed, ω, tilt angle, θ, and diameter of the tube. Through understanding that the fluid exhibits resonance behaviours from the confining boundaries of the glass surface and the meniscus that determines the liquid film thickness, we have established specific topological mass transport regimes. These topologies have been established through materials processing, as spinning top flow normal to the surface of the tube, double-helical flow across the thin film, and spicular flow, a transitional region where both effects contribute. The manifestation of mass transport patterns within the film have been observed by monitoring the mixing time, temperature profile, and film thickness against increasing rotational speed, ω. In addition, these flow patterns have unique signatures that enable the morphology of nanomaterials processed in the VFD to be predicted, for example in reversible scrolling and crumbling graphene oxide sheets. Shear-stress induced recrystallisation, crystallisation and polymerisation, at different rotational speeds, provide moulds of high-shear topologies, as 'positive' and 'negative' spicular flow behaviour. 'Molecular drilling' of holes in a thin film of polysulfone demonstrate spatial arrangement of double-helices. The grand sum of the different behavioural regimes is a general fluid flow model that accounts for all processing in the VFD at an optimal tilt angle of 45°, and provides a new concept in the fabrication of novel nanomaterials and controlling the organisation of matter.

Defective Indium/Indium Oxide Heterostructures for Highly Selective Carbon Dioxide Electrocatalysis.

Electrochemical CO2 reduction to fuels and chemicals is a promising approach for CO2 utilization. Developing highly active, selective, and cost-effective electrocatalysts is the key to the large-scale application of this technology. Here, we report that defective indium/indium oxide heterostructures selectively catalyze CO2 electroreduction into C1 products in a broad potential range from -0.7 to -1.2 V vs RHE in aqueous media with the faradaic efficiency approaching 100%. This electrocatalyst enables an efficient CO2-to-formate conversion with excellent selectivity (up to 93%), activity (up to 50.8 mA cm-2), and durability (>25 h). The collaboration between metallic In and In oxide of the heterostructures attributes to the boosted electrochemical CO2 reduction: Metallic In mainly facilitates formate production, while In oxide suppresses the competing hydrogen evolution reaction. This study highlights the integration of different functional components/defects into heterostructures as an effective strategy for enhancing CO2 electrocatalysis.

Vitamin B12 on Graphene for Highly Efficient CO2 Electroreduction.

Combining the advantages of homogeneous and heterogeneous catalytic systems has emerged as a promising strategy for electrochemical CO2 reduction although developing robust, active, product-selective, and easily available, catalysts remains a major challenge. Herein, we report the electroreduction of CO2 catalyzed by cobalt and benzimidazole containing Vitamin B12 immobilized on the surface of reduced graphene oxide (rGO). This hybrid system with a naturally abundant molecular catalyst produces CO with high selectivity and a constant current density in an aqueous buffer solution (pH 7.2) for over 10 h. A Faradaic efficiency (FE) of 94.5% was obtained for converting CO2 to CO at an overpotential of 690 mV with a CO partial current density (jCO) of 6.24 mA cm-2 and a turnover frequency (TOF) of up to 28.6 s-1. A higher jCO (13.6 mA cm-2) and TOF (52.4 s-1) can be achieved with this system at a higher overpotential (790 mV) without affecting the product selectivity (∼94%) for CO formation. Our experimental findings are corroborated with density functional theory (DFT) studies to understand the influence of the covalently attached and redox-active benzimidazole unit. To the best of our knowledge, this is the first example of naturally abundant vitamin being immobilized on a conductive surface for highly efficient CO2 electroreduction.

Metal-Sulfur Linkages Achieved by Organic Tethering of Ruthenium Nanocrystals for Enhanced Electrochemical Nitrogen Reduction.

Inspired by the metal-sulfur (M-S) linkages in the nitrogenase enzyme, here we show a surface modification strategy to modulate the electronic structure and improve the N2 availability on a catalytic surface, which suppresses the hydrogen evolution reaction (HER) and improves the rate of NH3 production. Ruthenium nanocrystals anchored on reduced graphene oxide (Ru/rGO) are modified with different aliphatic thiols to achieve M-S linkages. A high faradaic efficiency (11 %) with an improved NH3 yield (50 µg h-1 mg-1 ) is achieved at -0.1 V vs. RHE in acidic conditions by using dodecanethiol. DFT calculations reveal intermediate N2 adsorption and desorption of the product is achieved by electronic structure modification along with the suppression of the HER by surface modification. The modified catalyst shows excellent stability and recyclability for NH3 production, as confirmed by rigorous control experiments including 15 N isotope labeling experiments.

Surface Reconstruction of Ultrathin Palladium Nanosheets during Electrocatalytic CO2 Reduction.

A surface reconstructing phenomenon is discovered on a defect-rich ultrathin Pd nanosheet catalyst for aqueous CO2 electroreduction. The pristine nanosheets with dominant (111) facet sites are transformed into crumpled sheet-like structures prevalent in electrocatalytically active (100) sites. The reconstruction increases the density of active sites and reduces the CO binding strength on Pd surfaces, remarkably promoting the CO2 reduction to CO. A high CO Faradaic efficiency of 93 % is achieved with a site-specific activity of 6.6 mA cm-2 at a moderate overpotential of 590 mV on the reconstructed 50 nm Pd nanosheets. Experimental and theoretical studies suggest the CO intermediate as a key factor driving the structural transformation during CO2 reduction. This study highlights the dynamic nature of defective metal nanosheets under reaction conditions and suggests new opportunities in surface engineering of 2D metal nanostructures to tune their electrocatalytic performance.

Efficient Oxygen Evolution and Gas Bubble Release Achieved by a Low Gas Bubble Adhesive Iron-Nickel Vanadate Electrocatalyst.

Surface chemistry is a pivotal prerequisite besides catalyst composition toward advanced water electrolysis. Here, an evident enhancement of the oxygen evolution reaction (OER) is demonstrated on a vanadate-modified iron-nickel catalyst synthesized by a successive ionic layer adsorption and reaction method, which demonstrates ultralow overpotentials of 274 and 310 mV for delivering large current densities of 100 and 400 mA cm-2 , respectively, in 1 m KOH, where vigorous gas bubble evolution occurs. Vanadate modification augments the OER activity by i) increasing the electrochemical surface area and intrinsic activity of the active sites, ii) having an electronic interplay with Fe and Ni catalytic centers, and iii) inducing a high surface wettability and a low-gas bubble-adhesion for accelerated mass transport and gas bubble dissipation at large current densities. Ex situ and operando Raman study reveals the structural evolution of ß-NiOOH and γ-FeOOH phases during the OER through vanadate-active site synergistic interactions. Operando dynamic specific resistance measurement evidences an accelerated gas bubble dissipation by a significant decrease in the variation of the interfacial resistance during the OER for the vanadate-modified surface. Achievement of a high catalytic turnover of 0.12 s-1 suggests metallic oxo-anion modification as a versatile catalyst design strategy for advanced water oxidation.

Calixarene-mediated assembly of water-soluble C60-attached ultrathin graphite hybrids for efficient activation of reactive oxygen species to treat neuroblastoma cells.

Unprecedented nano-carbon hybrids consisting of exfoliated ultrathin graphite (or single-walled carbon nanotubes) with pristine C60 molecules attached on the surfaces have been produced in water in the presence of p-phosphonic acid calix[8]arene. The amphiphilic calixarene plays multiple roles in these processes to provide water dispersibility and π-π interactions with flexible conformations complementing curvatures of the carbon surfaces. The significantly increased water solubility and area of exposure of C60 enable efficient activation of reactive oxygen species for enhanced phototoxicity to SH-SY5Y human neuroblastoma cell line under laser irradiation.

Large-area single-crystal AB-bilayer and ABA-trilayer graphene grown on a Cu/Ni(111) foil.

High-quality AB-stacked bilayer or multilayer graphene larger than a centimetre has not been reported. Here, we report the fabrication and use of single-crystal Cu/Ni(111) alloy foils with controllable concentrations of Ni for the growth of large-area, high-quality AB-stacked bilayer and ABA-stacked trilayer graphene films by chemical vapour deposition. The stacking order, coverage and uniformity of the graphene films were evaluated by Raman spectroscopy and transmission electron microscopy including selected area electron diffraction and atomic resolution imaging. Electrical transport (carrier mobility and band-gap tunability) and thermal conductivity (the bilayer graphene has a thermal conductivity value of about 2,300 W m-1 K-1) measurements indicated the superior quality of the films. The tensile loading response of centimetre-scale bilayer graphene films supported by a 260-nm thick polycarbonate film was measured and the average values of the Young's modulus (478 GPa) and fracture strength (3.31 GPa) were obtained.

Shock Exfoliation of Graphene Fluoride in Microwave.

An unprecedented microwave-based strategy is developed to facilitate solid-phase, instantaneous delamination and decomposition of graphite fluoride (GF) into few-layer, partially fluorinated graphene. The shock reaction occurs (and completes in few seconds) under microwave irradiation upon exposing GF to either "microwave-induced plasma" generated in vacuum or "catalyst effect" caused by intense sparking of graphite at ambient conditions. A detailed analysis of the structural and compositional transformations in these processes indicates that the GF experiences considerable exfoliation and defluorination, during which sp2 -bonded carbon is partially recovered despite significant structural defects being introduced. The exfoliated fluorinated graphene shows excellent electrochemical performance as anode materials in potassium ion batteries and as catalysts for the conversion of O2 to H2 O2 . This simple and scalable method requires minimal energy input and does not involve the use of other chemicals, which is attractive for extensive research in fluorine-containing graphene and its derivatives in laboratories and industrial applications.

Synergistic bimetallic CoFe2O4 clusters supported on graphene for ambient electrocatalytic reduction of nitrogen to ammonia.

The energy-intensive nature, high level of CO2 emission and sophisticated infrastructure requirement hampered the utilization of the Haber-Bosch process as a green and decentralized system for NH3 production. The electrochemical N2 reduction reaction (NRR) provides a promising alternative to fix N2 under ambient conditions. Here, we report CoFe2O4 nanoclusters anchored on reduced graphene oxide for enhanced nitrogen reduction. In contrast to monometallic counterparts, this composite catalyst achieves a faradaic efficiency of 6.2% with a high rate of NH3 production of 4.2 × 10-11 mol s-1 cm-2 in 0.1 M Na2SO4 aqueous electrolyte. Amelioration of NRR performance could be attributed to the availability of different types of adsorption and active sites for N2 after the incorporation of Co in the Fe3O4 structure. Also, the homogeneous dispersion of nanoclusters on a 2D support can achieve higher active site density. This work provides a new category of binary metal oxides catalysts for NRR under ambient conditions.

Dual-responsive, Methotrexate-loaded, Ascorbic acid-derived Micelles Exert Anti-tumor and Anti-metastatic Effects by Inhibiting NF-κB Signaling in an Orthotopic Mouse Model of Human Choriocarcinoma.

Gestational trophoblastic neoplasia (GTN), the most aggressive form of which is choriocarcinoma, can result from over-proliferation of trophoblasts. Treating choriocarcinoma requires high doses of systemic chemotherapeutic agents, which result in nonspecific drug distribution and severe toxicity. To overcome these disadvantages and enhance chemotherapeutic efficacy, we synthesized redox- and pH-sensitive, self-assembling, ascorbic acid-derived (PEG-ss-aAPP) micelles to deliver the drug methotrexate (MTX). Methods: We developed and tested self-assembling PEG-ss-aAPP micelles, which release their drug cargo in response to an intracellular reducing environment and the acidity of the early lysosome or tumoral microenvironment. Uptake into JEG3 choriocarcinoma cancer cells was examined using confocal microscopy and transmission electron microscopy. We examined the ability of MTX-loaded PEG-ss-aAPP micelles to inhibit metastasis in an orthotopic mouse model of human choriocarcinoma. Results: Drug-loaded micelles had encapsulation efficiency above 95%. Particles were spherical based on transmission electron microscopy, with diameters of approximately 229.0 nm based on dynamic light scattering. The drug carrier responded sensitively to redox and pH changes, releasing its cargo in specific environments. PEG-ss-aAPP/MTX micelles efficiently escaped from lysosome/endosomes, and they were effective at producing reactive oxygen species, strongly inducing apoptosis and inhibiting invasion and migration. These effects correlated with the ability of PEG-ss-aAPP/MTX micelles to protect IκBα from degradation, which in turn inhibited translocation of NF-κB p65 to the nucleus. In an orthotopic mouse model of human choriocarcinoma, PEG-ss-aAPP/MTX micelles strongly inhibited primary tumor growth and significantly suppressed metastasis without obvious side effects. Conclusions: Our results highlight the potential of PEG-ss-aAPP micelles for targeted delivery of chemotherapeutic agents against choriocarcinoma.

Ultrastiff, Strong, and Highly Thermally Conductive Crystalline Graphitic Films with Mixed Stacking Order.

A macroscopic film (2.5 cm × 2.5 cm) made by layer-by-layer assembly of 100 single-layer polycrystalline graphene films is reported. The graphene layers are transferred and stacked one by one using a wet process that leads to layer defects and interstitial contamination. Heat-treatment of the sample up to 2800 °C results in the removal of interstitial contaminants and the healing of graphene layer defects. The resulting stacked graphene sample is a freestanding film with near-perfect in-plane crystallinity but a mixed stacking order through the thickness, which separates it from all existing carbon materials. Macroscale tensile tests yields maximum values of 62 GPa for the Young's modulus and 0.70 GPa for the fracture strength, significantly higher than has been reported for any other macroscale carbon films; microscale tensile tests yield maximum values of 290 GPa for the Young's modulus and 5.8 GPa for the fracture strength. The measured in-plane thermal conductivity is exceptionally high, 2292 ± 159 W m-1 K-1 while in-plane electrical conductivity is 2.2 × 105 S m-1 . The high performance of these films is attributed to the combination of the high in-plane crystalline order and unique stacking configuration through the thickness.

p-Phosphonic acid calix[8]arene mediated synthesis of ultra-large, ultra-thin, single-crystal gold nanoplatelets.

Single-crystal Au nanoplatelets, as large as 28 µm in cross section and as thin as 6 nm, are generated by bubbling hydrogen gas into an aqueous solution of HAuCl4 in the presence of p-phosphonic acid calix[8]arene, which acts as both a catalyst and stabiliser. The use of the ultrathin Au nanoplatelets in oxygen gas sensing has also been established.

Raman Spectral Band Oscillations in Large Graphene Bubbles.

Raman spectra of large graphene bubbles showed size-dependent oscillations in spectral intensity and frequency, which originate from optical standing waves formed in the vicinity of the graphene surface. At a high laser power, local heating can lead to oscillations in the Raman frequency and also create a temperature gradient in the bubble. Based on Raman data, the temperature distribution within the graphene bubble was calculated, and it is shown that the heating effect of the laser is reduced when moving from the center of a bubble to its edge. By studying graphene bubbles, both the thermal conductivity and chemical reactivity of graphene were assessed. When exposed to hydrogen plasma, areas with bubbles are found to be more reactive than flat graphene.

Porous Two-Dimensional Monolayer Metal-Organic Framework Material and Its Use for the Size-Selective Separation of Nanoparticles.

Rational bottom-up construction of two-dimensional (2D) covalent or noncovalent organic materials with precise structural control at the atomic or molecular level remains a challenge. The design and synthesis of metal-organic frameworks (MOFs) based on new building blocks is of great significance in achieving new types of 2D monolayer MOF films. Here, we demonstrate that a complexation between copper(II) ions and tri(ß-diketone) ligands yields a novel 2D MOF structure, either in the form of a powder or as a monolayer film. It has been characterized by Fourier transform infrared, Raman, ultraviolet-visible, X-ray photoelectron, and electron paramagnetic resonance spectroscopies. Selected area electron diffraction and powder X-ray diffraction results show that the MOF is crystalline and has a hexagonal structure. A MOF-based membrane has been prepared by vacuum filtration of an aqueous dispersion of the MOF powder onto a porous Anodisc filter having pore size 0.02 µm. The porous MOF membrane filters gold nanoparticles with a cutoff of ∼2.4 nm.

Controlled Folding of Single Crystal Graphene.

Folded graphene in which two layers are stacked with a twist angle between them has been predicted to exhibit unique electronic, thermal, and magnetic properties. We report the folding of a single crystal monolayer graphene film grown on a Cu(111) substrate by using a tailored substrate having a hydrophobic region and a hydrophilic region. Controlled film delamination from the hydrophilic region was used to prepare macroscopic folded graphene with good uniformity on the millimeter scale. This process was used to create many folded sheets each with a defined twist angle between the two sheets. By identifying the original lattice orientation of the monolayer graphene on Cu foil, or establishing the relation between the fold angle and twist angle, this folding technique allows for the preparation of twisted bilayer graphene films with defined stacking orientations and may also be extended to create folded structures of other two-dimensional nanomaterials.