Doxorubicin Encapsulation in Carbon Nanotubes Having Haeckelite or Stone–Wales Defects as Drug Carriers: A Molecular Dynamics Approach

Doxorubicin (DOX), a recognized anticancer drug, forms stable associations with carbon nanotubes (CNTs). CNTs when properly functionalized have the ability to anchor directly in cancerous tumors where the release of the drug occurs thanks to the tumor slightly acidic pH. Herein, we study the armchair and zigzag CNTs with Stone–Wales (SW) defects to rank their ability to encapsulate DOX by determining the DOX-CNT binding free energies using the MM/PBSA and MM/GBSA methods implemented in AMBER16. We investigate also the chiral CNTs with haeckelite defects. Each haeckelite defect consists of a pair of square and octagonal rings. The armchair and zigzag CNT with SW defects and chiral nanotubes with haeckelite defects predict DOX-CNT interactions that depend on the length of the nanotube, the number of present defects and nitrogen doping. Chiral nanotubes having two haeckelite defects reveal a clear dependence on the nitrogen content with DOX-CNT interaction forces decreasing in the order 0N > 4N > 8N. These results contribute to a further understanding of drug-nanotube interactions and to the design of new drug delivery systems based on CNTs.     

Surface Polymers on Multiwalled Carbon Nanotubes for Selective Extraction and Electrochemical Determination of Rhodamine B in Food Samples

In this study, we combine magnetic solid phase extraction (MSPE), with the screen-printed carbon electrode (SPCE) modified by a molecular imprinted polymer (MIP) for sensitive and selective extraction and electrochemical determination of Rhodamine B in food samples. A magnetic solid phase extraction (MSPE) was carried out using magnetic poly(styrene-co-divinylbenzene) (PS-DVB) and magnetic nanoparticles (MNPs) synthetized on the surface of multiwalled carbon nanotubes (MWCNTs). An MIP was prepared on the surface of MWCNTs in the presence of titanium oxide nanoparticles (TiO₂NPs) modifying the SPCE for the rapid electrochemical detection of Rhodamine B. The MIPs synthesis was optimized by varying the activated titanium oxide (TiO₂) and multiwalled carbon nanotubes (MWCNTs) amounts. The MSPE and electrochemical detection conditions were optimized as well. The present method exhibited good selectivity, high sensitivity, and good reproducibility towards the determination of Rhodamine B, making it a suitable method for the determination of Rhodamine B in food samples.     

The green synthesis of exceptional braided,helical carbon nanotubes and nanospiral platelets made directly from CO2

Helical carbon nanotubes currently cost ~15,000–19,000 USD/kg commercially and are ~10–15 times the price of straight carbon nanotubes of similar dimensions. They have not previously been made from the greenhouse gas CO₂ nor had new variants of the helical morphology been demonstrated. In this study, a novel, inexpensive electrosynthesis of these helical nanocarbon materials from CO₂ is presented. This material may be produced by molten carbon growth conditions that (1) maximize torsional stresses, such as those that may occur during rapid, nucleated carbon reduction, (2) enhance defects that cause formation of heptagonal, rather than the conventional hexagonal building blocks of graphene cylindrical walls, and (3) uniformly control those enhanced defects to repeatedly induce a uniform spiral conformation. These conditions are achieved with at least two of the following experimental conditions: (i) high electrolysis current density, (ii) sp³ defect-inducing agents, such as added oxide, and (iii) controlled concentration of iron added to the electrolyte or cathode. Here, it is shown with SEM, TEM, EDX, XRF, and Raman spectroscopy that a molten controlled electrolyte carbonate synthesis to induce defect formation, and a high rate of electrolysis (0.6 A/cm²) leads to a high yield of helical nanotubes, helical nanofibers, or helical nanoplatelet carbon morphologies.     

g-C3N4催化石墨化碳质材料的制备及光催化性能研究

通常采用以氢氧化物作为造孔剂,过渡金属硝酸盐或氯化物作为石墨化催化剂的传统两步法策略制备多孔石墨化碳材料。然而制备过程中多涉及有毒和腐蚀性试剂,且多步骤的过程耗时较长。本文以双氰胺为原料通过热缩聚反应得到g-C₃N₄,采用高铁酸钾为催化剂一步法实现g-C₃N₄的同步碳化-石墨化,并研究其光催化性能。与传统的两步法相比,该方法耗时少、效率高、无污染。与初始的g-C₃N₄材料相比,石墨化g-C₃N₄衍生碳质材料不仅显著改善了可见光的吸收,而且大大增强了光催化活性。研究了不同石墨化温度对g-C₃N₄衍生碳质材料在可见光下降解甲基橙溶液的影响。700 ℃下制备的衍生碳质材料的降解率为12.4 mg/g。光电化学测试结果表明,多孔g-C₃N₄衍生碳质材料的光生载流子密度、电荷分离和光电流(提高了5.4倍)均得到显著提高。因此,该简便、灵活方法为提高g-C₃N₄衍生碳质材料的吸附和光催化性能提供了一种有前景的、高效的途径。     

On the mechanism of microporous carbon supercapacitors

Microporous carbon shows the highest supercapacitor performance among other carbon nanomaterials, and thus, is considered as the most promising candidate for the fabrication of high-performance supercapacitors. However, it has puzzled the researchers as micropores do not have enough space for the formation of the so-called double layer. Several models have been proposed to explain the mechanism of energy storage by microporous supercapacitors. The most common one is that the micropores are initially filled by both anions and cations, and charging/discharging is via ion-exchange through these single row-filled micropores. Although this theory has been supported by several computational calculations, it is discussed here that this model is in disagreement with the experimental facts commonly accepted in the literature.     

Molecularly engineering polymeric membranes for H2/CO2 separation at 100–300 °C

Over the last two decades, polymers with superior H₂/CO₂ separation properties at 100–300 °C have gathered significant interest for H₂ purification and CO₂ capture. This timely review presents various strategies adopted to molecularly engineer polymers for this application. We first elucidate the Robeson's upper bound at elevated temperatures for H₂/CO₂ separation and the advantages of high-temperature operation (such as improved solubility selectivity and absence of CO₂ plasticization), compared with conventional membrane gas separations at ~35 °C. Second, we describe commercially relevant membranes for the separation and highlight materials with free volumes tuned to discriminate H₂ and CO₂, including functional polymers (such as polybenzimidazole) and engineered polymers by cross-linking, blending, thermal treatment, thermal rearrangement, and carbonization. Third, we succinctly discuss mixed matrix materials containing size-sieving or H₂-sorptive nanofillers with attractive H₂/CO₂ separation properties.     

Structure and gas transport characteristics of triethylene oxide-grafted polystyrene-b-poly(ethylene-co-butylene)-b-polystyrene

Polymeric membrane-based gas separation technology has significant advantages compared with traditional amine-based CO₂ separation method. In this work, SEBS block copolymer is used as a polymer matrix to incorporate triethylene oxide (TEO) functionality. The short ethylene oxide segment is chosen to avoid crystallization, which is confirmed by differential scanning calorimetry and wide-angle X-ray scattering characterizations. The gas permeability results reveal that CO₂/N₂ selectivity increased with increasing content of TEO functional group. The highest CO₂ permeability (281 Barrer) and CO₂/N₂ selectivity (31) were obtained for the membrane with the highest TEO incorporation (57 mol%). Increasing the TEO content in these copolymers results in an increase in CO₂ solubility and a decrease in C₂H₆ solubility. For example, as the grafted TEO content increased from 0 to 57 mol%, the CO₂ solubility and CO₂/C₂H₆ solubility selectivity increased from 0.72 to 1.3 cm³(STP)/cm³ atm and 0.47 to 1.3 at 35°C, respectively. The polar ether linkage in TEO-grafted SEBS copolymers exhibits favorable interaction with CO₂ and unfavorable interaction with nonpolar C₂H₆, thus enhancing CO₂/C₂H₆ solubility selectivity.     

Hierarchical Mn3O4 Anchored on 3D Graphene Aerogels via C−O−Mn Linkage with Superior Electrochemical Performance for Flexible Asymmetric Supercapacitor

Flexible asymmetric supercapacitors are more appealing in flexible electronics because of high power density, wide cell voltage, and higher energy density than symmetric supercapacitors in aqueous electrolyte. In virtues of excellent conductivity, rich porous structure and interconnected honeycomb structure, three dimensional graphene aerogels show great potential as electrode in asymmetric supercapacitors. However, graphene aerogels are rarely used in flexible asymmetric supercapacitors because of easily re-stacking of graphene sheets, resulting in low electrochemical activity. Herein, flower-like hierarchical Mn₃O₄ and carbon nanohorns are incorporated into three dimensional graphene aerogels to restrain the stack of graphene sheets, and are applied as the positive and negative electrode for asymmetric supercapacitors devices, respectively. Besides, a strong chemical coupling between Mn₃O₄ and graphene via the C-O-Mn linkage is constructed and can provide a good electron-transport pathway during cycles. Consequently, the asymmetric supercapacitor device shows high rate cycle stability (87.8 % after 5000 cycles) and achieves a high energy density of 17.4 μWh cm⁻² with power density of 14.1 mW cm⁻² (156.7 mW cm⁻³) at 1.4 V.     

Platinum Oxide Nanoparticles for Electrochemical Hydrogen Evolution: Influence of Platinum Valence State

Electrochemical hydrogen generation is a rising prospect for future renewable energy storage and conversion. Platinum remains a leading choice of catalyst, but because of its high cost and low natural abundance, it is critical to optimize its use. In the present study, platinum oxide nanoparticles of approximately 2 nm in diameter are deposited on carbon nitride (C3N4) nanosheets by thermal refluxing of C3N4 and PtCl₂ or PtCl₄ in water. These nanoparticles exhibit apparent electrocatalytic activity toward the hydrogen evolution reaction (HER) in acid. Interestingly, the HER activity increases with increasing Pt⁴⁺ concentration in the nanoparticles, and the optimized catalyst even outperforms commercial Pt/C, exhibiting an overpotential of only −7.7 mV to reach the current density of 10 mA cm⁻² and a Tafel slope of −26.3 mV dec⁻¹. The results from this study suggest that the future design of platinum oxide catalysts should strive to maximize the Pt⁴⁺ sites and minimize the formation of the less active Pt²⁺ species.     

Synthesis and Systematic Structural Analysis of Cationic Half-Sandwich Ruthenium Chalcogenocarbonyl Complexes

Although the chemistry of transition-metal complexes with carbonyl (CO) and thiocarbonyl (CS) ligands has been well developed, their heavier analogues, namely selenocarbonyl (CSe) and tellurocarbonyl (CTe) complexes remain scarce. The limited availability of such CSe and CTe complexes has so far hampered our understanding of the differences between such chalcogenocarbonyl (CE: E=O, S, Se, Te) ligands. Herein, we report the synthesis and properties of a series of cationic half-sandwich ruthenium CE complexes of the type [CpRu(CE)(H₂IMes)(CNCH₂Ts)][BAr^F₄] (Cp=η⁵-C₅H₅⁻; H₂IMes=1,3-dimesitylimidazolin-2-ylidene; Ar^F=3,5-(CF₃)₂C₆H₃). A combination of X-ray diffraction analyses, NMR spectroscopic analyses, and DFT calculations revealed an increasing π-accepting ability of the CE ligands in the order O<S<Se<Te. A variable-temperature NMR analysis of the thus obtained chiral-at-metal CE complexes indicated high stereochemical stability.