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.     

Methyl methacrylate polymerization initiated by triethylborane–peroxide mixtures

The polymerization of methyl methacrylate initiated by triethylborane or triethylborane–peroxide mixtures was studied. The rate of initiation by a mixture of triethylborane and tert-butyl peroxide was found to be first-order in peroxide. The order in triethylborane changes from one at low triethylborane/peroxide to nearly zero at high triethylborane/peroxide. The possibility of a mechanism involving a fast reaction followed by a slow reaction that would initiate the polymerization is discussed.     

Are covering (enveloping) morphisms minimal?

We prove that for certain classes of modules such that direct sums of -covers ( -envelopes) are -covers ( -envelopes), -covering ( -enveloping) homomorphisms are always right (left) minimal. As a particular case we see that over noetherian rings, essential monomorphisms are left minimal. The same type of results are given when direct products of -covers are -covers. Finally we prove that over commutative noetherian rings, any direct product of flat covers of modules of finite length is a flat cover.     

Theoretical study of neutral and protonated triple bonded molecules formed between C, N, Si, P, B and Al

A theoretical study of the possible protonation sites of simple molecules formed by C, N, Si, P, B and Al that present a triple bond between those atoms has been carried out. The calculations performed include MP2 and CCSD(T) methods with the aug-cc-pVTZ basis set. The nature of the protonated species has been analyzed with the Atoms In Molecules methodology. To Serafin, a free spirit and a good friend. Contribution to the Serafin Fraga Memorial Issue.     

Exploring the structural and electronic properties of nitrogen-containing exohydrogenated carbon nanotubes: a quantum chemistry study

Saturated nanotubes consisting of 2–10 and 20 layers of cyclic units of six-membered rings, each one having a pyrimidine-like framework (i.e., –C–C–C–N–C–N–), were studied by quantum chemistry methods using Density Functional Theory (DFT) at the B3LYP/6-31G* level of theory. Four different nanotube (NT) configurations were theoretically studied in this work. They were formed by covalently arranging each layer over the other, with uniform relative rotations of 0°, 60°, 120°, and 180° with respect to each of the layers. Different structures can be created by modulating the relative rotation as layers are added to the main nanostructure. NTs with a relative rotation of 60° showed both greater stabilities and highest potential for catalytic activity. All of them showed band gaps of around 0.2 eV. Charges and other properties can be controlled by appropriate layer arrangement. The studied families of NTs have a very small diameter and could find potential applications in chemistry, physics, and medicine.     

Stereoisomer discrimination in complexes of halogen-substituted difuranes and Li or Na cations

The theoretical study of the stereoisomer discrimination of the 2:1 homo- and heterochiral complexes between chiral 5,5'-dihalogen bifuranes and lithium or sodium cations has been carried out using DFT methods. To understand the chiral effect produced by the introduction of a second bifurane molecule, the 1:1 complexes also have been calculated. All the 2:1 heterochiral complexes computed showed a nonplanar configuration around the metallic cation, but in the case of the homochiral complexes, the dibromo- and dichloro-bifurane systems around Na+ were quasi-planar. The nature of the interactions established between cations and bifurane systems has been analyzed by means of AIM and NBO, and correlations between the electron density topological parameters with the O...M distance and with the orbital interaction energy have been found. Stereodiscrimination is observed favoring the heterochiral complexes except for the Na+ complexes with chloro and bromo substituents in which the homochiral forms are more stable. Stereodiscrimination values correlate with the difference in electron density at the bond critical point and orbital interaction energy between homo- and heterochiral systems.     

Rugged modules: The opposite of flatness

Relative notions of flatness are introduced as a mean to gauge the extent of the flatness of any given module. Every module is thus endowed with a flatness domain and, for every ring, the collection of flatness domains of all of its modules is a lattice with respect to class inclusion. This lattice, the flatness profile of the ring, allows us, in particular, to focus on modules which have a smallest flatness domain (namely, one consisting of all regular modules.) We establish that such modules exist over arbitrary rings and we call them Rugged Modules. Rings all of whose (cyclic) modules are rugged are shown to be precisely the von Neumann regular rings. We consider rings without a flatness middle class (i.e., rings for which modules must be either flat or rugged.) We obtain that, over a right Noetherian ring every left module is rugged or flat if and only if every right module is poor or injective if and only if R = S×T, where S is semisimple Artinian and T is either Morita equivalent to a right PCI-domain, or T is right Artinian whose Jacobson radical properly contains no nonzero ideals. Character modules serve to bridge results about flatness and injectivity profiles; in particular, connections between rugged and poor modules are explored. If R is a ring whose regular left modules are semisimple, then a right module M is rugged if and only if its character left module M⁺ is poor. Rugged Abelian groups are fully characterized and shown to coincide precisely with injectively poor and projectively poor Abelian groups. Also, in order to get a feel for the class of rugged modules over an arbitrary ring, we consider the homological ubiquity of rugged modules in the category of all modules in terms of the feasibility of rugged precovers and covers for arbitrary modules.     

Covering morphisms

Let (R, m) be a two-dimensional regular local ring and let A be a finitely generated torsion-free R-module. If A is a complete module, then Dan Katz and Vijay Kodiyalam show A satisfies five conditions. They ask whether these five conditions are equivalent without assuming A to be complete. In a previous paper we determined all implications among these five conditions with one exception. In this paper, with an additional hypothesis on the units of R, we resolve the remaining case.     

Molecular dynamics assessment of doxorubicin–carbon nanotubes molecular interactions for the design of drug delivery systems

Carbon nanotubes (CNTs) constitute an interesting material for nanomedicine applications because of their unique properties, especially their ability to penetrate membranes, to transport drugs specifically and to be easily functionalized. In this work, the energies of the intermolecular interactions of single-walled CNTs and the anticancer drug doxorubicin (DOX) were determined using the AMBER 12 molecular dynamics MM/PBSA and MM/GBSA methods with the aim of better understanding how the structural parameters of the nanotube can improve the interactions with the drug and to determine which structural parameters are more important for increasing the stability of the complexes formed between the CNTs and DOX. The armchair, zigzag, and chiral nanotubes were finite hydrogen-terminated open tubes, and the DOX was encapsulated inside the tube or adsorbed on the nanotube surface. Pentagon/heptagon bumpy defects and polyethylene glycol (PEG) nanotube functionalization were also studied. The best interaction occurred when the drug was located inside the cavity of the nanotube. Armchair and zigzag nanotubes doped with nitrogen, favored interaction with the drug, whereas chiral nanotubes exhibited better drug interactions when having bumpy defects. The π-π stacking and N-H…π electrostatic interactions were important components of the attractive drug-nanotube forces, enabling significant flattening of the nanotube to favor a dual strong interaction with the encapsulated drug, with DOX–CNT equilibrium distances of 3.1–3.9 Å. These results can contribute to the modeling of new drug-nanotube delivery systems.