Stability of nano-sized permethrin in its colloidal state and its effect on the physiological and biochemical profile of Culex tritaeniorhynchus larvae.

The occurrence of pesticidal pollution in the environment and the resistance in the mosquito species makes an urge for the safer and an effective pesticide. Permethrin, a poorly water-soluble pyrethroid pesticide, was formulated into a hydrodispersible nanopowder through rapid solvent evaporation of pesticide-loaded oil in water microemulsion. Stability studies confirmed that the nanopermethrin dispersion was stable in paddy field water for 5 days with the mean particle sizes of 175.3 ± 0.75 nm and zeta potential of -30.6 ± 0.62 mV. The instability rate of the nanopermethrin particles was greater in alkaline (pH 10) medium when compared with the neutral (pH 7) and acidic (pH 4) dispersion medium. The colloidal dispersion at 45°C was found to be less stable compared with the dispersions at 25 and 5°C. The 12- and 24-h lethal indices (LC50) for nanopermethrin were found to be 0.057 and 0.014 mg l-1, respectively. These results were corroborative with the severity of damages observed in the mosquito larvae manifested in epithelial cells and the evacuation of the midgut contents. Further, the results were substantiated by the decrease in cellular biomolecules and biomarker enzyme activity in nanopermethrin treated larvae when compared to bulk and control treatment.

Formation of hydrophilic nanofibers from nanoemulsions through electrospinning.

This study presents a method for one step incorporation of lipophilic compounds in hydrophilic nanofibers. By this method nanodroplets of oil and of volatile solvent are entrapped within polymer nanofibers during an electrospinning process. While performing the process with a volatile oil with dissolved lipophilic material, such as the drug celecoxib, nanofiber-nanoparticle composites are formed. The polymer used to form the fibers is a high molecular weight poly(vinyl alcohol) which enables rapid dissolution and release of the incorporated lipophilic material. The resulting celecoxib nanoparticles that are embedded within the nanofiber are amorphous and their average size is in between 21 and 93 nm, thus potentially lead to their increased dissolution rate. The preparation of such a solid matrix containing nanodroplets or nanoparticles may be applied as a fast dissolving delivery system for water insoluble materials.

Active curcumin nanoparticles formed from a volatile microemulsion template.

We report on biological performance of organic nanoparticles formed by a simple method based on rapid solvent removal from a volatile microemulsion. The particular focus of the study was on testing the suitability of the method for substances soluble in partially water-miscible organic solvents as well as on evaluating the therapeutic activity of the resultant nanoparticles. Curcumin was employed as a model for hydrophobic drug, and, as it is soluble in water-miscible organic solvents, it was successfully incorporated into a new cyclopentanone-water microemulsion system. During rapid solvent removal by spray-drying, the nanometric droplets of the microemulsion were converted into nanoparticles containing amorphous curcumin with the average size of 20.2±3.4 nm, having ζ potential of -36.2 ±1.8 mV. These nanoparticles were dispersible in water and retained the high loading of the active substance. The therapeutic activity of the resulting nanoparticles was demonstrated in a pancreatic cancer cell line Panc-1. The effective concentration for reducing the metabolic activity was found to be 11.5 µM for nanoparticles compared with 19.5 µM for free curcumin.

Three-dimensional printing of scintillating materials.

We demonstrate, for the first time, the applicability of three-dimensional printing techniques to the manufacture of scintillation detectors. We report on the development of a formulation, usable in stereolithographic printing, that exhibits scintillation efficiency on the order of 30% of that of commercial polystyrene based scintillators. We discuss the applicability of these techniques and propose future enhancements that will allow tailoring the printed scintillation detectors to various applications.

VO2/Si-Al gel nanocomposite thermochromic smart foils: largely enhanced luminous transmittance and solar modulation.

VO2 nanoparticles with a dimension of approximately 20 nm were obtained by simple mechanical bead-milling method, which were well dispersed in transparent silica-alumina (Si-Al) gel matrix to form nanocomposites. The VO2/Si-Al gel thermochromic nanocomposite foils were fabricated with various VO2 solid contents and foil thickness. With 10% VO2 loading and 3 µm foil thickness, high luminous transmittance (T(lum(20°C))=63.7% and T(lum(90°C))=54.4%), and large solar modulation ability (ΔTsol=12%) can be obtained which surpasses the best reported results (nanoporous films:T(lum(20°C))=43.3%, T(lum(90°C))=39.9% and ΔTsol=14.1%). This current approach provided a simple and scalable preparation method with the best combined thermochromic performance.

Regulation of acid phosphatase in reverse micellar system by lipids additives: structural aspects.

Reverse micelles system is suggested as a direct tool to study the influence of membrane matrix composition on the activity and structure of membrane-associated enzymes with the use of acid phosphatase (AP) as an example. In reverse micelles the functioning of the monomeric and dimeric forms of AP could be separately observed by variation of the size of the micelles. We found that including the lipids into the micellar system can dramatically affect the enzyme functioning even at low lipid content (2% w/w), and this effect depends on the lipid nature. Structural studies using CD spectroscopy and DLS methods have shown that the influence of lipid composition on the enzyme properties might be caused by the interaction of lipids with the enzyme as well as by the influence of lipids on structure and properties of the micellar matrix.

Nanostructures formed by self-assembly of negatively charged polymer and cationic surfactants.

The formation of nanoparticles by interaction of an anionic polyelectrolyte, sodium polyacrylate (NaPA), was studied with a series of oppositely charged surfactants with different chain lengths, alkyltrimethylammonium bromide (CnTAB). The binding and formation of nanoparticles was characterized by dynamic light scattering, zeta-potential, and self-diffusion NMR. The inner nanostructure of the particles was observed by direct-imaging cryogenic-temperature transmission electron microscopy (cryo-TEM), indicating aggregates of hexagonal liquid crystal with nanometric size.

Induced crystallization of polyelectrolyte-surfactant complexes at the gas-water interface.

Synchrotron x-ray and surface-tension studies of a strong polyelectrolyte (PE) in the semidilute regime (approximately 0.1 M monomer charges) with varying surfactant concentrations show that minute surfactant concentrations induce the formation of a PE-surfactant complex at the gas-solution interface. X-ray reflectivity and grazing angle x-ray diffraction show the complex PE-surfactant resides at the interface and the alkyl chains of the surfactant form a two-dimensional liquidlike monolayer. With the addition of salt (NaCl), columnar crystals with distorted-hexagonal symmetry are formed.

Structure of microemulsions with gemini surfactant studied by solvatochromic probe and diffusion NMR.

The structure of microemulsions prepared by the anionic gemini surfactant didodecyl diphenyl ether disulfonate (C12-DADS) was investigated by a solvatochromic probe and nuclear magnetic resonance (NMR) diffusion measurements. The NMR measurements indicate the presence of bicontinuous and oil-in-water microemulsions depending on microemulsion composition. The absorbance spectra of the solvatochromic probe, Nile red, indicate the solubilization of the probe in different sites, in agreement with the NMR findings. It was also found that the microemulsions were capable of dissolving the hydrophobic probe, Nile red, up to four times better than expected if it were simply dissolved in the toluene phase.

Microstructural characterization of micro- and nanoparticles formed by polymer-surfactant interactions.

We have studied the nano- and microparticles formed by complexation of PDAC [poly(diallyldimethyl-ammoniumchloride)] and SDS (sodium dodecyl sulfate). The complexation phenomenon was characterized by light scattering and zeta-potential measurements. The nature of the complexes was revealed by direct-imaging cryogenic temperature transmission electron microscopy (cryo-TEM), showing nanometric details of the complexes formed around the point of neutralization. The images also reveal how those aggregates are solubilized by excess surfactant, first into faceted particles with threadlike micelles attached to their surfaces, prior to complete solubilization, then into lacelike aggregates, and finally into spheroidal micelles. The nanostructure of the complexes strongly suggests they are made of a hexagonal liquid crystalline phase. This was further supported by small-angle X-ray scattering (SAXS).

Native and Hydrophobically Modified Human Immunoglobulin G at the Air/Water Interface.

The adsorption of human immunoglobulin G (IgG) at the air/water interface was monitored both by the in situ radiotracer technique using [(14)C] labeled IgG and by surface tension measurements. The results reveal that adsorption of IgG from single protein systems displays bimodality due to molecular rearrangements at the interface. Above the threshold value of 1.5x10(-2) mg/ml solution concentration, adsorbed IgG molecules reoriented from the side-on to the end-on configuration. The existence of a lag time which did not appear in Gamma=f(t) curves, was observed in Pi=f(t) relationships at low protein concentrations and was due to the limits of the surface pressure technique to detect protein adsorption. The adsorption of native IgG was also carried out in the presence of a hydrophobized IgG obtained by grafting capryloyl residues to its lysine groups by reaction with N-hydroxysuccinimide ester of caprylic acid, which yielded 19 covalently bound alkyl chains to the IgG molecule (19C(8)-IgG). This modified IgG exhibited enhanced adsorption at the air/water interface, as manifested by its increased adsorption efficiency relative to the native protein. Sequential and competitive adsorption experiments from binary mixtures of native IgG and 19C(8)-IgG clearly demonstrate that the displacement of the native protein from the air/water interface strongly depended on the manner of how 19C(8)-IgG and native IgG competed with each other. When the two proteins competed simultaneously, 19C(8)-IgG predominantly occupied the available area but when native IgG was adsorbed first, for 2 h, the sequentially adsorbed 19C(8)-IgG was incapable of substantially displacing it from the interface. Copyright 2001 Academic Press.

Chemically Modified Glucose Oxidase with Enhanced Hydrophobicity: Adsorption at Polystyrene, Silica, and Silica Coated by Lipid Monolayers.

Covalent modification of glucose oxidase from Aspergillus niger by the palmitic acid ester of N-hydroxysuccinimide at a molar ratio ester:protein of 56:1 results in the formation of the enzyme derivative with 11 attached palmitic chains. Surface hydrophobicity measurements by a fluorescent probe, 8-anilino-1-naphthalenesulfonate, indicate a drastic increase in the hydrophobicity index of glucose oxidase after such a modification. The modified glucose oxidase displays a much higher adsorption affinity for hydrophilic (silica) as well as for hydrophobic (silica coated by phosphatidyl choline and cholesterol monolayers and polystyrene latex beads) surfaces, and forms more compact surface layers compared to the native glucose oxidase. Such a difference results from a spontaneous formation of micelle-like aggregates (clusters) of the hydrophobized enzyme molecules (average size 500 nm), which come into contact with a surface. A possible structure of the glucose oxidase surface layers and the nature of the forces determining the adsorption of the enzyme on various adsorbents are discussed. Copyright 1999 Academic Press.

Chemically Modified Human Immunoglobulin G: Hydrophobicity and Surface Activity at Air/Solution Interface.

Covalent modification of human IgG by fatty acid esters (C8 and C16) of N-hydroxysuccinimide was carried out. Surface hydrophobicity measurements, using the fluorescent probe 8-anilino-1-naphthalenesulfonate, indicate an increase in the surface protein hydrophobicity with an increase in the number and in the length of the attached alkyl chains. The modified IgGs decrease surface tension at the air/solution interface more effectively than the native protein. The values of the molecular cross-sectional areas (DeltaA) estimated from the kinetic data are in the range of 100-300 Å2 and reflect the size of protein segments at the interface during the adsorption process. About 40-50% increase in the DeltaA was observed upon attachment of the C8 groups to the native IgG. The lengthening of the bound alkyl chain from C8 to C16 results in a further increase in this value. The influence of the overall IgG hydrophobicity and the length of the attached alkyl chain on the dimensions of the mobile protein segment at the surface are discussed. Copyright 1999 Academic Press.

Penetration of Glucose Oxidase and of the Hydrophobically Modified Enzyme into Phospholipid and Cholesterol Monolayers.

The penetrant ability of the native glucose oxidase, GOx, and of the hydrophobically modified enzyme GO(mod) realized by grafting to its lysine residues alkyl C16 chains, into phosphatidylcholine dibehenoyl (DBPC), phosphatidylcholine dipalmitoyl (DPPC), phosphatidyl-ethanolamine dipalmitoyl (DPPE), phosphatidyl-serine dipalmitoyl (DPPS), and cholesterol (CHOL) monolayers was assessed by surface pressure measurements at constant area by enzyme injection to the aqueous phase beneath spread monolayers. As revealed by the magnitude of surface pressure increments (DeltaPi), both the quantities and the rates of penetration of the enzymes into these monolayers were lipid chemical nature and enzyme concentration dependent. When compared with GOx, GO(mod) displayed an enhanced penetrant ability into all the studied monolayers that resulted in rapidly attained DeltaPi plateau values, characteristic of stable systems. The influence of lipid hydrocarbon chain length and of the polar headgroup charge on the efficiency and effectiveness of GOx and GO(mod) penetration into these monolayers is discussed. Copyright 1999 Academic Press.

Formation of Surface Active Gelatin by Covalent Attachment of Hydrophobic Chains

Surface active gelatin was formed by covalent attachment of hydrophobic groups to gelatin molecules. The modification was carried out at various degrees of attachment and with various chain lengths. These modified gelatins (MGs) were synthesized in dry DMSO by a simple and rapid method. The new method leads to high yields and allows high degrees of modification. The MGs, which have various hydrophobicities, have better surface activity than the native gelatin, as determined by surface tension reduction. The surface tension reduction is correlated to the hydrophobicity of the modified molecule, which was determined by a fluorescent probe. It appears that both the increase in the number of the hydrophobic groups and the increase in the chain lengths lead to decreased surface tension. Copyright 1997 Academic Press. Copyright 1997Academic Press

Adsorption of Hydrophobized Glucose Oxidase at Solution/Air Interface

The modification of glucose oxidase by palmitic acid ester of N -hydroxysuccinimide leads to the formation of a new hydrophobized enzyme with five covalently bound C16 groups. Such a modification was shown not to alter noticeably the native structure of the enzyme. The modified glucose oxidase displays enhanced surface activity at the water/air interface in comparison with the native enzyme. The maximum reduction of surface tension at all concentrations studied was higher for the modified glucose oxidase than for the native one. The modified enzyme also displayed a much steeper rise of the surface potential with time and a much more rapid attainment of the saturation plateau than the unmodified enzyme.

Formation of positively charged microcapsules based on chitosan-lecithin interactions.

The formation of microcapsules which contain rosemary oil, is herewith described. The process is based on two steps: (a) formation of oil-in-water emulsions, by using lecithin as emulsifier, thus imparting negative charges on the oil droplets; (b) addition of a cationic biopolymer, chitosan, in conditions that favor the formation of an insoluble chitosan-lecithin complex. Zeta potential measurements revealed that addition of very low concentrations of chitosan to lecithin stabilized emulsions, led to reversal of charge. At a suitable pH range the chitosan precipitated around the oil droplets, forming positively charged microcapsules. The chitosan-lecithin insoluble complex is composed of a 1:1 molar ratio of the chitosan monomeric unit and lecithin, as evaluated by elementary analysis and turbidity measurements.

Solubilization in Colloidal Immunoclusters

Micelle-like clusters of antibody molecules were prepared by covalent attachment of various hydrophobic groups to the protein molecules. These colloidal clusters were capable of solubilizing two hydrophobic probes, while the solubilizate:solubilizer molar ratio was dependent on the chain length of the hydrophobic groups, the degree of modification, and hence, on the size of the colloidal clusters. By using a fluorescent solubilizate, it was demonstrated that the immunoclusters may have a specific recognition ability.

Dead Sea mineral-based cosmetics--facts and illusions.

Modern Dead Sea cosmetics have developed in order to meet the demands of new regulations, technical opportunities, and today's consumer expectations for higher quality standards and proven performance. As an example of the application of this approach, the authors describe the development of a new cosmetic formulation, based on "Osmoter", a special Dead Sea mineral composition, and the evaluation of this formulation's effect on the depth of skin wrinkles, by a controlled assay. Possible mode of action is discussed.

Microencapsulation of O/W emulsions by formation of a protein-surfactant insoluble complex.

A method for obtaining microcapsules of oil droplets by the formation of an insoluble complex of protein-surfactant is described. The gelatin type A studied, which is positively charged at the pH range studied, may form insoluble and soluble complexes with sodium dodecyl sulphate (SDS), an anionic surfactant. The binding isotherms were studied and the specific molar ratios of SDS to gelatin, in which the insoluble complex is formed, was determined. These specific ratios also led to the formation of microcapsules, in which the wall encapsulating the oil droplets, is composed of the insoluble gelatin SDS complex.