Controlling the spacing of the linked graphene oxide system with dithiol linkers under confinement.

2D nanoscale confined systems exhibit behavior that is markedly different from that observed at the macroscale. Confinement can be tuned by controlling the interlayer spacing between confining layers using organic dithiol linkers. Adjusting spacing and selective intercalation have important impacts for catalysis, superconductivity, spin engineering, sodium ion batteries, 2D magnets, optoelectronics, and many other applications. In this study, we report how reaction conditions and organic linkers can be used to create variable, reproducible spacings between graphene oxide to provide confinement systems. We determined the conditions under which the spacing can be variably adjusted by the type of linker used, the concentration of the linker, and the reaction conditions. Employing dithiol linkers of different lengths, such as three (TPDT) and four (QPDT) aromatic rings, we can adjust the spacing between graphene oxide layers under varied reaction conditions. Here, we show that by varying dithiol linker length and using different reaction conditions, we can reproducibly control the spacing between graphene oxide layers from 0.37 nm to over 0.50 nm.

Strategic preparation of porous magnetic molecularly imprinted polymers via a simple and green method for high-performance adsorption and removal of meropenem.

In this study, a facile method has been developed to synthesize a novel type of porous magnetic molecularly imprinted polymers (Fe3O4-MER-MMIPs) for the selective adsorption and removal of meropenem. The Fe3O4-MER-MMIPs, with abundant functional groups and sufficient magnetism for easy separation, are prepared in aqueous solutions. The porous carriers reduce the overall mass of the MMIPs, greatly improving their adsorption capacity per unit mass and optimizing the overall value of the adsorbents. The green preparation conditions, adsorption performance, and physical and chemical properties of Fe3O4-MER-MMIPs have been carefully studied. The developed submicron materials exhibit a homogeneous morphology, satisfactory superparamagnetism (60 emu g-1), large adsorption capacity (11.49 mg g-1), quick adsorption kinetics (40 min), and good practical implementation in human serum and environmental water. Finally, the protocol developed in this work delivers a green and feasible method for synthesizing highly efficient adsorbents for the specific adsorption and removal of other antibiotics as well.

Spatially-directed magnetic molecularly imprinted polymers with good anti-interference for simultaneous enrichment and detection of dual disease-related bio-indicators.

As the changes of biomarkers directly reflect the occurrence of degenerative diseases, accurate detection of biomarkers is of great significance for disease diagnosis and control. However, single index detection has high uncertainties to accurately reflect the pathological characteristics because of the complexity of the human internal environment and the extremely trace concentration of indicators. To this end, a method for simultaneous detection of dual-biomarkers based on anti-interference magnetic molecularly imprinted polymers (D-mag-MIPs) is thereby proposed, and successfully applied in human urine analysis for the detection of Parkinson's disease bio-indicators 4-dihydroxyphenylacetic acid (DOPAC) and dopamine (DA). In this work, carboxyl functionalized ferric oxide served as a magnetic core, laying a solid foundation for batch detection. Hyperbranched polyethylenimine, whose abundant amino groups can provide multiple interaction forces to templates with high affinity, is employed as a functional monomer. Relative to single-template MIPs, D-mag-MIPs achieve the detection of dual bio-indicators in a one-time test, reducing the false positive result probability and enhancing the detection accuracy. The proposed methodology has been evaluated to exhibit good anti-interference, satisfactory precision, low detection limits, wide linear ranges and fast batch detection for DA and DOPAC. This work thus offers an alternative and efficient pathway for convenient batch detection of dual bio-indicators from biofluids at once.

In situ temperature measurements in sooting methane/air flames using synchrotron x-ray fluorescence of seeded krypton atoms.

Synchrotron x-ray fluorescence has been used to measure temperatures in optically dense gases where traditional methods would fail. These data provide a benchmark for stringent tests of computational fluid dynamics models for complex systems where physical and chemical processes are intimately linked. The experiments measured krypton number densities in a sooting, atmospheric pressure, nonpremixed coflow flame that is widely used in combustion research. The experiments not only form targets for the models, but the simulations also identify potential sources of uncertainties in the measurements, allowing for future improvements.

Novel bayberry-and-honeycomb-like magnetic surface molecularly imprinted polymers for the selective enrichment of rutin from Sophora japonica.

Rutin (RT), a widely distributed natural flavonoid compound, has been generally utilized as an important active ingredient owing to its considerable biomedical and economic value. Inspired by the structure features of densely-packed bayberry and well-orientated honeycomb, a novel type of magnetic molecularly imprinted polymers (HB-TI-MMIPs) with abundant high-affinity and uniformly-distributed binding sites was rationally constructed for the selective enrichment of RT from Sophora japonica. The polymerization conditions, physicochemical properties, and adsorption performance of the imprinted nanomaterials were systematically investigated. The optimized HB-TI-MMIPs display a high adsorption capacity, fast adsorption rate, and satisfactory selectivity towards RT. Meanwhile, the proposed analytical methodology using HPLC, with HB-TI-MMIPs as adsorbents, successfully applied to enrich and detect RT from Sophora japonica with high recoveries (87.2-94.6%) and good RSDs (lower than 4.3%). Therefore, the fabricated HB-TI-MMIPs with a fast magnetic responsivity and desirable adsorption performance would be attractive in plant active ingredients extraction fields.

Nano-structural effects on Hematite (α-Fe2O3) nanoparticle radiofrequency heating.

Nano-sized hematite (α-Fe2O3) is not well suited for magnetic heating via an alternating magnetic field (AMF) because it is not superparamagnetic-at its best, it is weakly ferromagnetic. However, manipulating the magnetic properties of nano-sized hematite (i.e., magnetic saturation (Ms), magnetic remanence (Mr), and coercivity (Hc)) can make them useful for nanomedicine (i.e., magnetic hyperthermia) and nanoelectronics (i.e., data storage). Herein we study the effects of size, shape, and crystallinity on hematite nanoparticles to experimentally determine the most crucial variable leading to enhancing the radio frequency (RF) heating properties. We present the synthesis, characterization, and magnetic behavior to determine the structure-property relationship between hematite nano-magnetism and RF heating. Increasing particle shape anisotropy had the largest effect on the specific adsorption rate (SAR) producing SAR values more than 6 × greater than the nanospheres (i.e., 45.6 ± 3 W/g of α-Fe2O3 nanorods vs. 6.89 W/g of α-Fe2O3 nanospheres), indicating α-Fe2O3 nanorods can be useful for magnetic hyperthermia.

In Situ Identification of Reaction Intermediates and Mechanistic Understandings of Methane Oxidation over Hematite: A Combined Experimental and Theoretical Study.

Effective methane utilization for either clean power generation or value-added chemical production has been a subject of growing attention worldwide for decades, yet challenges persist mostly in relation to methane activation under mild conditions. Here, we report hematite, an earth-abundant material, to be highly effective and thermally stable to catalyze methane combustion at low temperatures (<500 °C) with a low light-off temperature of 230 °C and 100% selectivity to CO2. The reported performance is impressive and comparable to those of precious-metal-based catalysts, with a low apparent activation energy of 17.60 kcal·mol-1. Our theoretical analysis shows that the excellent performance stems from a tetra-iron center with an antiferromagnetically coupled iron dimer on the hematite (110) surface, analogous to that of the methanotroph enzyme methane monooxygenase that activates methane at ambient conditions in nature. Isotopic oxygen tracer experiments support a Mars van Krevelen redox mechanism where CH4 is activated by reaction with a hematite surface oxygen first, followed by a catalytic cycle through a molecular-dioxygen-assisted pathway. Surface studies with in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and density functional theory (DFT) calculations reveal the evolution of reaction intermediates from a methoxy CH3-O-Fe, to a bridging bidentate formate b-HCOO-Fe, to a monodentate formate m-HCOO-Fe, before CO2 is eventually formed via a combination of thermal hydrogen-atom transfer (HAT) and proton-coupled electron transfer (PCET) processes. The elucidation of the reaction mechanism and the intermediate evolutionary profile may allow future development of catalytic syntheses of oxygenated products from CH4 in gas-phase heterogeneous catalysis.

Semiconductor-to-conductor transition in 2D copper(ii) oxide nanosheets through surface sulfur-functionalization.

Functionalization is a widely-used strategy to modulate and optimize the properties of materials towards various applications, including sensing, catalysis, and energy generation. While the influence of sulfur-functionalization of carbon materials and oxides like ZnO and TiO2 has been studied, far less research has been devoted to analyzing sulfur-functionalization of CuO and other transition metal oxide nanomaterials. Here, we report sulfur-functionalization of copper(ii) oxide nanosheets synthesized by using a soft-templating procedure, with sulfur-addition based on hydrogen sulfide gas as a source. The resulting sulfur-functionalization does not change the overall crystal structure and morphology of the CuO nanosheets, but leads to a decrease in surface hydroxyl groups. Sulfur induces a semiconductor-to-conductor state transition of the CuO nanosheets, which is supported by computational modeling. The metallic transition results from shifting of the Fermi level into the valence band due to formation of Cu-S bonds on the surface of the CuO nanosheets.

Reactive Molecular Dynamics Simulations and Quantum Chemistry Calculations To Investigate Soot-Relevant Reaction Pathways for Hexylamine Isomers.

Sooting tendencies of a series of nitrogen-containing hydrocarbons (NHCs) have been recently characterized experimentally using the yield sooting index (YSI) methodology. This work aims to identify soot-relevant reaction pathways for three selected C6H15N amines, namely, dipropylamine (DPA), diisopropylamine (DIPA), and 3,3-dimethylbutylamine (DMBA) using ReaxFF molecular dynamics (MD) simulations and quantum mechanical (QM) calculations and to interpret the experimentally observed trends. ReaxFF MD simulations are performed to determine the important intermediate species and radicals involved in the fuel decomposition and soot formation processes. QM calculations are employed to extensively search for chemical reactions involving these species and radicals based on the ReaxFF MD results and also to quantitatively characterize the potential energy surfaces. Specifically, ReaxFF simulations are carried out in the NVT ensemble at 1400, 1600, and 1800 K, where soot has been identified to form in the YSI experiment. These simulations account for the interactions among test fuel molecules and pre-existing radicals and intermediate species generated from rich methane combustion, using a recently proposed simulation framework. ReaxFF simulations predict that the reactivity of the amines decrease in the order DIPA > DPA > DMBA, independent of temperature. Both QM calculations and ReaxFF simulations predict that C2H4, C3H6, and C4H8 are the main nonaromatic soot precursors formed during the decomposition of DPA, DIPA, and DMBA, respectively, and the associated reaction pathways are identified for each amine. Both theoretical methods predict that sooting tendency increases in the order DPA, DIPA, and DMBA, consistent with the experimentally measured trend in YSI. This work demonstrates that sooting tendencies and soot-relevant reaction pathways of fuels with unknown chemical kinetics can be identified efficiently through combined ReaxFF and QM simulations. Overall, predictions from ReaxFF simulations and QM calculations are consistent, in terms of fuel reactivity, major intermediates, and major nonaromatic soot precursors.

Performance-advantaged ether diesel bioblendstock production by a priori design.

Lignocellulosic biomass offers a renewable carbon source which can be anaerobically digested to produce short-chain carboxylic acids. Here, we assess fuel properties of oxygenates accessible from catalytic upgrading of these acids a priori for their potential to serve as diesel bioblendstocks. Ethers derived from C2 and C4 carboxylic acids are identified as advantaged fuel candidates with significantly improved ignition quality (>56% cetane number increase) and reduced sooting (>86% yield sooting index reduction) when compared to commercial petrodiesel. The prescreening process informed conversion pathway selection toward a C11 branched ether, 4-butoxyheptane, which showed promise for fuel performance and health- and safety-related attributes. A continuous, solvent-free production process was then developed using metal oxide acidic catalysts to provide improved thermal stability, water tolerance, and yields. Liter-scale production of 4-butoxyheptane enabled fuel property testing to confirm predicted fuel properties, while incorporation into petrodiesel at 20 vol % demonstrated 10% improvement in ignition quality and 20% reduction in intrinsic sooting tendency. Storage stability of the pure bioblendstock and 20 vol % blend was confirmed with a common fuel antioxidant, as was compatibility with elastomeric components within existing engine and fueling infrastructure. Technoeconomic analysis of the conversion process identified major cost drivers to guide further research and development. Life-cycle analysis determined the potential to reduce greenhouse gas emissions by 50 to 271% relative to petrodiesel, depending on treatment of coproducts.

Shape-Dependent Interactions of Manganese Oxide Nanomaterials with Lipid Bilayer Vesicles.

Interactions of transition-metal-oxide nanomaterials with biological membranes have important environmental implications and applications in ecotoxicity and life-cycle assessment analysis. In this study, we quantitatively assess the impact of MnO2 nanomaterial morphology-one-dimensional (1D) nanowires, 2D nanosheets, and 3D nanoflowers-on their interaction with phospholipid vesicles as a model for biological membranes. Confocal microscopy suggests visual evidence for the interaction of undisrupted vesicles with dispersed MnO2 nanomaterials of different morphologies, and it further supports the observation that minimal dye leakage of the vesicle inner solution was detected during the interaction with MnO2 nanomaterials during the dye leakage assay. Upon titration of vesicles to dispersions of MnO2 nanowires, nanosheets, and nanoflowers, each roughly 10 times larger than the vesicles, dynamic light scattering reveals two diffusive time scales associated with aggregates in the mixture. While the longer time scale corresponds to the dispersed MnO2 control population, the appearance of a shorter timescale with vesicle addition indicates interaction between the dispersed metal oxide nanomaterials and the vesicles. The interaction is shape-dependent, being more pronounced for MnO2 nanowires than for nanosheets and nanoflowers. Furthermore, the shorter diffusive time scale is intermediate between the vesicle and nanomaterial controls, which may suggest a degree of metal oxide aggregate breakup. Vesicle adsorption isotherms and zeta potential measurements during titration corroborate vesicle attachment on the nanomaterials. Our results suggest that the dispersed nanomaterial shape plays an important role in mediating nondestructive vesicle-nanomaterial interactions and that lipid vesicles act as efficient surfactants for MnO2 nanomaterials.

Catalytic manganese oxide nanostructures for the reverse water gas shift reaction.

Understanding the fundamental structure-property relationships of nanomaterials is critical for many catalytic applications as they comprise of the catalyst designing principles. Here, we develop efficient synthetic methods to prepare various MnO2 structures and investigate their catalytic performance as applied to the reverse Water Gas Shift (rWGS) reaction. We show that the support-free MnO derived from MnO2 1D, 2D and 3D nanostructures are highly selective (100% CO2 to CO), thermally stable catalysts (850 °C) and differently effective in the rWGS. Up to 50% conversion is observed, with a H2/CO2 feed-in ratio of 1 : 1. From both experiments and DFT calculations, we find the MnO2 morphology plays a critical role in governing the catalytic behaviors since it affects the predominant facets exposed under reaction conditions as well as the intercalation of K+ as a structural building block, substantially affecting the gas-solid interactions. The relative adsorption energy of reactant (CO2) and product (CO), ΔE = Eads(CO2) -Eads(CO), is found to correlate linearly with the catalytic activity, implying a structure-function relationship. The strong correlation found between Eads(CO2) -Eads(CO), or more generally, Eads(R) -Eads(P), and catalytic activity makes ΔE a useful descriptor for characterization of efficient catalysts involving gas-solid interactions beyond the rWGS.

A Promising Carbon/g-C3 N4 Composite Negative Electrode for a Long-Life Sodium-Ion Battery.

2D graphitic carbon nitride (g-C3 N4 ) nanosheets are a promising negative electrode candidate for sodium-ion batteries (NIBs) owing to its easy scalability, low cost, chemical stability, and potentially high rate capability. However, intrinsic g-C3 N4 exhibits poor electronic conductivity, low reversible Na-storage capacity, and insufficient cyclability. DFT calculations suggest that this could be due to a large Na+ ion diffusion barrier in the innate g-C3 N4 nanosheet. A facile one-pot heating of a mixture of low-cost urea and asphalt is strategically applied to yield stacked multilayer C/g-C3 N4 composites with improved Na-storage capacity (about 2 times higher than that of g-C3 N4 , up to 254 mAh g-1 ), rate capability, and cyclability. A C/g-C3 N4 sodium-ion full cell (in which sodium rhodizonate dibasic is used as the positive electrode) demonstrates high Coulombic efficiency (ca. 99.8 %) and a negligible capacity fading over 14 000 cycles at 1 A g-1 .

Highly conductive carbon-based aqueous inks toward electroluminescent devices, printed capacitive sensors and flexible wearable electronics.

Carbon-based conductive inks are one of the most important materials in the field of printing electronics. However, most carbon-based conductive inks with small electrical resistance are expensive, such as graphene. It limits the commercial use of carbon inks in the fields of flexible electronics and printed electronics. Here, we propose a low-cost and environmentally friendly formula based on dihydroxyphenyl-functionalized multi-walled carbon nanotubes (MWNT-f-OH)/carbon black/graphite as conductive fillers and waterborne acrylic resins as binders for preparing highly conductive carbon-based aqueous inks (HCCA-inks). Our study showed that when the mass fraction of carbon black, graphite and MWNT-f-OH was 3.0%, 10.2% and 4.1%, respectively, on a thickness of 40 µm, optimal conductivity (sheet resistance up to 29 Ω sq-1) was achieved, and the printed HCCA-inks on a paper could withstand extremely high folding cycles (>2000 cycles) while the resistance value of the flexible circuit only increased by 11%. The carbon-based aqueous inks showed high electrical conductivity and excellent mechanical stability, which makes it possible for them to be used as flexible wearable electronics, electroluminescent (EL) devices and printed capacitive sensors.

Hydrophobic CuO Nanosheets Functionalized with Organic Adsorbates.

A new class of hydrophobic CuO nanosheets is introduced by functionalization of the cupric oxide surface with p-xylene, toluene, hexane, methylcyclohexane, and chlorobenzene. The resulting nanosheets exhibit a wide range of contact angles from 146° (p-xylene) to 27° (chlorobenzene) due to significant changes in surface composition induced by functionalization, as revealed by XPS and ATR-FTIR spectroscopies and computational modeling. Aromatic adsorbates are stable even up to 250-350 °C since they covalently bind to the surface as alkoxides, upon reaction with the surface as shown by DFT calculations and FTIR and 1H NMR spectroscopy. The resulting hydrophobicity correlates with H2 temperature-programmed reduction (H2-TPR) stability, which therefore provides a practical gauge of hydrophobicity.

Hard templating ultrathin polycrystalline hematite nanosheets: effect of nano-dimension on CO2 to CO conversion via the reverse water-gas shift reaction.

Understanding how nano-dimensionality impacts iron oxide based catalysis is central to a wide range of applications. Here, we focus on hematite nanosheets, nanowires and nanoparticles as applied to catalyze the reverse water gas shift (RWGS) probe reaction. We introduce a novel approach to synthesize ultrathin (4-7 nm) hematite nanosheets using copper oxide nanosheets as a hard template and propose a reaction mechanism based on density functional theory (DFT) calculations. Hematite nanowires and nanoparticles were also synthesized and characterized. H2 temperature programmed reduction (H2-TPR) and RWGS reactions were performed to glean insights into the mechanism of CO2 conversion to CO over the iron oxide nanomaterials and were compared to H2 binding energy calculations based on density functional theory. While the nanosheets did exhibit high CO2 conversion, 28% at 510 °C, we found that the iron oxide nanowires had the highest CO2 conversion, reaching 50% at 750 °C under atmospheric pressure. No products besides CO and H2O were detected.

Fundamental Role of Oxygen Stoichiometry in Controlling the Band Gap and Reactivity of Cupric Oxide Nanosheets.

CuO is a nonhazardous, earth-abundant material that has exciting potential for use in solar cells, photocatalysis, and other optoelectronic applications. While progress has been made on the characterization of properties and reactivity of CuO, there remains significant controversy on how to control the precise band gap by tuning conditions of synthetic methods. Here, we combine experimental and theoretical methods to address the origin of the wide distribution of reported band gaps for CuO nanosheets. We establish reaction conditions to control the band gap and reactivity via a high-temperature treatment in an oxygen-rich environment. SEM, TEM, XRD, and BET physisorption reveals little to no change in nanostructure, crystal structure, or surface area. In contrast, UV-vis spectroscopy shows a modulation in the material band gap over a range of 330 meV. A similar trend is found in H2 temperature-programmed reduction where peak H2 consumption temperature decreases with treatment. Calculations of the density of states show that increasing the oxygen to copper coverage ratio of the surface accounts for most of the observed changes in the band gap. An oxygen exchange mechanism, supported by (18)O2 temperature-programmed oxidation, is proposed to be responsible for changes in the CuO nanosheet oxygen to copper stoichiometry. The changes induced by oxygen depletion/deposition serve to explain discrepancies in the band gap of CuO, as reported in the literature, as well as dramatic differences in catalytic performance.

Shape-Dependent Surface Reactivity and Antimicrobial Activity of Nano-Cupric Oxide.

Shape of engineered nanomaterials (ENMs) can be used as a design handle to achieve controlled manipulation of physicochemical properties. This tailored material property approach necessitates the establishment of relationships between specific ENM properties that result from such manipulations (e.g., surface area, reactivity, or charge) and the observed trend in behavior, from both a functional performance and hazard perspective. In this study, these structure-property-function (SPF) and structure-property-hazard (SPH) relationships are established for nano-cupric oxide (n-CuO) as a function of shape, including nanospheres and nanosheets. In addition to comparing these shapes at the nanoscale, bulk CuO is studied to compare across length scales. The results from comprehensive material characterization revealed correlations between CuO surface reactivity and bacterial toxicity with CuO nanosheets having the highest surface reactivity, electrochemical activity, and antimicrobial activity. While less active than the nanosheets, CuO nanoparticles (sphere-like shape) demonstrated enhanced reactivity compared to the bulk CuO. This is in agreement with previous studies investigating differences across length-scales. To elucidate the underlying mechanisms of action to further explain the shape-dependent behavior, kinetic models applied to the toxicity data. In addition to revealing different CuO material kinetics, trends in observed response cannot be explained by surface area alone. The compiled results contribute to further elucidate pathways toward controlled design of ENMs.

Highly conductive single-walled carbon nanotube thin film preparation by direct alignment on substrates from water dispersions.

A safe, scalable method for producing highly conductive aligned films of single-walled carbon nanotubes (SWNTs) from water suspensions is presented. While microfluidic assembly of SWNTs has received significant attention, achieving desirable SWNT dispersion and morphology in fluids without an insulating surfactant or toxic superacid is challenging. We present a method that uniquely produces a noncorrosive ink that can be directly applied to a device in situ, which is different from previous fabrication techniques. Functionalized SWNTs (f-SWNTs) are dispersed in an aqueous urea solution to leverage binding between the amine group of urea and the carboxylic acid group of f-SWNTs and obtain urea-SWNT. Compared with SWNTs dispersed using conventional methods (e.g., superacid and surfactants), the dispersed urea-SWNT aggregates have a higher aspect ratio with a rodlike morphology as measured by light scattering. The Mayer rod technique is used to prepare urea-SWNT, highly aligned films (two-dimensional nematic order parameter of 0.6, 5 µm spot size, via polarized Raman) with resistance values as low as 15-1700 Ω/sq in a transmittance range of 2-80% at 550 nm. These values compete with the best literature values for conductivity of SWNT-enabled thin films. The findings offer promising opportunities for industrial applications relying on highly conductive thin SWNT films.

A carbon nanotube-polymer composite for T-cell therapy.

Clinical translation of cell therapies requires strategies that can manufacture cells efficiently and economically. One promising way to reproducibly expand T cells for cancer therapy is by attaching the stimuli for T cells onto artificial substrates with high surface area. Here, we show that a carbon nanotube-polymer composite can act as an artificial antigen-presenting cell to efficiently expand the number of T cells isolated from mice. We attach antigens onto bundled carbon nanotubes and combined this complex with polymer nanoparticles containing magnetite and the T-cell growth factor interleukin-2 (IL-2). The number of T cells obtained was comparable to clinical standards using a thousand-fold less soluble IL-2. T cells obtained from this expansion were able to delay tumour growth in a murine model for melanoma. Our results show that this composite is a useful platform for generating large numbers of cytotoxic T cells for cancer immunotherapy.