Supramolecular [60]fullerene chemistry on surfaces

This critical review documents the exceptional range of research avenues in [60]fullerene-based monolayers showing unique and spectacular physicochemical properties which prompted such materials to have potential applications in several directions, ranging from sensors and photovoltaic cells to nanostructured devices for advanced electronic applications, that have been pursued during the past decade. It illustrates how progress in covalent [60]fullerene functionalisation led to the development of spectacular surface-immobilised architectures, including dyads and triads for photoinduced electron and energy transfer, self-assembled on a wide variety of surfaces. All of these molecular assemblies and supramolecular arrays feature distinct properties as a consequence of the presence of different molecular units and their spatial arrangement. Since the properties of [60]fullerene-containing films are profoundly controlled by the deposition conditions, substrate of adsorption, and influenced by impurities or disordered surface structures, the progress of such new [60]fullerene-based materials strongly relies on the development of new versatile and broad preparative methodologies. Therefore, the systematic exploration of the most common approaches to prepare and characterise [60]fullerene-containing monolayers embedded into two- or three-dimensional networks will be reviewed in great detail together with their main limitations. Recent investigations hinting at potential technological applications addressing many important fundamental issues, such as a better understanding of interfacial electron transfer, ion transport in thin films, photovoltaic devices and the dynamics associated with monolayer self-assembly, are also highlighted.     

Solvent-dependent host–guest complexation of two homologous merocyanines by a water-soluble calix[8]arene: Spectroscopic analysis and structural calculations

The sulfonated calixarene I₈C₁₂ acts as a host for homologous merocyanines Mc1 and Mc2 in organic solvents, exhibiting neither selectivity towards the guest dyes nor solvent dependence of the complexation equilibria. In water, on the contrary, only the lower homologue, Mc1, is solubilized in the presence of the calixarene. A combination of UV–visible and fluorescence spectroscopic and photophysical analysis and MD structural simulation of the calixarene-dye complexes was employed to account for the observations, and suggests that a radical change in the complexation mode occurs upon moving from an organic to an aqueous environment.     

Rapid access to 3-(N-substituted)-aminoquinolin-2(1H)-ones using palladium-catalyzed C-N bond coupling reaction

A series of 3-(N-substituted)-aminoquinolin-2(1H)-ones have been synthesized by the palladium-catalyzed C-N coupling reaction starting from 3-bromoquinolin-2-(1H)-ones. Various nucleophiles including amines, amides, sulfonamides, carbamates and ureas have been used successfully. In all the cases, the reactions take place rapidly in 1,4-dioxane and proceed in good to excellent yield using palladium acetate as a catalyst, Xantphos as a ligand and Cs₂CO₃ as a base.     

Oxytetracycline as environmental contaminant in arable lands

Oxytetracycline (OXY) is a broad-range antimicrobial routinely used in pig production, at doses in the range of few g/kg of medicated feed, during the weaning period. It could persist at ppm level in pig liquid manure that routinely is used for organic fertilisation. In the present work we describe a methodology to study OXY environmental fate in arable land where crops are cultivated for animal feeding purposes. A liquid-liquid extraction followed by metal chelate affinity chromatography was applied to environmental samples of manures and soils drawn within a case-control study. Extracts were then analysed by high performance liquid chromatography with UV/DAD detection, using a reverse phase column, and expressing the results as 4-epioxytetracycline epimer. Results indicate OXY is well retained at mg kg(-1) levels in soil exposed to contaminated pig manure fertilisation. Such compartment could constitute an abiotic reservoir for the systemic and/or for the external contamination of corn.     

Attempted Oxidative Deamination of N-Deacetylcolchicinoids with 3,5-Di(tert-butyl)-1,2-benzoquinone: Synthesis of 2H-1,4-Benzoxazine-Type Adducts

In an attempt to use 3,5-di(tert-butyl)-1,2-benzoquinone for the oxidative deamination of N-deacetylcolchicine ( 4 ) and N-deacetylthiocolchicine (=N-deacetyl-10-demethoxy-10-(methylthio)colchicine; 5 ) to give the corresponding ketones 2 and 3 , the 2H-1,4-benzoxazine-type adducts 8 / 9 and 11 / 12 , respectively, were formed instead, showing a new and unexpected behavior of Corey's reagent. The adducts were separated and spectroscopically characterized, and a plausible scheme of formation is reported.     

Binding and condensation of plasmid DNA onto functionalized carbon nanotubes: toward the construction of nanotube-based gene delivery vectors

Carbon nanotubes (CNTs) constitute a class of nanomaterials that possess characteristics suitable for a variety of possible applications. Their compatibility with aqueous environments has been made possible by the chemical functionalization of their surface, allowing for exploration of their interactions with biological components including mammalian cells. Functionalized CNTs (f-CNTs) are being intensively explored in advanced biotechnological applications ranging from molecular biosensors to cellular growth substrates. We have been exploring the potential of f-CNTs as delivery vehicles of biologically active molecules in view of possible biomedical applications, including vaccination and gene delivery. Recently we reported the capability of ammonium-functionalized single-walled CNTs to penetrate human and murine cells and facilitate the delivery of plasmid DNA leading to expression of marker genes. To optimize f-CNTs as gene delivery vehicles, it is essential to characterize their interactions with DNA. In the present report, we study the interactions of three types of f-CNTs, ammonium-functionalized single-walled and multiwalled carbon nanotubes (SWNT-NH3+; MWNT-NH3+), and lysine-functionalized single-walled carbon nanotubes (SWNT-Lys-NH3+), with plasmid DNA. Nanotube-DNA complexes were analyzed by scanning electron microscopy, surface plasmon resonance, PicoGreen dye exclusion, and agarose gel shift assay. The results indicate that all three types of cationic carbon nanotubes are able to condense DNA to varying degrees, indicating that both nanotube surface area and charge density are critical parameters that determine the interaction and electrostatic complex formation between f-CNTs with DNA. All three different f-CNT types in this study exhibited upregulation of marker gene expression over naked DNA using a mammalian (human) cell line. Differences in the levels of gene expression were correlated with the structural and biophysical data obtained for the f-CNT:DNA complexes to suggest that large surface area leading to very efficient DNA condensation is not necessary for effective gene transfer. However, it will require further investigation to determine whether the degree of binding and tight association between DNA and nanotubes is a desirable trait to increase gene expression efficiency in vitro or in vivo. This study constitutes the first thorough investigation into the physicochemical interactions between cationic functionalized carbon nanotubes and DNA toward construction of carbon nanotube-based gene transfer vector systems.     

On the cycle index of point groups

In this brief work we express the cycle index of the molecular point groups as a function of a limited number of initial geometrical parameters. Such parameters are the number of elements composing the domain D of sites of substitutions in the molecule belonging to the point group G, and the numbers of sites of D lying on the symmetry elements for G.     

Diradicals Photogeneration from Chloroaryl-Substituted Carboxylic Acids

With the aim of generating new, thermally inaccessible diradicals, potentially able to induce a double-strand DNA cleavage, the photochemistry of a set of chloroaryl-substituted carboxylic acids in polar media was investigated. The photoheterolytic cleavage of the Ar−Cl bond occurred in each case to form the corresponding triplet phenyl cations. Under basic conditions, the photorelease of the chloride anion was accompanied by an intramolecular electron-transfer from the carboxylate group to the aromatic radical cationic site to give a diradical species. This latter intermediate could then undergo CO₂ loss in a structure-dependent fashion, according to the stability of the resulting diradical, or abstract a hydrogen atom from the medium. In aqueous environment at physiological pH (pH=7.3), both a phenyl cation and a diradical chemistry was observed. The mechanistic scenario and the role of the various intermediates (aryl cations and diradicals) involved in the process was supported by computational analysis.     

High refractive index hyperbranched polyvinylsulfides for planar one‐dimensional all‐polymer photonic crystals

We report on the growth and characterization of one‐dimensional (1D) planar all‐polymer photonic crystals (PhC) with high dielectric contrast (Δn = 0.3) prepared by spin coating using hyperbranched polyvinylsulfide polymers (HB‐PVS) as high refractive index material and cellulose acetate as low refractive index material. Solution processable HB‐PVS show a near ultraviolet absorption inducing an increased refractive index in the visible‐near infrared (n = 1.68, λ = 1000 nm). HBPVS:Cellulose Acetate Distributed Bragg Reflectors show a very clear fingerprint of the photonic band gap possessing the expected polarized dispersion properties as a function of the incidence angle. Moreover, engineered microcavities tuned on the weak fluorescence spectrum of the HB‐PVS show directional fluorescence enhancement effects due to spectral redistribution of the emission oscillator strength. The combination of all these properties testifies the high optical quality of the obtained photonic structures thus indicating HB‐PVS as an interesting material for the preparation of such PhC. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 73–80