Nanoaggregates of copper porphyrazine in floating layers and Langmuir-Schaefer films

Aggregation behavior of unsubstituted copper porphyrazine (CuPaz) on the water surface was studied by analysis of compression curves, Brewster angle microscopy (BAM), and optical spectroscopy. The structure and stability of the CuPaz aqua aggregates in the floating layers are determined by hydration degree that depends on initial surface concentration and surface pressure. Langmuir-Schaefer (LS) films of CuPaz were prepared by deposition of the variously structured floating layers and studied by X-ray scattering technique and optical spectroscopy. Stable and labile structures were detected and compared with the floating CuPaz aqua aggregates. Conditions of formation of the stable four-stacked nanoaggregates in LS films were determined. A model comprising both nucleation of CuPaz on the water surface and structural transformations in the solid films is proposed.     

Crystallographic and morphological characterization of thin pentacene films on polycrystalline copper surfaces

The degree of crystallinity, the structure and orientation of crystallites, and the morphology of thin pentacene films grown by vapor deposition in an ultrahigh vacuum environment on polycrystalline copper substrates have been investigated by x-ray diffraction and tapping-mode scanning force microscopy (TM-SFM). Depending on the substrate temperature during deposition, very different results are obtained: While at 77 K a long-range order is missing, the films become crystalline at elevated temperatures. From a high-resolution x-ray-diffraction profile analysis, the volume-weighted size of the crystallites perpendicular to the film surface could be determined. This size of the crystallites increases strongly upon changing temperature between room temperature and 333 K, at which point the size of individual crystallites typically exceeds 100 nm. In this temperature region, three different polymorphs are identified. The vast majority of crystallites have a fiber texture with the (001) net planes parallel to the substrate. In this geometry, the molecules are oriented standing up on the substrate (end-on arrangement). This alignment is remarkably different from that on single-crystalline metal surfaces, indicating that the growth is not epitaxial. Additionally, TM-SFM images show needlelike structures which suggest the presence of at least one additional orientation of crystallites (flat-on or edge-on). These results indicate that properties of thin crystalline pentacene films prepared on technologically relevant polycrystalline metal substrates for fast electronic applications may be compromised by the simultaneous presence of different local molecular aggregation states at all temperatures.     

Optical and morphological characterization of bispyrazole thin films for gas sensing applications

The optical gas recognition capabilities of thin film layer of 4-[bis[(3,5-dimethyl-1H-pyrazol-1-yl)methyl]-amino]phenol deposed on quartz substrates were studied. The dynamic gas responses to the following analytes have been investigated as air pollutants (SO₂, NO₂, CO, CH₄ and NH₃). The spin-coated bispyrazole layer appears to have reversible response towards SO₂ and a very low and irreversible response to NO₂. The selectivity of the thin film based on bispyrazole layer with respect to other analytes was also examined and the present data show that the thin sensing layer in the presence of CO, CH₄ and NH₃ in low concentration does not influence its optical properties.     

Optical and electrochemical properties of poly(o-toluidine) multiwalled carbon nanotubes composite Langmuir-Schaefer films

Conducting poly(o-toluidine) (POT) with multiwalled carbon nanotubes (MWNTs) nanocomposite (POT-MWNTs) was synthesized by oxidative polymerization. Chloroform solutions of the material were used for the optical characterizations by means of UV-visible spectroscopy and for the fabrication of Langmuir-Schaefer (LS) films. LS films were fabricated at the air-liquid interface by using 0.1 M HCl aqueous solution as the subphase to study the electrochemical properties of the nanocomposite by means of cyclic voltammetry and photoelectrochemical techniques. The optical characterizations gave proof that the presence of MWNTs inside the polymeric matrix produced no change in the (pi-pi*) transition of POT structure, indicating that the polymeric chains were simply wrapped around and not doped by MWNTs. The electrochemical investigations highlighted significant changes in the redox properties of POT-MWNTs LS films with respect to pure POT. The cyclic voltammetric study also revealed high electrochemical stability, confirmed by the estimation of the diffusion coefficient and the photoelectrochemical response of the nanocomposite LS films. This characteristic turned out to be more evident than that obtained in our earlier studied poly(o-anisidine)-MWNTs (POAS-MWNTs) system.     

Synthesis, characterization, and antifouling potential of functionalized copper nanoparticles

The synthesis, characterization, and antimicrobial properties of functionalized copper nanoparticle/polymer composites are reported. Copper nanoparticles (Cu NPs) are stabilized by surface attachment of the acrylic functionality that can be copolymerized with other acrylic monomers, thus, becoming an integral part of the polymer backbone. Biological experiments show that Cu NP/polymer composites exhibit antimicrobial activity similar to that of conventional copper-based biocides. Atomic absorption spectroscopy shows the smallest amount of copper ions leaching from chemically bound acrylated Cu NPs compared to the nonfunctionalized biocides. These composites have a strong potential for use in antibacterial or marine antifouling coatings.     

Evolution of ordered films of copper phthalocyanine according to EPR data

The procedure for calculating the orientation distribution of molecules using the angular dependence of EPR spectra was employed to study copper(II) phthalocyanine (CuPc) films varying in thickness and obtained by depositing the molecular complex on flat quartz plates. At the first stage of deposition, a layer of the α-CuPc phase with preferable orientation of molecular stacks along the plate surface is formed. At the second stage, a layer with an orthogonal arrangement of molecular stacks is condensed over the first layer. The interaction with NO₂ forms CuPc binuclear associates. Analysis of the EPR spectra made it possible to determine the symmetry of the structure and the distance between the paramagnetic Cu²⁺ ions; the structure of the associates has been proposed. The orientation distribution of CuPc dimers in the film depends both on the initial ordering in the film and on processing conditions. Strong disordering of molecular stacks in ordered films during the α-CuPc to α-CuPc phase transition has been found.     

Synthesis and characterization of a benzene-centered, phthalocyanine hexamer

The first benzene-centered, phthalocyanine hexamer has been synthesized by a dicobaltoctacarbonyl-catalyzed trimerization reaction of an ethynyl-bridged bisphthalocyanine and characterized by different spectrometric and spectroscopic techniques.     

Synthesis,structural characterization,and immunological properties of carbon nanotubes functionalized with peptides

Carbon nanotubes (NTs) are becoming highly attractive molecules for applications in medicinal chemistry. The main problem of insolubility in aqueous media has been solved by developing a synthetic protocol that allows highly water-soluble carbon NTs to be obtained. As a result, biologically active peptides can be easily linked through a stable covalent bond to carbon NTs. We have demonstrated that a bound peptide from the foot-and-mouth disease virus, corresponding to the 141-159 region of the viral envelope protein VP1, retained the structural integrity and was recognized by monoclonal and polyclonal antibodies. In addition, this peptide-NT conjugate is immunogenic, eliciting antibody responses of the right specificity. Such a system could be greatly advantageous for diagnostic purposes and could find future applications in vaccine delivery.     

Synthesis and structural characterization of functionalized dimeric aluminophosphonates and a monomeric gallophosphonate anion

Reaction of t-BuP(O)(OSiMe(3))(OH) with Me(3)Al leads to the formation of [Me(2)Al(mu-O)(2)P(OSiMe(3))(t-Bu)](2) (1) whereas Me(2)AlCl reacts with Ph(2)P(O)(OH) to yield [(Cl)(Me)Al(mu-O)(2)PPh(2)](2) (2). These compounds represent the first examples of functionalized dimeric four-ring type aluminophosphonate systems. The double four-ring type gallophosphonate, namely, [t-BuPO(3)GaMe](4), reacts with n-Bu(4)NHF(2) under ambient conditions, resulting in the formation of a monomeric gallophosphonate [n-Bu(4)N][MeGa[t-BuPO(2)(OH)](3)] (3). These derivatives have been adequately characterized using various spectroscopic techniques and X-ray diffraction studies.     

NO2 gas detection by Langmuir-Blodgett films of copper phthalocyanine multilayer structures

Copper (II) phthalocyanine derivatives with four alkyl chains were synthesized. Langmuir-Blodgett (LB) films of the following two compounds were deposited: Cu(II)[tetrakis(3,3-dimethyl-butoxycarbonyl)] phthalocyanine and Cu(II)[tetrakis(n-butoxycarbonyl)] phthalocyanine. Moreover, LB films from a 1:1 mixture of the two compounds were prepared. All isotherms and optical data were consistent with the molecules being stacked nearly edge-on to the substrate, with the molecular faces having a preferred orientation perpendicular to the dipping direction. The dynamic response characteristics of the electrical conductance of the LB films to different NO₂ concentrations in dry air are described. A relationship has been observed between the anisotropic molecular orientation and the electrical conductivity parallel to the substrate.     

Mesoscopic organization of two-dimensional J-aggregates of thiacyanine in Langmuir-Schaefer films

When dioctadecyl dimethylammonium bromide (DODAB) is compressed on a subphase containing 3,3'-disulfopropyl-5,5'-dichlorothiacyanine (THIAMS), adsorption of the dye to the DODAB monolayer results in the formation of J-aggregates which spontaneously organize into polygonal domains of micron size. The features of the domains depend on the surface pressure. The fluorescence of the individual domains is polarized. The shapes of the domains determined by fluorescence microscopy and atomic force microscopy (AFM) are identical. The domains differ however significantly from those observed after injection of a 3,3'-disulfopropyl-5,5'-dichloro-9-ethylthiacarbocyanine (THIATS) or THIAMS solution below a precompressed DODAB film, as well as from the domains observed upon compression of a DODAB monolayer on a subphase containing 10(-6) M THIATS.     

Dry etching of copper phthalocyanine thin films: effects on morphology and surface stoichiometry

We investigate the evolution of copper phthalocyanine thin films as they are etched with argon plasma. Significant morphological changes occur as a result of the ion bombardment; a planar surface quickly becomes an array of nanopillars which are less than 20 nm in diameter. The changes in morphology are independent of plasma power, which controls the etch rate only. Analysis by X-ray photoelectron spectroscopy shows that surface concentrations of copper and oxygen increase with etch time, while carbon and nitrogen are depleted. Despite these changes in surface stoichiometry, we observe no effect on the work function. The absorbance and X-ray diffraction spectra show no changes other than the peaks diminishing with etch time. These findings have important implications for organic photovoltaic devices which seek nanopillar thin films of metal phthalocyanine materials as an optimal structure.     

酞菁和酞菁铜的三阶非线性光学性质

用INDO/SDCI方法研究了酞菁和酞菁铜的电子结构, 紫外-可见光谱, 三阶非线性光学系数及其色散效应, 发现酞菁铜中Cu^2+对γ的贡献很小, 故酞菁与酞菁铜的γ几乎相等, 我们的计算结果对此进行了合理的解释。     

Degradation of agar films in a humid tropical climate: Thermal, mechanical, morphological and structural changes

Agar films were subjected to natural weathering exposure in a humid tropical climate for 90 days to determine their biodegradation behavior and functionality. Exposed samples were taken at 15, 30, 45, 60 and 90 days. Mechanical, thermal, structural and morphological properties were determined using tensile test, differential scanning calorimetry (DSC), attenuated reflectance infrared spectroscopy (ATR-FTIR), X-ray diffraction and environmental scanning electron microscopy (ESEM). The photodegradation process and temperature-relative humidity fluctuations promoted a decrease in agar mechanical properties in early exposure stages (30-45 days) caused by a reduction in agar molecular size and a decrease in the number of sulfate groups. These changes alter agar crystallinity, causing contraction that leads to formation of micro-fractures and embrittlement, and promote microbial attack. Accelerated weathering exposure of agar films showed that outdoor climate parameters play an important role in their degradation. These results will aid in further research to determine the potential use of agar as an environmentally friendly solution to the problem of biodegradable composites disposal.     

Controlled reactions on a copper surface: synthesis and characterization of nanostructured copper compound films

We report the synthesis of nanostructured copper compound films on a copper surface under mild conditions. A series of low-dimensional structures including Cu(OH)(2) fibers and scrolls, CuO sheets and whiskers, and Cu(2)(OH)(2)CO(3) rods have been successfully grown on the copper surfaces at ambient temperature and pressure. Most of the structures are phase-pure single crystallites. The films were formed by the direct oxidation of copper in aqueous solutions of NaOH with an oxidant (NH(4))(2)S(2)O(8). The evolution of the ultrafine structures as a function of the reaction conditions has been revealed, from fibers of Cu(OH)(2) to scrolls of Cu(OH)(2) to sheets or whiskers of CuO. By replacing NaOH with NaHCO(3) in the synthesis, square/rectangular rod arrays of Cu(2)(OH)(2)CO(3) were obtained. The controlled reactions allow the large-scale, template-free, cost-effective synthesis of copper compound films with ordered, uniform, stable, ultrafine structures.     

Thermal stability of lysozyme Langmuir-Schaefer films by FTIR spectroscopy

Fourier transform infrared spectroscopy has been applied to study the thermal stability of multilayer Langmuir-Schaefer (LS) films of lysozyme deposited on silicon substrates. The study has confirmed previous structural findings that the LS protein films have a high thermal stability that is extended in a lysozyme multilayer up to 200 degrees C. 2D infrared analysis has been used here to identify the correlated molecular species during thermal denaturation. Asynchronous 2D spectra have shown that the two components of water, fully and not fully hydrogen bonded, in the high-wavenumber range (2800-3600 cm-1) are negatively correlated with the amine stretching band at 3300 cm-1. On the grounds of the 2D spectra the FTIR spectra have been deconvoluted using three main components, two for water and one for the amine. This analysis has shown that, at the first drying stage, up to 100 degrees C, only the water that is not fully hydrogen bonded is removed. Moreover, the amine intensity band does not change up to 200 degrees C, the temperature at which the structural stability of the multilayer lysozyme films ceases.     

Nanostructured films from phthalocyanine and carbon nanotubes: surface morphology and electrical characterization

We report on the investigation of the surface morphology and DC conductivity of nanostructured layer-by-layer (LbL) films from nickel tetrasulfonated phthalocyanine (NiTsPc) alternated with either multi-walled carbon nanotubes (MWNTs/NiTsPc) or multi-walled carbon nanotubes dispersed in chitosan (MWNTs+Ch/NiTsPc). We have explored the surface morphology of the films by using fractal concepts and dynamic scale laws. The MWNTs/NiTsPc LbL films were found to have a fractal dimension of ca. 2, indicating a quasi Euclidean surface. MWNTs+Ch/NiTsPc LbL films are described by the Lai-Das Sarma-Villain (LDV) model, which predicts the deposition of particles and their subsequent relaxation. An increase in the wetting contact angle of MWNTs+Ch/NiTsPc LbL films was observed, as compared with MWNTs/NiTsPc LbL films, which presented an increase in the fractal dimension of the first system. Room temperature conductivities were found be ca. 0.45 S/cm for MWNTs/NiTsPc and 1.35 S/cm for MWNTs+Ch/NiTsPc.     

Optical and electrical measurements on CO2 covered copper films

Thin polycrystalline copper films are deposited in a special UHV cell on glass substrates and are covered step by step with CO₂. The optical and electrical properties of the films are studied in-situ by means of ellipsometry and resistivity measurements. The properties of the clean films correspond to literature data. In the case of monolayer adsorption of CO₂, the changes in the ellipsometrical angles are δΔ≈+1° and δψ≈+0.1°, similar to the Cu/O and Cu/CO systems. Three-dimensional island growth leads to a drastical increase of δΔ and δψ by several orders of magnitude. The resistivity first quickly decreases and then slowly reapproaches the initial value. This marked kinetics is quantitatively interpreted on the basis of a diffusion model.