Allelopathic potential of bark and leaves of Esenbeckia leiocarpa Engl. (Rutaceae)

We investigated the inhibitory potential of aqueous extracts of bark and leaves of Esenbeckia leiocarpa Engl. on lettuce germination and early seedling growth. We compared the effects of four concentrations (100, 75, 50 and 25%) of each extract to water and polyethylene glycol (PEG 6000) solution controls for four replicates of 50 seeds tor germination and four replicates of ten seedlings for seedling growth. The inhibitory effects of E. leiocarpa extracts on the percentage of germination and on the germination speed seemed to be inure than simply an osmotic effect, except for the percentage of seeds germinated in bark extracts. When compared to water control. both bark and leaf extracts delayed germination, and leaf extracts also affected the percentage of germinated seeds. Leaf ex tracts of all concentrations strongly inhibited the development of seedlings and caused them some degree of abnormality; bark extracts also caused abnormalities and reduced seedling growth. Root development was more sensitive to the extracts than hypocotyl growth. The negative effects of leaf extracts on germination and seedling growth were more pronounced than those of bark extracts, and the overall effects of both extracts were positively correlated with extract concentrations.

A poloxamer/chitosan in situ forming gel with prolonged retention time for ocular delivery

The aim of the present work was to obtain an ophthalmic delivery system with improved mechanical and mucoadhesive properties that could provide prolonged retention time for the treatment of ocular diseases. For this, an in situ forming gel comprised of the combination of a thermosetting polymer, poly (ethylene oxide)-poly (propylene oxide)-poly (ethylene oxide) (PEO-PPO-PEO, poloxamer), with a mucoadhesive agent (chitosan) was developed. Different polymer ratios were evaluated by oscillatory rheology, texture and mucoadhesive profiles. Scintigraphy studies in humans were conduced to verify the retention time of the formulations developed. The results showed that chitosan improves the mechanical strength and texture properties of poloxamer formulations and also confers mucoadhesive properties in a concentration-dependent manner. After a 10-min instillation of the poloxamer/chitosan 16:1 formulation in human eyes, 50-60% of the gel was still in contact with the cornea surface, which represents a fourfold increased retention in comparison with a conventional solution. Therefore, the developed formulation presented adequate mechanical and sensorial properties and remained in contact with the eye surface for a prolonged time. In conclusion, the in situ forming gel comprised of poloxamer/chitosan is a promising tool for the topical treatment of ocular diseases. (C) 2010 Elsevier B.V. All rights reserved.

Calcium Carbonate Particle Growth Depending on Coupling among Adjacent Layers in Hybrid LB/LbL Films

There are practical and academic situations that justify the study of calcium carbonate crystallization and especially of systems that are associated with organic matrices and a confined medium. Despite the fact that many different matrices have been studied, the use of well-behaved, thin organic films may provide new knowledge about this system. In this work, we have studied the growth of calcium carbonate particles on well-defined organic matrices that were formed by layer-by-layer (LbL) polyelectrolyte films deposited on phospholipid Langmuir-Blodgett films (LB). We were able to change the surface electrical charge density of the LB films by changing the proportions of a negatively charged lipid, the sodium salt of dimyristoyl-sn-glycero-phosphatidyl acid (DMPA), and a zwitterionic lipid. dimyristoyl-sn-glycero-phosphatidylethanolamine (DMPE). This affects the subsequent polyelectrolyte LbL film deposition, which also changes the the nature of the bonding (electrostatic interaction or hydrogen bonding). This approach allowed for the formation of calcium carbonate particles of different final shapes, roughnesses, and sizes. The masses of deposited lipids, polyelectrolytes, and calcium cabonate were quantified by the quartz crystal microbalance technique. The structures of obtained particles were analyzed by scanning electron microscopy.

Tripolyphosphate as precursor for REPO4: Eu3+ (RE = Y, La, Gd) by a polymeric method

A modification of the Pechini method was applied to obtain luminescent rare earth orthophosphates. The developed synthetic route is based on the ability of the tripolyphosphate anion (P3O105-) to act both as a complexing agent and as an orthophosphate precursor. Heating of aqueous solutions containing RE3+, Eu3+, P3O105-, citric acid, and ethylene glycol led to polymeric resins. The ignition of these resins at different temperatures yielded luminescent orthophosphates. The produced nanosized phosphors (YPO4:Eu3+, (Y,Gd)PO4:Eu3+, and LaPO4:Eu3+) were analyzed by infrared and luminescence spectroscopies, X-ray diffractometry, and scanning electron microscopy.

Self-assembled films from WO(3): Electrochromism and lithium ion diffusion

WO(3)/chitosan and WO(3)/chitosan/poly(ethylene oxide) (PEO) films were prepared by the layer-by-layer method. The presence of chitosan enabled PEO to be carried into the self-assembled structure, contributing to an increase in the Li(+) diffusion rate. On the basis of the galvanostatic intermittent titration technique (GITT) and the quadratic logistic equation (QLE), a spectroelectrochemical method was used for determination of the ""optical"" diffusion coefficient (D(op)), enabling analysis of the Li(+) diffusion rate and, consequently, the coloration front rate in these host matrices. The D(op) values within the WO(3)/chitosan/PEO film were significantly higher than those within the WO(3)/chitosan film, mainly for higher values of injected charge. The presence of PEO also ensured larger accessibility to the electroactive sites, in accordance with the method employed here. Hence, this spectroelectrochemical method allowed us to separate the contribution of the diffusion process from the number of accessible electroactive sites in the materials, thereby aiding a better understanding of the useful electrochemical and electrochromic properties of these films for use in electrochromic devices. (C) 2010 Elsevier B.V. All rights reserved.

Fluorescence spectroscopy of small peptides interacting with microheterogeneous micelles

Many peptides containing tryptophan have therapeutic uses and can be studied by their fluorescent properties. The biological activity of these peptides involves interactions with many cellular components and micelles can function as carriers inside organisms. We report results from the interaction of small peptides containing tryptophan with several microheterogeneous systems: sodium dodecyl sulphate (SDS) micelles; sodium dodecyl sulphate-poly(ethylene oxide) (SDS-PEO) aggregates; and neutral polymeric micelles. We observed that specific parameters, such as wavelength of maximum emission and fluorescence anisotropy, could be used to ascertain the occurrence of interactions. Affinity constants were determined from changes in the intensity of emission while structural modifications in rotameric conformations were verified from time-resolved measurements. Information about the location and diffusion of peptides in the microheterogeneous systems were obtained from tryptophan emission quenching experiments using N-alkylpyridinium ions. The results show the importance of electrostatic and hydrophobic effects, and of the ionization state of charged residues, in the presence of anionic and amphiphilic SDS in the microheterogeneous systems. Conformational stability of peptides is best preserved in the interaction with the neutral polymeric micelles. (C) 2009 Elsevier B.V. All rights reserved.

Interaction of adrenocorticotropin peptides with microheterogeneous systems - A fluorescence study

Adrenocorticotropin (ACM) and alpha-melanocyte stimulating hormone (alpha-MSH) are peptides which present many physiological effects related to pigmentation, motor and sexual behavior, learning and memory, analgesia, anti-inflammatory and antipyretic processes. The 13 amino acid residues of alpha-MSH are the same initial sequence of ACM and due to the presence of a tryptophan residue in position 9 of the peptide chain, fluorescence techniques could be used to investigate the conformational properties of the hormones in different environments and the mechanisms of interaction with biomimetic systems like sodium dodecyl sulphate (SDS) micelles, sodium dodecyl sulphate-poly(ethylene oxide) (SDS-PEO) aggregates and neutral polymeric micelles. In buffer solution, fluorescence parameters were typical of peptides containing tryptophan exposed to the aqueous medium and upon addition of surfactant and polymer molecules, the gradual change of those parameters demonstrated the interaction of the peptides with the microheterogeneous systems. From time-resolved experiments it was shown that the interaction proceeded with conformational changes in both peptides, and further information was obtained from quenching of Trp fluorescence by a family of N-alkylpyridinium ions, which possess affinity to the microheterogeneous systems dependent on the length of the alkyl chain. The quenching of Trp fluorescence was enhanced in the presence of charged micelles, compared to the buffer solution and the accessibility of the fluorophore to the quencher was dependent on the peptide and the alkylpyridinium: in ACTH(1-21) highest collisional constants were obtained using ethylpyridinium as quencher, indicating a location of the residue in the surface of the micelle, while in alpha-MSH the best quencher was hexylpyridinium, indicating insertion of the residue into the non-polar region of the micelles. The results had shown that the interaction between the peptides and the biomimetic systems where driven by combined electrostatic and hydrophobic effects: in ACTH(1-24) the electrostatic interaction between highly positively charged C-terminal and negatively charged surface of micelles; and aggregates predominates over hydrophobic interactions involving residues in the central region of the peptide; in alpha-MSH, which presents one residual positive charge, the hydrophobic interactions are relevant to position the Trp residue in the non-polar region of the microheterogeneous systems. (C) 2008 Elsevier B.V. All rights reserved.

Molecular motion in miscible polymer blends .1. Motion in blends of PEO and PVPh studied by solid-state C-13 T-1 rho measurements

Changes in molecular motion in blends of PEO-PVPh have been studied using measurements of C-13 T-1 rho relaxation times. C-13 T-1 rho relaxation has been confirmed as arising from spin-lattice interactions by observation of the variation in T-1 rho with rf field strength and temperature. In the pure homopolymers a minimum in T-1 rho is observed at ca. 50 K above the glass transition temperatures detected by DSC. After blending, the temperature of the minimum in T-1 rho for PEO increased, while that for PVPh decreased, however, the minima, which correspond to the temperatures where the average correlation times for reorientation are close to 3.1 mu s, are separated by 45 K (in a 45% PEO-PVPh blend). These phenomena are explained in terms of the local nature of T-1 rho measurements. The motions of the individual homopolymer chains are only partially coupled in the blend. A short T-1 rho has been observed for protonated aromatic carbons, and assigned to phenyl rings undergoing large-angle oscillatory motion, The effects of blending, and temperature, on the proportion of rings undergoing oscillatory motion are analyzed.

Vitrification with Glutamine Improves Maturation Rate of Vitrified/Warmed Immature Bovine Oocytes

Contents The current study examined the protective effects of l-glutamine and cytochalasin B during vitrification of immature bovine oocytes. Oocyte vitrification solution (PBS supplemented with 10% FCS, 25% EG, 25% DMSO and 0.5 m trehalose) was the vitrification control. Treatments were the addition of 7 mu g/ml cytochalasin B, 80 mm glutamine or both cytochalasin and glutaminine for 30 s. After warming, oocytes were matured in vitro for 24 h, fixed and stained with Hoechst (33342) for nuclear maturation evaluation. l-glutamine improved the vitrified/warmed immature bovine oocytes viability (32.8%), increasing the nuclear maturation rates compared to other treatments and the no treatment vitrified control (17.4%). There was, however, no effect of cytochalasin B on in vitro maturation (14.4%).

Ultracentrifugal studies of the effect of molecular crowding by trimethylamine N-oxide on the self-association of muscle glycogen phosphorylase b

The suitability of sedimentation equilibrium for characterizing the self-association of muscle glycogen phosphorylase b has been reappraised. Whereas sedimentation equilibrium distributions for phosphorylase b in 40 mM Hepes buffer (pH 6.8) supplemented with 1 mM AMP signify a lack of chemical equilibrium attainment, those in buffer supplemented additionally with potassium sulfate conform with the requirements of a dimerizing system in chemical as we:ll as sedimentation equilibrium. Because the rate of attainment of chemical equilibrium under the former conditions is sufficiently slow to allow resolution of the dimeric and tetrameric enzyme species by sedimentation velocity, this procedure has been used to examine the effects of thermodynamic nonideality arising from molecular crowding try trimethylamine N-oxide on the self-association behaviour of phosphorylase b. In those terms the marginally enhanced extent of phosphorylase b self-association observed in the presence of high concentrations of the cosolute is taken to imply that the effects of thermodynamic nonideality on the dimer-tetramer equilibrium are being countered by those displacing the T reversible arrow R isomerization equilibrium for dimer towards the smaller, nonassociating T state. Because the R state is the enzymically active form, an inhibitory effect is the predicted consequence of molecular crowding by high concentrations of unrelated solutes. Thermodynamic nonideality thus provides an alternative explanation for the inhibitory effects of high concentrations of glycerol, sucrose and ethylene glycol on phosphorylase b activity, phenomena that have been attributed to extremely weak interaction of these cryoprotectants with the T state of the enzyme.

How cracks in SiOx-coated polyester films affect gas permeation

In this paper theoretical models have been established that can account for the gas transmission through nanocomposite laminates, consisting of an oxide layer of finite permeability containing defects, on a polymer sheet of finite thickness. The defect shapes can either be in the form of long cracks or rectangular holes. The models offer a choice of exact numerical calculations or fast and intuitive analytical approximations. The experimental measurements of oxygen permeation through four different SiOx/poly (ethylene terephthalate) samples that were strained to produce distributions or cracks showed good agreement when compared with predicted results from the approximate analytic model. As a consequence of this observation, a key practical conclusion is that, because of the logarithmic dependence of transmission on the width of a crack, for a given strain it is better to have a small number of large cracks rather than a large number of small cracks. (C) 2001 Elsevier Science B.V. All rights reserved.

Gas permeation in silicon-oxide/polymer (SiOx/PET) barrier films: role of the oxide lattice, nano-defects and macro-defects

We propose a model for permeation in oxide coated gas barrier films. The model accounts for diffusion through the amorphous oxide lattice, nano-defects within the lattice, and macro-defects. The presence of nano-defects indicate the oxide layer is more similar to a nano-porous solid (such as zeolite) than silica glass with respect to permeation properties. This explains why the permeability of oxide coated polymers is much greater, and the activation energy of permeation much lower, than values expected for polymers coated with glass. We have used the model to interpret permeability and activation energies measured for the inert gases (He, Ne and Ar) in evaporated SiOx films of varying thickness (13-70 nm) coated on a polymer substrate. Atomic force and scanning electron microscopy were used to study the structure of the oxide layer. Although no defects could be detected by microscopy, the permeation data indicate that macro-defects (>1 nm), nano-defects (0.3-0.4 nm) and the lattice interstices (<0.3 nm) all contribute to the total permeation. (C) 2002 Elsevier Science B.V. All rights reserved.

Novel composites of TiO2 (anatase) and silicate nanoparticles

Thermally stable composite nanostructures of titanium dioxide (anatase) and silicate nanoparticles were prepared from Laponite clay and a sol of titanium hydrate in the presence of poly(ethylene oxide) (PEO) surfactants. Laponite is a synthetic clay that readily disperses in water and exists as exfoliated silicate layers of about 1-nm thick in transparent dispersions of high pH. The acidic sol solution reacts with the clay platelets and leaches out most of the magnesium in the clay, while the sol particles hydrolyze further due to the high pH of the clay dispersion. As a result, larger precursors of TiO2 nanoparticles form and condense on the fragmentized pieces of the leached silicate. Introducing PEO surfactants into the synthesis can significantly increase the porosity and surface area of the composite solids. The TiO2 exists as anatase nanoparticles that are separated by silicate fragments and voids such that they are accessible to organic molecules. The size of the anatase particle can be tailored by manipulating the experimental parameters at various synthesis stages. Therefore, we can design and engineer composite nanostructures to achieve better performance. The composite solids exhibit superior properties as photocatalysts for the degradation of Rhodamine 6G in aqueous solution.

PHB-PEO electrospun fiber membranes containing chlorhexidine for drug delivery applications

Fiber meshes of poly(hydroxybutyrate) (PHB) and poly(hydroxybutyrate)/ poly(ethylene oxide) (PHB/PEO) with different concentrations of chlorhexidine (CHX) were prepared by electrospinning, for assessment as a polymer based drug delivery system. The electrospun fibers were characterized at morphological, molecular and mechanical levels. The bactericidal potential of PHB and PHB/PEO electrospun fibers with and without CHX was investigated against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) by disk diffusion susceptibility tests. Electrospun fibers containing CHX exhibited bactericidal activity. PHB/PEO-1%CHX displayed higher CHX release levels and equivalent antibacterial activity when compared to PHB/PEO with 5 and 10 wt% CHX. Bactericidal performance of samples with 1 wt% CHX was assessed by Colony Forming Units (CFU), where a reduction of 100 % and 99.69 % against E. coli and S. aureus were achieved, respectively.

A new chemical route to synthesise TM-doped (TM = Co, Fe) TiO2 nanoparticles

Since the discovery of ferromagnetism well above room temperature in the Co-doped TiO2 system, diluted magnetic semiconductors based on TiO2 doped with transition metals have generated great interest because of their potential use in the development of spintronic devices. The purpose of this paper is to report on a new and swift chemical route to synthesise highly stable anatase single-phase Co- and Fe-doped TiO2 nanoparticles, with dopant concentrations of up to 10 at.-% and grain sizes that range between 20 and 30 nm. Complementary structural, microstructural and chemical analyses of the different nanopowders synthesised strongly support the hypothesis that a homogeneous distribution of the dopant element in the substitutional sites of the anatase structure has been achieved. Moreover, UV/Vis diffuse reflectance spectra of powder samples show redshifts to lower energies and decreasing bandgap energies with increasing Co or Fe concentration, which is consistent with n-type doping of the TiO2 anatase matrix. Films of Co-doped TiO2 were successfully deposited onto Si (100) substrates by the dip-coating method, with suspensions of Ti1-xCOxO2 nanoparticles in ethylene glycol. ((C)Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).