Brownian dynamics simulation study of self-assembly of amphiphiles with large hydrophilic heads

We have studied the effect of shape of an amphiphilic molecule on micellization properties by carrying out stochastic molecular dynamics simulation on a bead-spring model of amphiphiles for several sizes of hydrophilic head group with a fixed hydrophobic tail length. Our studies show that the effect of geometry of an amphiphile on shape and cluster distribution of micelles is significant. We find the critical micelle concentration increases with the increasing size of the hydrophilic head. We demonstrate that the onset of micellization is accompanied by (i) a peak in the specific heat as found earlier in the simulation studies of lattice models, and (ii) a peak in the characteristic relaxation time of the cluster autocorrelation function. Amphiphiles with larger hydrophilic head form smaller micelles with sharper cluster distribution. Our studies are relevant to the controlled synthesis of nanostructures of desired shapes and sizes using self-assembling properties of amphiphiles.     

Thermal behavior and structure of clay/nylon-6 nanocomposite synthesized by in situ solution polymerization

This article discusses the effect of increasing mass percentage of nanoclay on the thermal, structural and morphological properties of nanoclay/nylon-6 nanocomposite. Polymerization of ε-caprolactam conducted in the presence of clay resulted in increased d-spacing and expansion of the clay galleries. A combination of differential scanning calorimetry, X-ray diffraction and electron microscopy was used to study the structure–property relationship. The effect of clay on the melting behavior of nylon-6 was studied by using quenched and normally cooled samples. The clay particles acted as external nucleating agents, and a dramatic effect on the crystallization behavior of nylon-6 was observed. The nylon-6 crystals formed are predominantly of the γ-type in the presence of clay. The presence of up to 1 % of clay lead to an increase in the heat of fusion. For nylon-6 samples containing greater than 1 % clay, the heat of fusion decreased significantly.     

Greener approach: Ionic liquid [Et3NH][HSO4]-catalyzed multicomponent synthesis of 4-arylidene-2-phenyl-5(4H)oxazolones under solvent-free condition

We have developed simple, greener, safer multicomponent synthesis series of 4-arylidene-2-phenyl-5(4H) oxazolones 4(a-r) catalyzed by Bronsted acid ionic liquid as triethylammonium hydrogen sulfate [Et₃NH][HSO₄] and catalytic amount of acetic anhydride and sodium acetate with excellent yields (90–99%). The protocol offers economical, environmentally benign, solvent-free conditions, and recycle–reuse of the catalyst and easily available starting as benzoyl chloride 1, amino acid 2 and a variety of aldehydes 3. The cyclization followed by condensation of benzoyl chloride, amino acid, and a variety of aldehydes catalyzed by ILs [Et₃NH][HSO₄] and catalytic amount of acetic anhydride and sodium acetate. The final products were confirmed by their characterization data such as FTIR, ¹H-NMR, ¹³C-NMR, Mass, high-resolution mass spectra and were compared with its reported method.     

Effects of surfactants on properties of polymer-coated magnetic nanoparticles for drug delivery application

The objective of this research was to compare the effects of two different surfactants on the physicochemical properties of thermo-responsive poly(N-isopropylacrylamide-acrylamide-allylamine) (PNIPAAm-AAm-AH)-coated magnetic nanoparticles (MNPs). Sodium dodecyl sulfate (SDS) as a commonly used surfactant in nanoparticle formulation process and Pluronic F127 as an FDA approved material were used as surfactants to synthesize PNIPAAm-AAm-AH-coated MNPs (PMNPs). The properties of PMNPs synthesized using SDS (PMNPs-SDS) and PF127 (PMNPs-PF127) were compared in terms of size, polydispersity, surface charge, drug loading efficiency, drug release profile, biocompatibility, cellular uptake, and ligand conjugation efficiency. These nanoparticles had a stable core–shell structure with about a 100-nm diameter and were superparamagnetic in behavior with no difference in the magnetic properties in both types of nanoparticles. In vitro cell studies showed that PMNPs-PF127 were more cytocompatible and taken up more by prostate cancer cells than that of PMNPs-SDS. Cells internalized with these nanoparticles generated a dark negative contrast in agarose phantoms for magnetic resonance imaging. Furthermore, a higher doxorubicin release at 40 °C was observed from PMNPs-PF127, and the released drugs were pharmacologically active in killing cancer cells. Finally, surfactant type did not affect the conjugation efficiency to the nanoparticles when folic acid was used as a targeting ligand model. These results indicate that PF127 might be a better surfactant to form polymer-coated magnetic nanoparticles for targeted and controlled drug delivery.     

Surface-assisted one-dimensional self-assembly of a perylene based semiconductor molecule

Chloroform-vapor annealing of thin films of propoxyethyl perylene tetracarboxylic diimide (PE-PTCDI, an n-type semiconductor) deposited on glass or mica leads to formation of well-defined one-dimensional self-assemblies (e.g. nanobelts), which show optically uniaxial properties as demonstrated by the linearly polarized emission.     

Effect of packing parameter on phase diagram of amphiphiles: an off-lattice Gibbs ensemble approach

We determine the phase diagram of several amphiphilic molecules as a function of the amphiphilic parameter alpha defined as the ratio of the volume of hydrophilic to hydrophobic segments using the Gibbs ensemble Monte Carlo method supplemented by configurational bias scheme. Specifically, we study amphiphilic molecules h(1)t(7), h(2)t(6), and h(3)t(5), for which alpha=0.14, 0.33, and 0.60 respectively, and demonstrate that the former two exhibit phase separation while h(3)t(5) forms micelles, supporting the contention that alpha=0.5 is the border line for phase separation and micellization, as observed in previous lattice Monte Carlo studies [Panagiotopoulos et al., Langmuir 18, 2940 (2002)]. Further, we study the phase separation in amphiphilic molecules as a function of the packing parameter by varying the size of the hydrophilic head for each molecule. We find that a larger hydrophilic head lowers the critical temperature T(c), and raises the critical density rho(c).     

Nanofibril self-assembly of an arylene ethynylene macrocycle

Nanofibril structures have been fabricated from an arylene ethynylene macrocycle (AEM), which consists of a square frame corner-joined by four carbazole moieties. The fabrication was performed through a gelating process by cooling a warm, homogeneous solution in cyclohexane at high temperature (e.g., 100 degrees C) to room temperature. During the gelation, the molecules become organized, with optimal pi-pi stacking in cooperation with the side-chain association. The favorable pi-pi stacking facilitates the 1D growth of molecular assembly.