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Interfacial Properties and Aggregates of Novel Redox-Active Surfactant to Synthesize Silver Nanoparticles at the Air/Water Interface

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Abstract

An anionic and amphiphilic molecule, AQua (AQ-NH-(CH2)10COOH; where AQ is anthraquinone), which has two stimuli responsive functional-groups, can form self-assembled interfacial aggregates at the air-water interface and, their morphologies can be controlled by changing the subphase conditions such as the pH of the subphase. These interfacial morphologies may be altered from planar structures to wormlike aggregates which is a very rare observation in the literature. Moreover, the unique functional groups of AQua give possibility to reduce metal cations and allow the formation of organic/inorganic nanocomposite structures at the interface. In this context, formation of silver nanoparticles (AgNPs) via AQua-based self-assembled structures at the interface was studied using Langmuir techniques. The kinetics of the reduction process as well as the effect of various parameters were systematically examined. This study demonstrates that interfacial configuration of the AQua molecule at the interface as well as its orientation has a vital role in the morphology of either organic or inorganic self-assemblies formed. The morphology may be adjusted and designed interfacial structures may be obtained. The interfacial properties of AQua, a novel material, may be used in a wide variety of fields such as biotechnology, medicine, energy and pharmaceuticals.

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Winnik, Manners, and others have reported that crystalline diblock copolymers can be used to self-assemble a range of complex hierarchical micellar nanostructures. The type of micellar structure that is formed depends on a number of factors such as relative size of the two blocks and the thermodynamics of interaction between the two blocks and the solvent. It is also found that the use of block copolymers with more complex structures such as three-armed star terpolymers, allows access to multicomponent micelles. Winnik and team members probed the potential of crystallization-driven polymerization concept to access much more complex micellar-like architectures. It is found that deposition of crystalline homopolymer poly(ferrocenyldimethylsilane) (PFS) onto a surface and exposing the crystalline surface to the cylindrical-micelle- forming brushes of the cylindrical micellar grow from the step edges on the surface.
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Pure-lipid films at the water interface have surface-pressures vs. area isotherms that are often interpreted as involving first-order phase transitions from a condensed region to a liquid-expanded region. Two phases are presumed to coexist in the intermediate part of the isotherm. We constructed a film balance that could be placed on the stage of an epifluorescence microscope. A dipalmitoyl phosphatidylcholine film containing a low concentration of a fluorescent lipid probe showed an inhomogeneous fluorescence distribution in the so-called liquid-expanded region of the isotherm. Only the intermediate and condensed regions could be prepared so as to be optically homogeneous below 25 degrees C. We investigated membrane flow and lateral lipid diffusion in the membrane on the trough. The isotherms and isochores were measured. The results require, at least, a modified description of the monolayer structure in various regions of the isotherms. The solid-condensed region corresponds to a gel phase of the lipids where there is no flow in the membrane, lateral diffusion is low, the compressibility is low, and the membrane is optically homogeneous. The "liquid-condensed/liquid-expanded" region appears to be a homogeneous membrane where lateral diffusion and membrane flow are both rapid. This is a region of high compressibility. The "liquid-expanded" region is not homogeneous as seen under the microscope, and the flow of the surface layer can be very fast.
Article
The organization of hydrophobized colloidal gold nanoparticles at air-water interface and the formation thereafter of lamellar, multilayer films of the gold nanoparticles by the Langmuir-Blodgett technique is described in this paper. The hydrophobization of the colloidal particles was accomplished by the direct chemisorption of laurylamine molecules on aqueous colloidal gold nanoparticles during a phase-transfer process. While monolayers of the laurylamine-capped gold nanoparticles at the air-water interface were not amenable to layer-by-layer transfer onto solid supports, it was observed that addition of the water-insoluble amphiphile octadecanol to the gold nanoparticle solution improved the stability of the monolayer at the interface as well as the multilayer assembly protocol. The organization of the gold nanoparticles at the air-water interface was followed by surface pressure-area isotherm measurements while the formation of multilayer films of the nanoparticles by the Langmuir-Blodgett technique was monitored by quartz crystal microgravimetry, UV-vis spectroscopy, Fourier transform infrared spectroscopy, and transmission electron microscopy.
Article
A seed-mediated growth method was used to control the morphology and dimensions of Au nanocrystals by the manipulation of the experimental parameters in aqueous solution at room temperature. This chemical route produces various structural architectures with rod-, rectangle-, hexagon-, cube-, triangle-, and starlike profiles and branched (such as bi-, tri-, tetra-, and multipod) Au nanocrystals of various dimensions in high yield in the presence of a single surfactant, cetyltrimethylammonium bromide.
Article
The need to improve miniaturization and device performance in the microchip and microelectronics industry has recently inspired many investigations into supramolecular chemistry. Specifically, the ability to precisely control the inner and outer diameters of self-assembled lipid nanotubes (LNTs) directly determines their suitability for technological applications. Understanding how structural variation affects nanotube dimensions at the molecular level would facilitate a more efficient and systematic approach to generating rationalized tubular libraries. This review summarizes recent advances as well as approaches to controlling the dimensions of lipid and polymer nanotubes, focusing on the outer and inner diameters, lengths, and membrane wall thickness. Some of the methods considered include chiral molecular self-assembly, packing-directed self-assembly, polymer assembly, molecular sculpting, and templated synthesis using a pore.
Article
Nanofibrillar micellar structures formed by the amphiphilic hyperbranched molecules within a Langmuir monolayer were utilized as matter for silver nanoparticle formation from the ion-containing water subphase. We observed that silver nanoparticles were formed within the multifunctional amphiphilic hyperbranched molecules. The diameter of nanoparticles varied from 2-4 nm and was controlled by the core dimensions and the interfibrillar free surface area. Furthermore, upon addition of potassium nitrate to the subphase, the Langmuir monolayer templated the nanoparticles' formation along the nanofibrillar structures. The suggested mechanism of nanoparticle formation involves the oxidation of primary amino groups by silver catalysis facilitated by "caging" of silver ions within surface areas dominated by multibranched cores. This system provides an example of a one-step process in which hyperbranched molecules with outer alkyl tails and compressed amine-hydroxyl cores mediated the formation of stable nanoparticles placed along/among/beneath the nanofibrillar micelles.
Article
The monodisperse silver nanoparticles were synthesized by one-step reduction of silver ions in the alkaline subphase beneath vitamin E (VE) Langmuir monolayers. The monolayers and silver nanocomposite LB films were characterized by surface pressure-area (pi-A) isotherms, transmission electron microscopy (TEM), ultraviolet-visible spectroscopy (UV-vis), selected area electron diffraction (SAED), Fourier transform infrared transmission spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS), respectively. The results showed that the limiting area/VE molecule on different subphases varied. The phenolic groups in the VE molecules were converted to a quinone structure, and the silver ions were mainly reduced to ellipsoidal and spherical nanoparticles. The arrangement of the nanoparticles changed from sparseness to compactness with reaction time. The electron diffraction pattern indicated that the silver nanoparticles were face-centered cubic (fcc) polycrystalline. Silver nanocomposite LB films with excellent quality could be formed on different substrates, indicating that the transfer ratio of monolayer containing silver nanoparticles is close to unity. The dynamic process of reduction of silver ions by VE LB films was also studied through monitoring the conductivity of an Ag2SO4 alkaline solution.
Article
The growth of gold nanoparticles by reduction by citrate and ascorbic acid has been examined in detail to explore the parameter space of reaction conditions. It is found that gold particles can be produced in a wide range of sizes, from 9 to 120 nm, with defined size distribution, following the earlier work of Turkevich and Frens. The reaction is initiated thermally or in comparison by UV irradiation, which results in similar final products. The kinetics of the extinction spectra show the multiple steps of primary and secondary clustering leading to polycrystallites.
Article
Phase-contrast transmission electron microscopy (PC-TEM) and quick freezing method have been combined to study the initial growing process of a self-assembled lipid nanotube in water. The PC-TEM enabled us to detect thin lamellar edge structure and the very fast growth of the newborn edge to a thin tube with high contrast. The thin tube acts as a core structure for further growth into thick complete lipid nanotube. The initially formed nanotube structure is denoted as a "core tube". The core tube has uniform wall structure that consists of five lamellar layers and the inner and outer diameters of the core tube are 130 and 180 nm, respectively. The evaluated lamellar spacing of 4.6 nm is well compatible with that measured by X-ray diffraction. We also discussed the molecular packing of the nanotube from the pitch angle determined by the PC-TEM images, X-ray diffraction pattern in wide-angle region, and IR spectroscopy. The subcell structure of the nanotube is assigned to an orthorhombic type. The twisting angle between the neighboring lipid molecules is determined as ca. 0.26 degrees for the first time; it is a crucial parameter for the formation of a lipid nanotube in chiral packing but has not been elucidated before.
How the interaction of PVP-stabilized Ag nanoparticles with models of cellular membranes at the air-water interface is modulated by the monolayer composition
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Micelles make a living
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Investigation of The Physical Interactions of Surfactant-Modified Nanoparticles with a Model Cell Membrane, Chemical Engineering
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