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.     

Gutmann's Donor Numbers Correctly Assess the Effect of the Solvent on the Kinetics of SNAr Reactions in Ionic Liquids

We report an experimental study on the effect of solvents on the model S_NAr reaction between 1‐chloro‐2,4‐dinitrobenzene and morpholine in a series of pure ionic liquids (IL). A significant catalytic effect is observed with reference to the same reaction run in water, acetonitrile, and other conventional solvents. The series of IL considered include the anions, NTf₂^?, DCN^?, SCN^?, CF₃SO₃^?, PF₆^?, and FAP^? with the series of cations 1‐butyl‐3‐methyl‐imidazolium ([BMIM]⁺), 1‐ethyl‐3‐methyl‐imidazolium ([EMIM]⁺), 1‐butyl‐2,3‐dimethyl‐imidazolium ([BM₂IM]⁺), and 1‐butyl‐1‐methyl‐pyrrolidinium ([BMPyr]⁺). The observed solvent effects can be attributed to an “anion effect”. The anion effect appears related to the anion size (polarizability) and their hydrogen‐bonding (HB) abilities to the substrate. These results have been confirmed by performing a comparison of the rate constants with Gutmann's donicity numbers (DNs). The good correlation between rate constants and DN emphasizes the major role of charge transfer from the anion to the substrate.     

Exo conformers of N‐(pyridin‐2‐yl)‐ and N‐(pyridin‐3‐yl)norbornene‐5,6‐dicarboximide crystals

Two isomeric pyridine‐substituted norbornenedicarboximide derivatives, namely N‐(pyridin‐2‐yl)‐exo‐norbornene‐5,6‐dicarboximide, (I), and N‐(pyridin‐3‐yl)‐exo‐norbornene‐5,6‐dicarboximide, (II), both C₁₄H₁₂N₂O₄, have been crystallized and their structures unequivocally determined by single‐crystal X‐ray diffraction. The molecules consist of norbornene moieties fused to a dicarboximide ring substituted at the N atom by either pyridin‐2‐yl or pyridin‐3‐yl in an anti configuration with respect to the double bond, thus affording exo isomers. In both compounds, the asymmetric unit consists of two independent molecules (Z′ = 2). In compound (I), the pyridine rings of the two independent molecules adopt different conformations, i.e. syn and anti, with respect to the methylene bridge. The intermolecular contacts of (I) are dominated by C—H...O interactions. In contrast, in compound (II), the pyridine rings of both molecules have an anti conformation and the two independent molecules are linked by carbonyl–carbonyl interactions, as well as by C—H...O and C—H...N contacts.     

Radical-Mediated Photocatalysis for Lignocellulosic Biomass Conversion into Value-Added Chemicals and Hydrogen: Facts,Opportunities and Challenges

Photocatalytic biomass conversion into high-value chemicals and fuels is considered one of the hottest ongoing research and industrial topics toward sustainable development. In short, this process can cleave C_β−O/C_α−C_β bonds in lignin to aromatic platform chemicals, and further conversion of the polysaccharides to other platform chemicals and H₂. From the chemistry point of view, the optimization of the unique cooperative interplay of radical oxidation species (which are activated via molecular oxygen species, ROSs) and substrate-derived radical intermediates by appropriate control of their type and/or yield is key to the selective production of desired products. Technically, several challenges have been raised that face successful real-world applications. This review aims to discuss the recently reported mechanistic pathways toward selective biomass conversion through the optimization of ROSs behavior and materials/system design. On top of that, through a SWOT analysis, we critically discussed this technology from both chemistry and technological viewpoints to help the scientists and engineers bridge the gap between lab-scale and large-scale production.     

Temperature spectra from a turbulent thermal plume by ultrasound scattering

This paper reports the results of a study on temperature inhomogeneities conducted on a thermal plume by using ultrasound scattering as a non-intrusive measurement technique. The plume rises from a metallic disk which can be heated up to 800 °C. The working fluid is air at atmospheric pressure. In the measurement technique, an incoming ultrasound wave is emitted towards the thermal plume. The incident wave is scattered because of non-linear couplings with the flow instabilities present in the measurement region. The scattered wave carries information about those flow instabilities. The technique allows for the retrieving of this information. The shape of the obtained spectrum of temperature fluctuations as a function of wave vector modulus is consistent with previous theoretical analysis. Three qualitatively different regions were identified: first, a production region characterized by a q² law; secondly, a region with behavior as per q⁻³ associated with a buoyancy region and; finally, a dissipation region associated with a q⁻⁷ law. These spectral regions characterize the energy transfers mechanisms among the length scales of flow investigated here. A coefficient of anisotropy γ was defined to analyze anisotropic features of the flow.     

On the accuracy of a nonlinear finite volume method for the solution of diffusion problems using different interpolations strategies

In this paper, we consider a nonlinear finite volume method to solve the steady‐state diffusion equation in nonhomogeneous and non‐isotropic media. The method is nonlinear even if the original problem is linear. In its original form, the scheme is monotone, because the coefficient matrix is monotone under certain assumptions and, as a consequence, whenever the analytic operator demands, it preserves the positivity of numerical solutions. On the other hand, the scheme is unable to reproduce piecewise linear solutions exactly. In order to recover this interesting feature, we use two different interpolation strategies. In this case, even though we are unable to prove monotonicity, we show some numerical evidences that the combined method has an improved behavior, producing second order accurate solutions, even for nonhomogeneous and strongly anisotropic media. Copyright © 2013 John Wiley & Sons, Ltd.     

Aspects of spin-orbit effects in compounds containing heavy elements

This perspective article discusses some widely-known and some less-known consequences of spin-orbit effects in inorganic chemistry, and provides a brief outline of the theoretical methods currently in use, along with a discussion of recent developments and selected applications. This is of critical importance in the interpretation of the electronic delocalization, optical and magnetic properties and Jahn–Teller effects of compounds containing heavy elements.     

Probing Substrate/Catalyst Effects Using QSPR Analysis on Friedel-Crafts Acylation Reactions over Hierarchical BEA Zeolites

Attempts to optimize heterogeneous catalysis often lack quantitative comparative analysis. The use of kinetic modelling leads to rate (k) and relative sorption equilibrium constants (K), which can be further rationalized using Quantitative Structure-Property Relationships (QSPR) based on Multiple Linear Regressions (MLR). Friedel-Crafts acylation using commercial and hierarchical BEA zeolites as heterogeneous catalysts, acetic anhydride as the acylating agent, and a set of seven substrates with different sizes and chemical functionalities were herein studied. Catalytic results were correlated with the physicochemical properties of substrates and catalysts. From this analysis, a robust set of equations was obtained allowing inferences about the dominant factors governing the processes. Not entirely surprising, the rate and sorption equilibrium constants were found to be explained in part by common factors but of opposite signs: higher and stronger adsorption forces increase reaction rates, but they also make the zeolite active sites less accessible to new reactant molecules. The most relevant parameters are related to the substrates’ molecular size, which can be associated with different reaction steps, namely accessibility to micropores, diffusion capacity, and polarizability of molecules. The relatively large set of substrates used here reinforces previous findings and brings further insights into the factors that hamper/speed up Friedel-Crafts reactions in heterogeneous media.