Induced-fit binding of π-electron donor substrates to macrocyclic aromatic ether-imide-sulfones: a versatile approach to molecular assembly

Novel macrocyclic receptors which bind electron-donor aromatic substrates via π-stacking donor- acceptor interactions are obtained by cyclo-imidization of an amine-functionalized arylether-sulfone with pyromellitic- and 1,4,5,8-naphthalene-tetracarboxylic dianhydrides. These macrocycles complex with a wide variety of π-donor substrates including tetrathiafulvalene, naphthalene, anthracene, pyrene, perylene, and functional derivatives of these polycyclic hydrocarbons. The resulting supramolecular assemblies range from simple 1:1 complexes, to [2]- and [3]-pseudorotaxanes, and even (as a result of crystallographic disorder) an apparent polyrotaxane. Direct, five-component self-assembly of a metal-centred [3]pseudorotaxane is also observed, on complexation of a macrocyclic ether-imide with 8-hydroxyquinoline in the presence of palladium(II) ions. Binding studies in solution were carried out by 1H NMR and UV-visible spectroscopy, and the stoichiometries of binding were confirmed by Job plots based on charge-transfer absorption bands. The highest association constants are found for strong π-donor guests with large surface-areas, notably perylene and 1-hydroxypyrene, for which Ka values of 1.4 x 103 and 2.3 x 103 M-1 respectively are found. Single crystal X-ray analyses of the receptors and their derived complexes reveal large, induced-fit distortions of the macrocyclic frameworks as a result of complexation. These structures provide compelling evidence for the existence of strong, attractive forces between the electronically-complementary aromatic π-systems of host and guest.

Optical VOCs detection using poly(3-alkylthiophenes) with different side-chain lengths

The use of conjugated polymers in the gas and volatile organic compounds (VOCs) detections represents an advance in the development of the electronic noses. Polythiophenes show good thermal and environmental stability, are easily synthesized and they have been studied as gas and VOCs sensors using different principles or transduction techniques. Among these techniques, optical sensing has been attracted attention, mainly due to its versatility. However, conjugated polymer-based optical sensors are still less studied. This paper describes the use of two poly(3-alkylthiophenes) for VOCs optical detection. The sensing measurements were carried out using visible spectroscopy. Both polymers showed good sensitivity to the VOCs, showing fast and reversible responses with some hysteresis, and were unable to detect hydroxylated samples. Furthermore, it was demonstrated that the thickness of polymer films influences the intensity of the optical response. Although there is similarity in the superficial composition of the polymers films, demonstrated by their surface energies, they showed significant differences in their optical properties upon exposure to the VOCs. (c) 2009 Elsevier B.V. All rights reserved.

Molecular modeling and UV-vis spectroscopic studies on the mechanism of action of reversed chloroquine (RCQ)

Reversed chloroquine (RCQ) is a multiple ligand compound active against chloroquine-sensitive and resistant falciparum malaria. It is composed by a 4-aminoquinoline moiety (like that present in chloroquine (CQ)) joined to imipramine (IMP), a modulating agent that also showed intrinsic antiplasmodial activity against Brazilian Plasmodium falciparum isolates resistant to CQ. Molecular modeling and ultraviolet-visible spectroscopy (UV-vis) studies strongly suggest that the interaction between RCQ and heme is predominant through the quinoline moiety in a mechanism of action similar to that observed for CQ. (C) 2010 Elsevier Ltd. All rights reserved.

Photocatalytic decomposition of methylene blue via Fenton mechanisms by silicon wafer doped with Au and Cu: a theoretical and experimental study

In this work, we studied the photocatalytic and the structural aspects of silicon wafers doped with Au and Cu submitted to thermal treatment. The materials were obtained by deposition of metals on Si using the sputtering method followed by fast heating method. The photocatalyst materials were characterized by synchrotron-grazing incidence X-ray fluorescence, ultraviolet-visible spectroscopy, X-ray diffraction, and assays of H(2)O(2) degradation. The doping process decreases the optical band gap of materials and the doping with Au causes structural changes. The best photocatalytic activity was found for thermally treated material doped with Au. Theoretical calculations at density functional theory level are in agreement with the experimental data.

Complexes of the tripodal nitrilotrimethylenetrisphosphonic (H6L) and P,P',P''-triphenylnitrilotrimethylenetrisphosphinic (H3L) acids with the copper(II) ion. Synthesis and charaterization of [Hpy][Cu(H3L)(H2O)] and [Cu(HL)(py)]2.2Me2CO

The complexes [Hpy][Cu(H₃L)(H2O)] 1 (L⁶ = nitrilotrimethylenetrisphosphonate) and [Cu(HL°)(py)]₂·2Me₂CO 2 [(L°)³ = P,P,P" -triphenylnitrilotrismethylenetrisphosphinate)] have been isolated and characterized by X-ray crystallography, near IR-visible spectroscopy and magnetic measurements. The structure determination has shown the complexes to be constituted by monomeric and dimeric units respectively. In the monomer the metal atom is surrounded by the phosphonate ligand and a water molecule, with a geometry between a trigonal bipyramid and a square pyramid. The two copper atoms in the dimer are held together by an arm of the tripod ligand, with a pyridine molecule as additional ligand, and display octahedral geometry. The presence of monomeric and dimeric species in aqueous solutions of 1 and 2 has been shown by ESMS studies. The formation in water solution of the dimer [{Cu(H₃L)}₂]^2-, as a minor species, has been supported by potentiometric measurements, whereas only the monomeric anion [CuL°] has been ascertained to be present. In general the ligand H₃L° forms less stable copper(II) complexes than H₆L.

Photodegradation, interaction with iron oxides and bioavailability of dissolved organic matter from forested floodplain sources

Photochemical degradation of dissolved organic matter (DOM) can influence food webs by altering the availability of carbon to microbial communities, and may be particularly important following periods of high DOM input (e.g. flooding of forested floodplains). Iron oxides can facilitate these reactions, but their influence on subsequent organic products is poorly understood. Degradation experiments with billabong (= oxbow lake) water and river red gum (Eucalyptus camaldulensis) leaf leachate were conducted to assess the importance of these reactions in floodplain systems. Photochemical degradation of DOM in sunlight-irradiated quartz tubes (with and without amorphous iron oxide) was studied using gas chromatography and UV-visible spectroscopy. Photochemical reactions generated gaseous products and small organic acids. Bioavailability of billabong DOM increased following irradiation, whereas that of leaf leachate was not significantly altered. Fluorescence excitation-emission spectra suggested that the humic component of billabong organic matter was particularly susceptible to degradation, and the source of DOM influenced the changes observed. The addition of amorphous iron oxide increased rates of photochemical degradation of leachate and billabong DOM. The importance of photochemical reactions to aquatic systems will depend on the source of the DOM and its starting bioavailability, whereas inputs of freshly formed iron oxides will accelerate the processes.

Synthesis and characterization of surface-enhanced Raman-scattered gold nanoparticles

In this paper, we report a simple, rapid, and robust method to synthesize surface-enhanced Raman-scattered gold nanoparticles (GNPs) based on green chemistry. Vitis vinifera L. extract was used to synthesize noncytotoxic Raman-active GNPs. These GNPs were characterized by ultraviolet-visible spectroscopy, dynamic light-scattering, Fourier-transform infrared (FTIR), transmission electron microscopy (TEM), X-ray diffraction (XRD), and Raman spectroscopy. The characteristic surface plasmon-resonance band at ~528 nm is indicative of spherical particles, and this was confirmed by TEM. The N–H and C–O stretches in FTIR spectroscopy indicated the presence of protein molecules. The predominant XRD plane at (111) and (200) indicated the crystalline nature and purity of GNPs. GNPs were stable in the buffers used for biological studies, and exhibited no cytotoxicity in noncancerous MIO-M1 (Müller glial) and MDA-MB-453 (breast cancer) cell lines. The GNPs exhibited Raman spectral peaks at 570, 788, and 1,102 cm-1. These new GNPs have potential applications in cancer diagnosis, therapy, and ultrasensitive biomarker detection.

An improved understanding of the dispersion of multi-walled carbon nanotubes in non-aqueous solvents

The homogeneous and stable dispersion of carbon nanotubes (CNTs) in solvents is often a prerequisite for their use in advanced materials. Dispersion procedures, reagent concentration as well as the interactions among reagent, defective CNTs and near-perfect CNTs will affect the resulting CNT dispersion properties. This study, for the first time, presents a detailed comparison between two different approaches for dispersing CNTs. The results enhance our understanding of the interactions between surfactant, defective CNTs and near-perfect CNTs and thus provide insight into the mechanism of CNT dispersion. Dispersions of "as-produced" short multi-walled carbon nanotubes (MWCNTs) in N,N-dimethylformamide were prepared by two different surfactant (Triton X-100) assisted methods: ultrasonication and ultrasonication followed by centrifugation, decanting the supernatant and redispersing the precipitate. Visual observation and UV-visible spectroscopy results showed that the latter method produce a more stable dispersion with higher MWCNT content compared to dispersions produced by ultrasonication alone. Transmission electron microscopy and Raman spectroscopic investigations revealed that the centrifugation/ decanting step removed highly defective nanotubes, amorphous carbon and excess surfactant from the readily re-dispersible near-perfect CNT precipitate. This is contrary to other published findings where the dispersed MWCNTs were found in the supernatant. Thermogravimetric analysis showed that 95 % of Triton X-100 was removed by centrifugation/decanting step, and the remainder of the Triton X-100 molecules is likely randomly adsorbed onto the MWCNT surface. Infrared spectral analysis suggests that the methylene groups of the polyoxyethylene (aliphatic ether) chains of the residual Triton X-100 molecules are interacting with the MWCNTs. © 2014 Springer Science+Business Media.

Determination of lipophilic and hydrophilic antioxidants in Solanum Lycopersicum L. tomato from Gordal variety by LL-USAE combined with UHPLC-PDA/FLR

Tomato (Lycopersicon esculentum L.) is one of the main constituents of the Mediterranean diet. Its consumption has been proposed to reduce the risk of cardiovascular diseases and certain types of cancer. It is therefore one of the most popular and extensively consumed vegetable crop worldwide. To gain insights on the potential of Lycopersicon esculentum L. as bioactive food, two analytical methodologies were developed to determine the levels of the lipophilic -tocopherol, α-tocopherol, β-carotene, lycopene; and hydrophilic antioxidants ascorbic acid. The quantification of total carotenoids (β-carotene and lycopene) was assessed through a liquid–liquid ultrasound assisted extraction (LL-USAE) in combination with ultraviolet-visible spectroscopy (UV-Vis), according to method of mean, for total carotenoids (λmáx = 450 nm. The ultra-high performance liquid chromatographic using both photodiode array and fluorescence detection (UHPLC-PDA/FLR), allows the identification and quantification of the target lipophilic and hydrophilic antioxidants. This methodology UHPLC-PDA/FLR is fast, simple and revealed a high sensitivity for the compounds under study. The limits of detection (LODs) and quantification (LOQs) obtained were much lower (about 10 times) than the reported in literature. The method LL-USAE/UV-Vis was validated and applied to different tomato foodstuffs. The results reveal a small increase of carotenoids content during maturation, reaching the maximum level when ripe. These results complement those obtained by the ORAC and TBARS assays that show an increase of antioxidant capacity during maturation. The LODs ans LOQs obtained were also about 10 times lower than reported in literature. The carotenoid content was also evaluated by LL-USAE/UV-Vis in different tomatoes varieties. Regional variety present the high carotenoid level, followed by campari and gordal, and at last grape. This methodology was also applied to different processed food samples containing tomatoes derivatives. Highest carotenoids content were obtained in concentrated tomato foodstuffs.

PEGylated polyethyleneimine-entrapped gold nanoparticles for enhanced and targeted gene delivery applications

Gene therapy, which involves the transfer of nucleic acid into target cells in patients, has become one of the most important and widely explored strategies to treat a variety of diseases, such as cancer, infectious diseases and genetic disorders. Relative to viral vectors that have high immunogenicity, toxicity and oncogenicity, non-viral vectors have gained a lot of interest in recent years. This is largely due to their ability to mimic viral vector features including the capacity to overcome extra- and intra-cellular barriers and to enhance transfection efficiency. Polyethyleneimine (PEI) has been extensively investigated as a non-viral vector. This cationic polymer, which is able to compact nucleic acid through electrostatic interactions and to transport it across the negatively charged cell membranes, has been shown to effectively transfect nucleic acid into different cell lines. Moreover, entrapment of gold nanoparticles (Au NPs) into such an amine-terminated polymer template has been shown to significantly enhance gene transfection efficiency. In this work, a novel non-viral nucleic acid vector system for enhanced and targeted nucleic acid delivery applications was developed. The system was based on the functionalization of PEI with folic acid (FA; for targeted delivery to cancer cells overexpressing FA receptors on their surface) using polyethylene glycol (PEG) as a linker molecule. This was followed by the preparation of PEI-entrapped Au NPs (Au PENPs; for enhancement of transfection efficiency). In the synthesis process, the primary amines of PEI were first partially modified with fluorescein isothiocyanate (FI) using a molar ratio of 1:7. The formed PEI-FI conjugate was then further modified with either PEG or PEGylated FA using a molar ratio of 1:1. This process was finally followed by entrapment of Au NPs into the modified polymers. The resulting conjugates and Au PENPs were characterized by several techniques, namely Nuclear Magnetic Resonance, Dynamic Light Scattering and Ultraviolet-Visible Spectroscopy, to assess their physicochemical properties. In the cell biology studies, the synthesized conjugates and their respective Au PENPs were shown to be non-toxic towards A2780 human ovarian carcinoma cells. The role of these materials as gene delivery agents was lastly evaluated. In the gene delivery studies, the A2780 cells were successfully transfected with plasmid DNA using the different vector systems. However, FA-modification and Au NPs entrapment were not determinant factors for improved transfection efficiency. In the gene silencing studies, on the other hand, the Au PENPs were shown to effectively deliver small interfering RNA, thereby reducing the expression of the B-cell lymphoma 2 protein. Based on these results, we can say that the systems synthesized in this work show potential for enhanced and targeted gene therapy applications.

Langmuir and Langmuir-Blodgett films containing a porphyrin-ruthenium complex

The fabrication of supramolecular structures from the tetraruthenated porphyrin-containing phosphines, {TPyP[RuCl3(dppb)](4)}, RuTPyP, is demonstrated with Langmuir and Langmuir-Blodgett films. The surface pressure-molecular area isotherms (pi-A) point to an edge-on arrangement for the RuTPyP molecules in the condensed state. Weak aggregation in the Langmuir films was indicated by non-zero surface potentials at large areas per molecule and a slight red shift in the ultraviolet-visible absorption spectrum in comparison to the spectrum in solution. Further aggregation occurs in the Z-type Lang muir-Blodgett films, which was confirmed with ultraviolet-visible spectroscopy of the deposited films. Fourier transform infrared and Raman spectroscopic data for powder and Langmuir-Blodgett films indicate that the RuTPyP molecules are chemically stable in Langmuir-Blodgett films regardless of the contact with water during film fabrication. The nanostructured nature of the Langmuir-Blodgett films was manifested in cyclic voltammetry due to the high sensitivity of the metallic centers in RuTPyR Electrodes modified with Langmuir-Blodgett films exhibit an anodic peak at 100 mV and a cathodic peak at 7 mV, which is assigned to RuIII/RuII redox processes. Furthermore, Langmuir-Blodgett films from RuTPyP showed electrocatalytic activity for oxidation of benzyl alcohol, illustrated by a large shift of 100 mV in the anodic peak at 400 mV, while electropolymerized and cast films of the same compound displayed smaller and no activities, respectively.

Order-disorder degree of self-assembled clusters: Influence on photoluminescence emission and morphology of BaxSr1-xTiO3 nanocrystals

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Study of optical properties and molecular structure of plasma polymerized diethylene glycol dimethyl ether

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Avaliação das propriedades físico-químicas de sistemas a base de carboximetilcelulose e poli (N-isopropilacrilamida) em soluções aquosas para aplicação na indústria do petróleo

Sustainable development is a major challenge in the oil industry and has aroused growing interest in research to obtain materials from renewable sources. Carboxymethylcellulose (CMC) is a polysaccharide derived from cellulose and becomes attractive because it is water-soluble, renewable, biodegradable and inexpensive, as well as may be chemically modified to gain new properties. Among the derivatives of carboxymethylcellulose, systems have been developed to induce stimuli-responsive properties and extend the applicability of multiple-responsive materials. Although these new materials have been the subject of study, understanding of their physicochemical properties, such as viscosity, solubility and particle size as a function of pH and temperature, is still very limited. This study describes systems of physical blends and copolymers based on carboxymethylcellulose and poly (N-isopropylacrylamide) (PNIPAM), with different feed percentage compositions of the reaction (25CMC, 50CMC e 75CMC), in aqueous solution. The chemical structure of the polymers was investigated by infrared and CHN elementary analysis. The physical blends were analyzed by rheology and the copolymers by UV-visible spectroscopy, small-angle X-ray scattering (SAXS), dynamic light scattering (DLS) and zeta potential. CMC and copolymer were assessed as scale inhibitors of calcium carbonate (CaCO3) using dynamic tube blocking tests and chemical compatibility tests, as well as scanning electron microscopy (SEM). Thermothickening behavior was observed for the 50 % CMC_50 % PNIPAM and 25 % CMC_75 % PNIPAM physical blends in aqueous solution at concentrations of 6 and 2 g/L, respectively, depending on polymer concentration and composition. For the copolymers, the increase in temperature and amount of PNIPAM favored polymer-polymer interactions through hydrophobic groups, resulting in increased turbidity of polymer solutions. Particle size decreased with the rise in copolymer PNIPAM content as a function of pH (3-12), at 25 °C. Larger amounts of CMC result in a stronger effect of pH on particle size, indicating pH-responsive behavior. Thus, 25CMC was not affected by the change in pH, exhibiting similar behavior to PNIPAM. In addition, the presence of acidic or basic additives influenced particle size, which was smaller in the presence of the additives than in distilled water. The results of zeta potential also showed greater variation for polymers in distilled water than in the presence of acids and bases. The lower critical solution temperature (LCST) of PNIPAM determined by DLS corroborated the value obtained by UV-visible spectroscopy. SAXS data for PNIPAM and 50CMC indicated phase transition when the temperature increased from 32 to 34 °C. A reduction in or absence of electrostatic properties was observed as a function of increased PNIPAM in copolymer composition. Assessment of samples as scale inhibitors showed that CMC performed better than the copolymers. This was attributed to the higher charge density present in CMC. The SEM micrographs confirmed morphological changes in the CaCO3 crystals, demonstrating the scale inhibiting potential of these polymers