facile-preparation-internally-self-assembled-lipid-particles

Facile Preparation of Internally Self-assembled Lipid Particles Stabilized by Carbon Nanotubes

We present a facile method to prepare nanostructured lipid particles stabilized by carbon nanotubes (CNTs). Single-walled (pristine) and multi-walled ...

University of Leeds

Repulsive electrostatic double-layer forces are responsible for the stabilization of charged colloidal particles in the presence of adsorbed polyelectrolytes of opposite and high line charge densities. This mechanism is revealed by studies of electrophoretic mobility and colloidal stability performed with dynamic light scattering as a function of the polyelectrolyte dose and the ionic strength for two different types of latex particles and four different types of polyelectrolytes. The dependence of these quantities is very similar for bare charged latex particles and the same particles in the presence of the different oppositely charged polyelectrolytes. Positively charged particles in the presence of anionic polyelectrolytes behave analogously to negatively charged particles in the presence of cationic polyelectrolytes.

Electrostatic stabilization of charged colloidal particles with adsorbed polyelectrolytes of opposite charge.

Highly charged polyelectrolytes adsorbed on oppositely charged colloidal particles are investigated by electrophoresis and dynamic light scattering. The dependence of the adsorbed amount and of the hydrodynamic layer thickness on the molecular mass and the salt level is analyzed. The adsorbed amount increases with increasing salt level and decreases with increasing molecular mass. The hydrodynamic layer thickness is independent of the molecular mass at low salt levels, but increases with the molecular mass as a power law with an exponent 0.10 ± 0.01 at high salt. The same behavior was observed for different polyelectrolytes and substrates and therefore is suspected to be generic. Due to semi-quantitative agreement with computer simulations carried out by Kong and Muthukumar in 1998, the observed behavior is interpreted with conformational changes of single adsorbed polyelectrolyte chains.

Molecular mass dependence of adsorbed amount and hydrodynamic thickness of polyelectrolyte layers.

Positively charged amidine latex particles are studied in the presence of poly(acrylic acid) (PAA) with different molecular masses under neutral and acidic conditions by electrophoresis and time-resolved dynamic light scattering. Under neutral conditions, where PAA is highly charged, the system is governed by the charge reversal induced by the quantitatively adsorbing polyelectrolyte and attractive patch-charge interactions. Under acidic conditions, where PAA is more weakly charged, the following two effects come into play. First, the lateral structure of the adsorbed layers becomes more homogeneous, which weakens the attractive patch-charge interactions. Second, polyelectrolyte adsorption is no longer quantitative and partitioning into the solution phase is observed, especially for PAA of low molecular mass.

Influence of the degree of ionization and molecular mass of weak polyelectrolytes on charging and stability behavior of oppositely charged colloidal particles.

Towards Angström resolution with dynamic light scattering.

The destabilization of charged colloidal suspensions is studied in the presence of polyelectrolytes and the corresponding oligomers. Two different systems are investigated, namely, negatively charged particles in the presence of polyamines and positively charged ones in the presence of polycarboxylates. Multivalent oligomers of low valence destabilize the particles by screening according to the Schulze-Hardy rule. Polyelectrolytes induce destabilization by overcharging. Both regimes can be observed for oligomers of intermediate valence. The stability data of any valence can be rather well described by the theory of Derjaguin, Landau, Verwey, and Overbeek (DLVO), indicating that the interactions are mainly governed by van der Waals and electrostatic double-layer forces.

Destabilization of colloidal suspensions by multivalent ions and polyelectrolytes: from screening to overcharging.

Charging and aggregation of negatively charged carboxyl latex particles in the presence of positively charged linear oligoamines containing 1-6 amine groups were investigated by electrophoretic mobility and dynamic light scattering. The oligoamines of low valence resemble simple inert salts and destabilize the suspensions by screening their charge. The oligoamines of higher valence induce overcharging at low concentrations, whereby destabilization is triggered by charge neutralization. At higher concentrations, destabilization is also induced by screening. The onset of first fast aggregation regime scales with the inverse six power of the valence in agreement with the Schulze-Hardy rule. The aggregation rates can be relatively well described by the DLVO theory which indicates that the interactions are governed by van der Waals and electrostatic double layer forces.

Charging and aggregation of negatively charged colloidal latex particles in the presence of multivalent oligoamine cations.

Oil-water Pickering emulsions of about 200 nm were stabilized by nanosized hydrophilic silica after a simple surface treatment method. We have modified the aqueous silica nanoparticle dispersions by simple adsorption of oleic acid to their surfaces, improving the hydrophobicity of the particles while maintaining their charge and stability. The adsorption was monitored by small-angle X-ray scattering and electrophoretic measurements to estimate the interparticle interactions and surface charges. The effect of various parameters, such as nanoparticle concentration, amount of oleic acid, ionic strength, and pH, on the droplets' size and stability was investigated by dynamic light scattering. Furthermore, the ability of these modified silica nanoparticles to stabilize long-chain alkanes, liquid paraffin, and liquid-crystalline phases was examined.

Submicrometer-sized Pickering emulsions stabilized by silica nanoparticles with adsorbed oleic acid.

In recent years, continuous-flow/microreactor processing for the preparation of colloidal nanocrystals has received considerable attention. The intrinsic advantages of microfluidic reactors have opened new opportunities for the size-controlled synthesis of nanocrystals either in the laboratory or on a large scale. Herein, an experimentally simple protocol for the size-tunable continuous-flow synthesis of rather monodisperse CdSe quantum dots (QDs) is presented. CdSe QDs are manufactured by using cadmium oleate as cadmium source, selenium dioxide as selenium precursor, and 1-octadecene as solvent. Exploiting selenium dioxide as selenium source and 1-octadecene as solvent allows execution of the complete process in open air without any requirement for air-free manipulations using a glove box or Schlenk line. Continuous-flow processing is performed with a stainless steel coil of 1.0 mm inner diameter pumping the combined precursor solution through the reactor by applying a standard HPLC pump. The effect of different reaction parameters, such as temperature, residence time, and flow rate, on the properties of the resulting CdSe QDs was investigated. A temperature increase from 240 to 260 °C or an extension of the residence time from 2 to 20 min affords larger nanocrystals (range 3-6 nm) whereas the size distribution does not change significantly. Longer reaction times and higher temperatures result in QDs with lower quantum yields (range 11-28 %). The quality of the synthesized CdSe QDs was confirmed by UV/Vis and photoluminescence spectroscopy, small-angle X-ray scattering, and high-resolution transmission electron microscopy. Finally, the potential of this protocol for large-scale manufacturing was evaluated and by operating the continuous-flow process for 87 min it was possible to produce 167 mg of CdSe QDs (with a mean diameter of 4 nm) with a quantum yield of 28 %.

Continuous-flow synthesis of CdSe quantum dots: a size-tunable and scalable approach.

The transfer kinetics of lipids between internally self-assembled droplets of O/W emulsions is studied. The droplets (isasomes) consist of various liquid-crystalline phases or W/O microemulsions stabilized by a polymeric stabilizer F127. The various internal phases were identified by the relative peak positions in the small-angle X-ray scattering (SAXS) curves. An arrested system composed of isasomes embedded in a gel matrix actually provides an additional possibility to control these systems in terms of the release of various host molecules. These experiments have been applied to examine the kinetics of the internal phase reorganization imposed by the lipids' release and uptake by the droplets embedded in a κ-carrageenan (KC) hydrogel network. Increasing the concentration of the gelling agent slows down the transfer from one droplet to the other through the aqueous phase. We examined the region where the free diffusion is stopped. i.e., the point where the system changes from the ergodic to the nonergodic state and the kinetics is essentially slowed down. This effect can be balanced by the addition of small amounts of free polymeric stabilizer, which speeds up the kinetics. This is even possible in the case of highly arrested dynamics of the emulsion droplets, as found for the highest KC hydrogel concentrations forming nonergodic systems.

Lipid transfer in oil-in-water isasome emulsions: influence of arrested dynamics of the emulsion droplets entrapped in a hydrogel.

The present article reviews recent progress in the measurement of aggregation rates in colloidal suspensions by light scattering. Time-resolved light scattering offers the possibility to measure absolute aggregation rate constants for homoaggregation as well as heteroaggregation processes. We further discuss the typical concentration dependencies of the aggregation rate constants on additives. Addition of simple salts containing monovalent counterions leads to screening of the electrostatic repulsion of the charged particles and a transition from slow to rapid aggregation. Addition of salts containing multivalent counterions may lead to a charge reversal, which results in a sequence of two instability regions. Heteroaggregation rates between oppositely charged particles decrease with increasing salt level. This decrease is caused by screening of the electrostatic attraction between these particles.

Probing colloidal particle aggregation by light scattering.

Transfer of lipids between droplets in Pickering emulsions has been studied by time-resolved small-angle X-ray scattering (SAXS). The special features of self-assembled liquid-crystalline phases have been applied to examine the kinetics of internal phase reorganization imposed by lipid release and uptake by the droplets. The findings reveal faster transfer kinetics in Pickering emulsions than in emulsions stabilized with Pluronic F127. It is shown that the transfer kinetics can be accelerated by adding free surfactant to the dispersions and that this acceleration becomes more dominant when micelles are formed. The effect of immobilization of the droplets has been studied by incorporating them into the appropriate hydrogel network. The droplets are arrested, and the transfer slows down significantly at high enough concentrations of the hydrogel where nonergodic systems are obtained.

Lipid transfer between submicrometer sized Pickering ISAsome emulsions and the influence of added hydrogel.

The coupling of fullerene (C60) to the structure and elasticity of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine bilayers has been explored by synchrotron small angle X-ray scattering. Multilamellar vesicles were loaded with 0, 2 and 10 mol.% of C60 and studied in a temperature range from 15 to 65 °C. The addition of C60 caused an increase in the bilayer undulations (∼ 20%), in the bilayer separation (∼ 15%), in the linear expansion coefficient and caused a drop in the bending rigidity of the bilayers (20-40%). Possible damaging effects of fullerene on biomembranes are mainly discussed on the basis of altered bilayer fluidity and elasticity changes.

Article	Year
Electrostatic stabilization of charged colloidal particles with adsorbed polyelectrolytes of opposite charge. Langmuir : the ACS journal of surfaces and colloids\| PubMed ID: 20822122	2010
Molecular mass dependence of adsorbed amount and hydrodynamic thickness of polyelectrolyte layers. Physical chemistry chemical physics : PCCP\| PubMed ID: 21687880	2011
Influence of the degree of ionization and molecular mass of weak polyelectrolytes on charging and stability behavior of oppositely charged colloidal particles. Langmuir : the ACS journal of surfaces and colloids\| PubMed ID: 21707034	2011
Towards Angström resolution with dynamic light scattering. Chimia\| PubMed ID: 21797175	2011
Destabilization of colloidal suspensions by multivalent ions and polyelectrolytes: from screening to overcharging. Langmuir : the ACS journal of surfaces and colloids\| PubMed ID: 22468583	2012
Charging and aggregation of negatively charged colloidal latex particles in the presence of multivalent oligoamine cations. Journal of colloid and interface science\| PubMed ID: 23116861	2013
Submicrometer-sized Pickering emulsions stabilized by silica nanoparticles with adsorbed oleic acid. Langmuir : the ACS journal of surfaces and colloids\| PubMed ID: 23650929	2013
Continuous-flow synthesis of CdSe quantum dots: a size-tunable and scalable approach. Chemistry (Weinheim an der Bergstrasse, Germany)\| PubMed ID: 23857757	2013
Lipid transfer in oil-in-water isasome emulsions: influence of arrested dynamics of the emulsion droplets entrapped in a hydrogel. Langmuir : the ACS journal of surfaces and colloids\| PubMed ID: 24274164	2013
Probing colloidal particle aggregation by light scattering. Chimia\| PubMed ID: 24388227	2013
Lipid transfer between submicrometer sized Pickering ISAsome emulsions and the influence of added hydrogel. Langmuir : the ACS journal of surfaces and colloids\| PubMed ID: 24559265	2014
Fullerene up-take alters bilayer structure and elasticity: A small angle X-ray study. Chemistry and physics of lipids\| PubMed ID: 25849256	2015

Amin Sadeghpour

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