Electrochemically formed fullerene-based polymeric films

The recent results of investigations involving the electrochemical formation of polymers containing fullerenes and studies of their properties and applications are critically reviewed. From a structural point of view, these polymers can be divided into four main categories including (1) polymers with fullerenes physically incorporated into the foreign polymeric network without forming covalent bonds, (2) fullerene homopolymers formed via [2+2] cycloaddition, (3) “pearl necklace” polymers with fullerenes mutually linked covalently to form polymer chains, and (4) “charm bracelet” polymers containing pendant fullerene substituents. The methods of electrochemical polymerization of these systems are described and assessed. The structural features and properties of the electrochemically prepared polymers and their chemically synthesized analogs are compared. Polymer films containing fullerenes are electroactive in the negative potential range due to electroreduction of the fullerene moieties. Related films made with fullerenes derivatized with electron-donating moieties as building blocks are electroactive in both the negative and positive potential range. These can be regarded as “double cables” as they exhibit both p- and n-doping properties. Fullerene-based polymers may find numerous applications. For instance, they can be used as charge-storage and energy-converting materials for batteries and photoactive units of photovoltaic cell devices, respectively. They can be also used as substrates for electrochemical sensors and biosensors. Films of the C₆₀/Pt and C₆₀/Pd polymers containing metallic nano-particles of platinum and palladium, respectively, effectively catalyze the hydrogenation of olefins and acetylenes. Laser ablation of electrochemically formed C₆₀/M and C₇₀/M polymer films (M=Pt or Ir) results in fragmentation of the fullerenes leading to the formation of hetero-fullerenes, such as [C₅₉M]⁺ and [C₆₉M]⁺.Dedicated to Professor Dr. Alan M. Bond on the occasion of his 60th birthday.     

Pore size control and gas permeation kinetics of silica membranes by pyrolysis of phenyl-substituted ethoxysilanes with cross-flow through a porous support wall

A silica membrane was produced by chemical vapor deposition using tetraethoxysilane (TEOS), phenyltriethoxysilane (PTES) or diphenyldiethoxysilane (DPDES) as the Si source. Amorphous silica was deposited in the mesopores of a γ-alumina film coated on a porous -alumina tube, by evacuating the reactant through the porous wall. Hydrogen permeance at a permeation temperature of 600°C was of the order of 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹, and was not greatly dependent on the Si sources. The silica membrane produced using TEOS contained micropores permeable to both helium and hydrogen, but CO₂ and larger molecules were only slightly permeated through those mesopores which were left unplugged. The silica membrane produced from DPDES showed a single-component CO₂ permeance equivalent to that of single-component He, and CO₂/N₂ selectivity was approximately 9 at a permeation temperature of 30°C. When a mixture of CO₂ and N₂ was fed, however, CO₂ permeance decreased to the level of N₂ permeance. The H₂/N₂ selectivity, determined from single-component permeances to H₂ and N₂, was approximately 100, and these permeances remained unchanged when an equimolar mixture of H₂ and N₂ was fed. Thus, the DPDES-derived membrane possessed two types of micropores, abundant pores through which helium and hydrogen permeated and a small number of pores in which molecules of CO₂ and N₂ were permeable but not able to pass one another. Neither meso or macropores remained in the DPDES membrane.     

Phosphorylated azahomo[60]fullerene: synthesis and electrochemical properties

A reaction of [60]fullerene with O,O-dibutyl azidophosphate affords a first representative of phosphorylated azahomo[60]fullerenes, which is easier to reduce electrochemically than the starting C₆₀.     

Comparison of the Bonding of Benzene and C60 to a Metal Cluster: Ru3(CO)9(μ3-η2,η 2,η2-C6H6) and Ru3(CO)9(μ3-η2,η2,η2-C60)

The electron distributions and bonding in Ru₃(CO)₉( ³- ², ², ²-C₆H₆) and Ru₃(CO)₉( ³- ², ², ²-C₆₀) are examined via electronic structure calculations in order to compare the nature of ligation of benzene and buckminsterfullerene to the common Ru₃(CO)₉ inorganic cluster. A fragment orbital approach, which is aided by the relatively high symmetry that these molecules possess, reveals important features of the electronic structures of these two systems. Reported crystal structures show that both benzene and C₆₀ are geometrically distorted when bound to the metal cluster fragment, and our ab initio calculations indicate that the energies of these distortions are similar. The experimental Ru–C_fullerene bond lengths are shorter than the corresponding Ru–C_benzene distances and the Ru–Ru bond lengths are longer in the fullerene-bound cluster than for the benzene-ligated cluster. Also, the carbonyl stretching frequencies are slightly higher for Ru₃(CO)₉( ³- ², ², ²-C₆₀) than for Ru₃(CO)₉( ³- ², ², ²-C₆H₆). As a whole, these observations suggest that electron density is being pulled away from the metal centers and CO ligands to form stronger Ru–C_fullerene than Ru–C_benzene bonds. Fenske-Hall molecular orbital calculations show that an important interaction is donation of electron density in the metal–metal bonds to empty orbitals of C₆₀ and C₆H₆. Bonds to the metal cluster that result from this interaction are the second highest occupied orbitals of both systems. A larger amount of density is donated to C₆₀ than to C₆H₆, thus accounting for the longer metal–metal bonds in the fullerene-bound cluster. The principal metal–arene bonding modes are the same in both systems, but the more band-like electronic structure of the fullerene (i.e., the greater number density of donor and acceptor orbitals in a given energy region) as compared to C₆H₆ permits a greater degree of electron flow and stronger bonding between the Ru₃(CO)₉ and C₆₀ fragments. Of significance to the reduction chemistry of M₃(CO)₉( ³- ², ², ²-C₆₀) molecules, the HOMO is largely localized on the metal–carbonyl fragment and the LUMO is largely localized on the C₆₀ portion of the molecule. The localized C₆₀ character of the LUMO is consistent with the similarity of the first two reductions of this class of molecules to the first two reductions of free C₆₀. The set of orbitals above the LUMO shows partial delocalization (in an antibonding sense) to the metal fragment, thus accounting for the relative ease of the third reduction of this class of molecules compared to the third reduction of free C₆₀.     

Headgroup Mobility in the Low Temperature Phase (Lσ′) of DPPC

The ¹H decoupled Phosphorus NMR lineshape of DPPC-water dispersions shows characteristic changes when passing through the three thermotropic phase transitions: subtransition (Lσ′ - Lβ′), pretransition (Lβ′ - Pβ′) and main transition (Pβ -Lα). At the subtransition the spectrum changes from a non-axial-symmetric powder spectrum (Lσ′) to an axial-symmetric one (Lβ′). The two higher phase transitions are characterized by decreases in the intrinsic ³¹P line widths and the chemical shift anisotropy.

Proton-enhanced ¹³C-spectra of the same compound, with natural isotope abundance, recorded at 76 MHz permit the resolved observation of different carbon-positions in the headgroup. In particular the N-(CH₃)₃-carbon nuclei exhibit a narrow isotropic lineshape throughout the entire observed temperature range (-20°C … 50°C). This implies that rotational motion in this moiety does not cease below the subtransition.

To summarize, the headgroup mobility in the Lσ'-phase can be described as follows: The rotation of the entire choline group about the chemical bonds between the phosphate group and the glycerol-backbone is slow on the ³¹P-NMR timescale, the N-(CH₃)₃ end of the choline moiety, however, still undergoes rapid rotational motion. This picture is in accordance with recent interpretations of our ‘H-NMR second moment analysis.     

Realizing the Promise—The Development of Research on Carbon Nanotubes

The present reflection on the development of research on carbon nanotubes (CNTs) stems from the publication of the report “Realizing the Promise of Carbon Nanotubes” by the US National Nanotechnology Initiative in 2015. The report is a critical assessment of the state‐of‐art of CNT research and highlights some unresolved issues related with this field. Starting from the results of this assessment, we carried out an analysis of the publications’ pool in CNTs and related domains, by exploiting bibliometric tools. We focused on the item of competition/collaboration between disciplines and nations, with the purpose of evaluating the position of chemistry (as a discipline) as well as the position of the main European countries and the European Union (EU) as a whole in the context of CNT research. The results of such analysis outline very clearly the interdisciplinary landscape wherein CNT research is situated and show the highly competitive place occupied by EU in the field.     

非化学专业无机及分析化学“讲练考”教学模式改革

This article discussed "teaching-practice-test" teaching mode with teaching practical experience and content matching.Results showed that this mode highlighted the proportion of practice and problem-solving in the process of learning; improved students' ability to solve problems using professional and disciplinary knowledge; changed learning styles from cramming way to autonomous learning step by step and trained students' creativity.     

Synthesis of Cationic Dumbbell-shaped Fullerene Nanostructures as Potential Photodynamic Sensitizers

A design of novel hydrophilic tetracationic dumbbell-shaped [60]fullerene nanostructures was made by balancing the hydrophilicity and hydrophobicity characteristics of the fullerene adduct for their potential application as photodynamic sensitizers in the PDT treatment. A sequential protection-deprotection reaction pathway was applied for the functional differentiation between primary and secondary amine moieties of pentaethylene hexamine. Synthesis of the target molecule involves two key steps of unsymmetrical esterification and amidation of malonic acid and subsequent fullerenation. The synthetic strategy was accomplished using mild reaction conditions in the intermediate molecule preparation and led a moderate overall product yield.     

Divergent Synthesis of Molecular Winch Prototypes

We report the synthesis of conceptually new prototypes of molecular winches with the ultimate aim to investigate the work performed by a single ruthenium-based molecular motor anchored on a surface by probing its ability to pull a load upon electrically-driven directional rotation. According to a technomimetic design, the motor was embedded in a winch structure, with a long flexible polyethylene glycol chain terminated by an azide hook to connect a variety of molecular loads. The structure of the motor was first derivatized by means of two sequential cross-coupling reactions involving a penta(4-halogenophenyl)cyclopentadienyl hydrotris(indazolyl)borate ruthenium(II) precursor and the resulting benzylamine derivative was next exploited as key intermediate in the divergent synthesis of a family of nanowinch prototypes. A one-pot method involving sequential peptide coupling and Cu-catalyzed azide-alkyne cycloaddition was developed to yield four loaded nanowinches, with load fragments encompassing triptycene, fullerene and porphyrin moieties.     

Designing liquid-crystalline dendronised hexa-adducts of [60]fullerene via click chemistry

ABSTRACT

Liquid-crystalline [60]fullerodendrimers were constructed via click chemistry based on the reaction between hexa-adducts of [60]fullerene (C₆₀) bearing 12 azide groups and alkyne-terminated cyanobiphenyl dendrons of first- and second-generation. The structure of all the new compounds was confirmed by IR, UV, ¹H and ¹³C NMR spectroscopies and mass spectrometry. The mesomorphic properties were studied by polarised optical microscopy, differential scanning calorimetry and small-angle X-ray scattering. The hexa-adduct of C₆₀ functionalised with the first-generation dendrons gave rise to the formation of a smectic A phase and a rectangular columnar phase (c2mm symmetry) while the hexa-adduct of C₆₀ decorated with the second-generation dendrons displayed only a rectangular columnar phase (c2mm symmetry). Our results show that the hexa-adduct of C₆₀ is a unique synthetic platform for the design of fullerodendrimers and dendronised materials.