Synthesis and characterization of a new porphyrin-fullerene dyad containing a β-pyrrolic linkage

Two new ß-substituted arylethynyl meso-tetraphenylporphyrins, 2[(4'-formyl)phenyl]ethynyl-5,10,15,20-tetraphenylporphyrin (System A) and 2-[(4'-methyl)phenyl]ethynyl-5,10,15,20tetraphenylporphyrin (System B) and their zinc derivatives were synthesized. Comparative UV/Visible and cyclic voltammetry studies of such macrocycles reveal the presence of an extensive conjugation between the tetrapyrrolic ring and the linker, through π-π orbitais interaction. This interaction was observed in form of a "push-pull" effect that moves the electronic charge between the porphyrin and the aldehyde group of the System A. System B, bearing a methyl instead of the formyl group, was synthesized in order to evaluate the effect of the substitution on the charge derealization, which is necessary to corroborate the push-pull mechanism hypothesis. The new porphyrin, System A, was also used as starting material for the synthesis of new porphyrinfullerene dyads in which the [60]fullerene is directly linked to the tetrapyrrolic rings by ethynylenphenylen subunits. Fluorescence and transient absorption measurements of the new dyads reveal that ultrafast energy and electron transfer occur respectively in non polar and polar solvents, with high values of the rate constant. Copyright The Electrochemical Society

Synthesis of Novel Porphyrin and its Complexes Covalently Linked to Multi-Walled Carbon Nanotubes and Study of their Spectroscopy

Novel covalent porphyrin and its complexes (Co2+, Zn2+) functionalized multi-walled carbon nanotubes (MWNTs) have been successfully synthesized by the reaction of the carboxyl on the surface of MWNTs which was synthesized to use carbon radicals generated by the thermal decomposition of azodiisobutyronitrile (AIBN) with 5-p-hydroxyphenyl-10,15,20-triphenyl-porphyrin and its complexes (Co2+, Zn2+). Three resulting nanohybrids were characterized by spectroscopy (FT-IR, Raman, and UV-vis), TGA, and TEM. The quality of porphyrin attached to the MWNTs was determined from thermogravimeric analysis (TGA) of the MWNTs, which showed a weight loss of about 60%. The Raman and absorption spectroscopy data showed that the electronic properties of modified MWNTs were mostly retained, without damaging their one-dimensional electronic properties. From fluorescence measurements, it was observed that the porphyrin and its complexes (Co2+, Zn2+) were nearly quenched by MWNTs, indicating that this covalently modified mode facilitated the effective energy or electron transfer between the excited porphyrin moiety and the extended π-system of MWNTs

Clay-fulleropyrrolidine nanocomposites

In this work, we describe the insertion of a water-soluble bisadduct fulleropyrrolidine derivative into the interlayer space of three layered smectite clays. The composites were characterized by a combination of powder X-ray diffraction, transmission electron microscopy, X-ray photoemission and FTIR spectroscopies, and laser flash photolysis measurements. The experiments, complemented by computer simulations, give insight into the formation process, structural details, and properties of the fullerene/clay nanocomposites. The reported composite materials constitute a new hybrid system, where C-60 differs from its crystals or its solutions, and open new perspectives for the design and construction of novel C-60-based organic/clay hybrid materials.</p

Shell-Controlled Photoluminescence in CdSe/CNT Nanohybrids

A new type of nanohybrids containing carbon nanotubes (CNTs) and CdSe quantum dots (QDs) was prepared using an electrostatic self-assembly method. The CdSe QDs were capped by various mercaptocarboxylic acids, including thioglycolic acid (TGA), dihydrolipoic acid (DHLA) and mercaptoundecanoic acid (MUA), which provide shell thicknesses of ~5.2, 10.6 and 15.2 Å, respectively. The surface-modified CdSe QDs are then self-assembled onto aridine orange-modified CNTs via electrostatic interaction to give CdSe/CNT nanohybrids. The photoluminescence (PL) efficiencies of the obtained nanohybrids increase significantly with the increase of the shell thickness, which is attributed to a distance-dependent photo-induced charge-transfer mechanism. This work demonstrates a simple mean for fine tuning the PL properties of the CdSe/CNT nanohybrids and gains new insights to the photo-induced charge transfer in such nanostructures

Organic-Inorganic Nanostructure Architecture via Directly Capping Fullerenes onto Quantum Dots

A new form of fullerene-capped CdSe nanoparticles (PCBA-capped CdSe NPs), using carboxylate ligands with [60] fullerene capping groups that provides an effective synthetic methodology to attach fullerenes noncovalently to CdSe, is presented for usage in nanotechnology and photoelectric fields. Interestingly, either the internal charge transfer or the energy transfer in the hybrid material contributes to photoluminescence (PL) quenching of the CdSe moieties.open2

Fabrication and Properties of Porphyrin Nano- and Micro-particles with Novel Morphology

New types of porphyrin nano- and micro-particles composed of J- and H-heteroaggregates were prepared by electrostatic self-assembly of two oppositely charged porphyrins, tetrakis(4-trimethylammoniophenyl)porphyrin (H2TAPP4+) and tetrakis(4-sulfonatophenyl)porphyrin cobalt(II) (CoTPPS4−), in aqueous solutions. Transmission electron microscopy (TEM) images showed novel morphology and size distribution of porphyrin particles fabricated under different experimental conditions. The assembly process of the nano- and micro-particles was monitored by UV–Vis spectra. Fluorescence spectra and UV–Vis spectra provided optical information on the formation of the nano- and micro-particles. Cyclic voltammograms of the porphyrin particles indicated that the electron gain and loss of the H2TAPP4+ion were restrained, and the electron transfer of the CoTPPS4−ion was promoted in the J- and H-type porphyrin heteroaggregates within the particles. The stability and constitution of the nano- and micro-particles were confirmed by UV-light irradiation, heat-treatment, and pH and ionic strength changes. Photoelectrochemical measurements showed that the photoelectron transfer of TiO2modified with the particles was more efficient than that of TiO2sensitized by either monomers. The photoelectronic and photocatalytic properties of the products indicated that the pyramidal or spherical configuration of the nano- and micro-particles was favorable for the absorption and transfer of the energy. It can be found that TiO2sensitized by the porphyrin nano- and micro-particles exhibits significant improvement in energy conversion and photocatalytic activity with reference to pure TiO2

Bioaccumulation and ecotoxicity of carbon nanotubes

Carbon nanotubes (CNT) have numerous industrial applications and may be released to the environment. In the aquatic environment, pristine or functionalized CNT have different dispersion behavior, potentially leading to different risks of exposure along the water column. Data included in this review indicate that CNT do not cross biological barriers readily. When internalized, only a minimal fraction of CNT translocate into organism body compartments. The reported CNT toxicity depends on exposure conditions, model organism, CNT-type, dispersion state and concentration. In the ecotoxicological tests, the aquatic organisms were generally found to be more sensitive than terrestrial organisms. Invertebrates were more sensitive than vertebrates. Single-walled CNT were found to be more toxic than double-/multi-walled CNT. Generally, the effect concentrations documented in literature were above current modeled average environmental concentrations. Measurement data are needed for estimation of environmental no-effect concentrations. Future studies with benchmark materials are needed to generate comparable results. Studies have to include better characterization of the starting materials, of the dispersions and of the biological fate, to obtain better knowledge of the exposure/effect relationships

Ruthenium oxide-carbon-based nanofiller-reinforced conducting polymer nanocomposites and their supercapacitor applications.

In this review article, we have presented for the first time the new applications of supercapacitor technologies and working principles of the family of RuO2-carbon-based nanofiller-reinforced conducting polymer nanocomposites. Our review focuses on pseudocapacitors and symmetric and asymmetric supercapacitors. Over the last years, the supercapacitors as a new technology in energy storage systems have attracted more and more attention. They have some unique characteristics such as fast charge/discharge capability, high energy and power densities, and long stability. However, the need for economic, compatible, and easy synthesis materials for supercapacitors have led to the development of RuO2-carbon-based nanofiller-reinforced conducting polymer nanocomposites with RuO2. Therefore, the aim of this manuscript was to review RuO2-carbon-based nanofiller-reinforced conducting polymer nanocomposites with RuO2 over the last 17 years

Stereochemical plasticity modulates cooperative binding in a CoII12L6 cuboctahedron

Biomolecular receptors are able to process information by responding differentially to combinations of chemical signals. Synthetic receptors that are likewise capable of multi-stimuli response can form the basis of programmable molecular systems, wherein specific input sequences create distinct outputs. Here we report a pseudo-cuboctahedral assembly capable of cooperatively binding anionic and neutral guest species. The binding of pairs of fullerene guests was observed to effect the all-or-nothing cooperative templation of an S6-symmetric host stereoisomer. This bis-fullerene adduct exhibits different cooperativity in binding pairs of anions from the fullerene-free parent: in one case, positive cooperativity is observed, while in another all binding affinities are enhanced by an order of magnitude, and in a third the binding events are only minimally perturbed. This intricate modulation of binding affinity, and thus cooperativity, renders our new cuboctahedral receptor attractive for incorporation into systems with complex, programmable responses to different sets of stimuli.This work was supported by the UK Engineering and Physical Sciences Research Council (EPSRC). F.J.R. acknowledges Cambridge Australia Scholarships and the Cambridge Trust for PhD funding