M. Teresa Martínez

Synthesis of a new polyaniline/nanotube composite: “in-situ” polymerisation and charge transfer through site-selective interaction

A new polyaniline/multi-wall carbon nanotube (PANI/MWNT) composite has been successfully synthesized by an “in-situ” polymerisation process; Raman studies indicate a site-selective interaction between the quinoid ring of the polymer and the MWNTs opening the way for charge transfer processes; transport measurements clearly reveal drastic changes in the electronic behaviour confirming the formation of a true composite material with enhanced electronic properties.

Solvent-Free Preparation of High-Toughness Epoxy−SWNT Composite Materials

Multicomponent nanocomposite materials based on a high-performance epoxy system and single-walled carbon nanotubes (SWNTs) have been prepared. The noncovalent wrapping of nitric acid-treated SWNTs with a PEO-based amphiphilic block copolymer leads to a highly disaggregated filler with a boosted miscibility in the epoxy matrix, allowing its dispersion without organic solvents. Although direct dispersion of acid-treated SWNTs results in modestly improved epoxy matrix mechanical properties, the incorporation of wrapped SWNTs produces a huge increase in toughness (276% improvement at 0.5 wt % loading) and impact strength (193% at 0.5 wt % loading) with no detrimental effect on the elastic properties. A synergistic effect between SWNTs and the block copolymer is revealed on the basis of tensile and impact strength results. Atomic force microscopy has been applied, obtaining stiffness mappings that identify nanostructure features responsible of the dynamic mechanical behavior. The electrical percolation threshold is greatly reduced, from 0.31 to 0.03 wt % SWNTs when block copolymer-wrapped SWNTs are used, and all the measured conductivity values increased up to a maximum of 7 orders of magnitude with respect to the baseline matrix (1 wt % wrapped-SWNTs loading). This approach provides an efficient way to disperse barely dispersible SWNTs without solvents into an epoxy matrix, and to generate substantial improvements with small amounts of SWNTs.

Carbon Nanotube Effect on Polyaniline Morphology in Water Dispersible Composites

A straightforward, template-free chemical oxidative polymerization of aniline was used to prepare nanofibrillar polyaniline (nf-PANI) and a set of corresponding composites with multiwall carbon nanotubes (MWNTs). All the products showed remarkable water dispersibility since they are formed by hydrophilic particles of nanometric size. A comparative study performed on composites in a wide range of MWNT loadings has led to two main conclusions: on one hand, the presence of MWNTs affects neither the chemical structure nor the crystallinity of polyaniline. On the other hand, even small amounts of MWNTs have a significant effect on the morphology of polyaniline in composites. This effect is noticeable not only in electron microscopy images but also in the UV-vis absorbance of water dispersions and electrical conductivity behavior in the solid state. Competition between nucleation sites during polymerization is proposed as an explanation for these phenomena.

A photo-induced electron transfer study of an organic dye anchored on the surfaces of TiO2 nanotubes and nanoparticles

We report on femtosecond-nanosecond (fs-ns) studies of the triphenylamine organic dye (TPC1) interacting with titania nanoparticles of different sizes, nanotubes and nanorods. We used time-resolved emission and absorption spectroscopy to measure the photoinduced dynamics of forward and back electron transfer processes taking place in TPC1-titania complexes in acetonitrile (ACN) and dichloromethane (DCM) solutions. We observed that the electron injection from the dye to titania occurs in a multi-exponential way with the main contribution of 100 fs from the hot excited charge-transfer state of anchored TPC1. This process competes with the relaxation of the excited state, mainly governed by solvation, that takes place with average time constants of 400 fs in ACN and 1.3 ps in DCM solutions. A minor contribution to the electron injection process takes place with longer time constants of about 1-10 ps from the relaxed excited state of TPC1. The latter times and their contribution do not depend on the size of the nanoparticles, but are substantially smaller in the case of nanotubes (1-3 ps), probably due to the caging effect. The contribution is also smaller in DCM than in ACN. The efficient back recombination takes place also in a multi-exponential way with times of 1 ps, 15 ps and 1 ns, and only 20-30% of the initial injected electrons in the conduction band are left within the first 1 ns after excitation. The faster recombination rates are suggested due to those originating from the free electrons in the conduction band of titania or the electrons in the shallow trap states, while the slower recombination is due to the electrons in the deep trap states. The results reported here should be relevant to a better understanding of the photobehaviour of an organic dye with promising potential for use in solar cells. They should also help to determine the important factors that limit the efficiency of solar cells based on the triphenylamine-based dyes for solar energy conversion.

Production of carbon nanotubes: the light approach

Abstract In this article we present an overview about the current state of the art using highly concentrated light in the production process of carbon nanotubes. Firstly, the most common approaches using laser light or solar radiation are described and their production possibilities are compared. Secondly, important growth parameters and their complex interactions are discussed. It is shown that a key issue in the production of nanotubes is the creation of the proper temperature conditions. This concerns the temperature of both the target surface and the gas-phase. While the first controls the number and kinetics of evaporated species, the second affects the assembling of nanotubes in the gas-phase. Thirdly, the problem of obtaining high-quality nanotube materials in an up-scaled production process is addressed. Here, a solution may be related to the finding of advantageous light–target interactions.

Application of biotechnological tools to Quercus improvement

The genus Quercus, which belongs to the family Fagaceae, is native to the northern hemisphere and includes deciduous and evergreen species. The trees of the different species are very important from both economic and ecological perspectives. Application of new technological approaches (which span the fields of plant developmental biology, genetic transformation, conservation of elite germplasm and discovery of genes associated with complex multigenic traits) to these long-rotation hardwoods may be of interest for accelerating tree improvement programs. This review provides a summary of the advances made in the application of biotechnological tools to specific oak species. Significant progress has been made in the area of clonal propagation via organogenesis and somatic embryogenesis (SE). Standardized procedures have been developed for micropropagating the most important European (Q. robur, Q. petarea, Q. suber) and American (Q. alba, Q. bicolor, Q. rubra) oaks by axillary shoot growth. Although regenerated plantlets are grown in experimental trials, large-scale propagation of oak species has not been carried out. The induction of SE in oaks from juvenile explants is generally not problematic, although the use of explants other than zygotic embryos is much less efficient. During the last decade, enormous advances have been made in inducing SE from selected adult trees, mainly specimens of pedunculate oak (Q. robur) and cork oak (Q. suber). Advances in the understanding of the maturation and germination steps are required for better use of embryogenic process in clonal forestry. Quercus species are late-maturing and late-flowering, exhibit irregular seed set, and produce seeds that are recalcitrant to storage by conventional procedures. Vitrification-based cryopreservation techniques were used successfully in somatic embryos of pedunculate oak and cork oak, and an applied genbank of cork oak selected genotypes is now under development. The feasibility of genetic transformation of pedunculate oak and cork oak somatic embryos by means of co-culture techniques with several strains of Agrobacterium tumefaciens has also been demonstrated. To date, most research on the genomics of Quercus species has concerned population genetics. Approaches using functional genomics to examine the molecular and cellular mechanisms that control organogenesis and or somatic embryogenesis are still scarce, and efforts on the isolation and characterization of genes related to other specific traits should be intensified in the near future, as this would help improve the practical application of clonal forestry in recalcitrant species such as oaks.

Maturation and germination of oak somatic embryos originated from leaf and stem explants: RAPD markers for genetic analysis of regenerants.

Experiments were performed to determine the influence of maturation medium carbohydrate content on the rates of germination and plantlet conversion (root and shoot growth) of somatic embryos from four embryogenic lines derived from leaf or internode explants of Quercus robur L. seedlings. The conversion rate was favoured by high carbohydrate content as long as the maturation medium contained at least 2% sucrose, which was necessary for healthy embryo development. Given this, sorbitol and mannitol favoured the conversion rate more efficiently than sucrose, the highest rate, 32%, being achieved by medium with 6% sorbitol and 3% sucrose. Maturation treatment did not affect the root or shoot lengths of converted embryos. In supplementary experiments, 2 weeks of gibberellic acid treatment between maturation and germination treatments did not improve germination rates, but did reduce root length and the number of leaves per regenerated plantlet. In the four embryogenic lines tested, plant recovery rate was enhanced by inclusion of benzyladenine into the germination medium following culture of the embryos on maturation medium with 6% sorbitol and 2-3% sucrose. In embryogenic systems it is important to assess the uniformity of the regenerants. Random amplified polymorphic DNA (RAPD) analysis using 32 arbitrary oligonucleotide primers was performed to study variability in DNA sequences within and between four embryogenic lines. No intraclonal nor interclonal polymorphism was detected between embryogenic lines originating from different types of explant from the same seedling, but every one of the primers detected enough polymorphism among clones originating from different plants to allow these three origins to be distinguished. No differences in DNA sequences between regenerated plantlets and their somatic embryos of origin were detected, but a nodular callus line that had lost its embryogenic capacity was found to be mutant with respect to three other clones originating from the same plantlet. This study shows that high carbohydrate levels in the maturation medium significantly increase plant conversion of oak somatic embryos, which exhibit no variation in DNA sequences when proliferated by secondary embryogenesis.

Nanofibrilar Polyaniline: Direct Route to Carbon Nanotube Water Dispersions of High Concentration

Water dispersible nanofibrilar polyaniline (NF-PANI) provides a novel and direct route towards carbon nanotube water dispersions of high concentration. Carrying out the chemical synthesis of NF-PANI in the presence of carbon nanotubes (CNTs) results in an entirely nanostructured nanofibrilar polyaniline/carbon nanotube (NF-PANI/CNT) composite material that contains well segregated CNTs partially coated by NF-PANI. This new approach is simple, fast, and inexpensive, and enables the direct preparation of stable and homogeneous dispersions of the composites in water at concentrations up to 10 mg · mL(-1) , even for the highest CNT loadings of 50 wt.-% without the participation of surfactants or stabilizers.

Influence of air oxidation on the surfactant-assisted purification of single-walled carbon nanotubes.

Arc discharge single-walled carbon nanotube (SWCNT) soot was treated under different experimental conditions including gas- and liquid-phase oxidation, heat treatment in an inert gas, and hydrogen gasification. Afterward, the samples were dispersed in a surfactant and centrifuged at a moderately high speed. Near-infrared spectra of all the dispersions were compared with that of raw SWCNT soot. The relative intensity of SWCNT characteristic spectral bands strongly increased for air-oxidized samples after centrifugation, while it did not substantially change for samples oxidized with nitric acid or reduced with hydrogen. The relative SWCNT spectral intensity was associated to the sample purity through the so-called purity index, which was calculated from the S(22) band transition of semiconducting SWCNTs. Air-oxidized samples experienced a 7-fold increase in the purity index during centrifugation, while it increased by only 2-3 times for nonoxidized samples. Air oxidation specifically improves the preferential stability of SWCNTs over carbonaceous impurities in the dispersions, leading to the highest purity index values reported so far.

Epoxy composites with covalently anchored amino-functionalized SWNTs: towards the tailoring of physical properties through targeted functionalization

Functionalization of single-walled carbon nanotubes (SWNTs) with covalently grafted amine moieties provides reactive fillers with potential for covalent anchoring to an epoxy matrix. Manufacturing and characterization of a high performance epoxy system reinforced with as-grown and aminated SWNTs are presented through four different approaches. Epoxy composite materials incorporating SWNTs aminated through sidewall addition reactions present enhanced mechanical, thermal and electrical properties, beyond the effect of unfunctionalized SWNTs. The functionalization pathways studied here lead to a composite with specific improvements in some of the physical properties of the epoxy matrix, which enables the tailored design of the composites properties through functionalization. The aminationviadiazonium reaction with 4-aminobenzylamine is especially effective in enhancing the tensile and impact properties of the epoxy composites (44% improvement in impact strength at 0.1 wt% loading) and leads to the highest increase in elastic modulus reported so far for the integration of aminated nanotubes into epoxy resin. Composites incorporating aminated SWNTs throughout the 1,3-dipolar cycloaddition reaction stand out for their thermo-oxidative stability and thermomechanical properties. The incorporation of as-produced arc-discharge SWNTs into the TGAP/DDS epoxy matrix leads to composite materials with the highest electrical conductivity among all the studied samples.