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.     

Stability Investigation of Colloidal FePt Nanoparticle Systems by Spectrophotometer Analysis

FePt magnetic nanoparticle systems are an excellent candidate for ultrahigh-density magnetic recording. Monodisperse FePt nanoparticles are synthesized by superhydride reduction of FECl2·4H2O and Pt （acac）2 at 263℃ under N2 atmosphere. Transmission electron microscopy （TEM） images show monosize EePt nanoparticles with diameter of 4 nm and a standard deviation of about 10%. The average distance between monodispesre particles is nearly 3 nm, and oleic acid and oleylamine surround the nanoparticles as surfactants. Stability investigation of nanoparticle colloidal solution is done via speetrophotometery analysis. The results for FePt nanoparticles dispersed in hexane indicate that adding surfactants with concentration of 3 × 10^-3 part by volume for centrifugation stage increases the stability of FePt nanoparticles solution with concentration of 16 mg/mL, about 67%.     

Generation and characterization of Nd-Fe-B-C nanoparticles by pulsed Nd:YAG laser ablation in liquid

We have generated Nd-Fe-B-C nanoparticles by Nd:YAG (1064 nm) laser irradiation in distilled water. Exposure times were 1, 5, and 10 min. Characterization of such nanoparticles in terms of their size distribution, shape, and chemical composition was carried out by transmission electron microscopy, energy-dispersive X-rays, and Fourier transform infrared spectroscopy. To investigate the nanoparticle stability, the size distribution of nanoparticles was measured two weeks after the nanoparticle generation, using dynamic light scattering. Investigations with the help of the atomic force microscope and magnetic force microscope showed other aspects of the generated nanoparticles.     

Synthesis and self-assembly of magnetic nanoparticles

We report the synthesis and self-assembly of different shapes and sizes of FePt nanoparticles. Our study shows that surfactants and solvent play an important role in the synthesis of different shapes and sizes of FePt nanoparticles. Higher boiling point solvents lead to the formation of spherical nanoparticles and low boiling point solvents form cubic nanoparticles. Our studies also indicate that self-assembly of FePt nanoparticles on substrates is a complex process that is sensitive to the concentration of excess surfactant in the nanoparticle solution.     

Effect of Different Ionic Surfactants on the Structural,Photophysical, and Morphological Properties of Water-Based P3HT:PCBM Nanoparticle Dispersions and Films

Aqueous suspensions of composite nanoparticles of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C₆₁ butyric acid methyl ester (PCBM) are fabricated by miniemulsion method using three different ionic surfactants. The aim is to study how the length and conformation of the surfactants alkyl chains affect the properties of the nanoparticles. While the morphology and dimensions of the nanoparticles are similar, UV–vis spectroscopy evidences that the internal aggregation and ordering of the P3HT chains varies within the three nanoparticle formulations. The surfactant with branched alkyl chains promote the highest degree of ordering of P3HT chains in the nanoparticles (leading to increased conjugation length). In contrast, the lowest ordering is found for the nanoparticles with the surfactant having the shortest linear alkyl chain. The optical/structural properties of nanoparticles are partially retained in the films. Besides, the surfactant with branched alkyl chains favors the strongest coalescence of nanoparticles in the thin film, promoting a further ordering of the polymeric chains in the most external shell of the nanoparticles as evidenced by steady-state and time-resolved UV–vis spectroscopy and confocal fluorescence microscopy. These findings might guide the engineering of new surfactants for composite nanoparticles for optoelectronic applications.     

Nanoparticle composites: FePt with wide-band-gap semiconductor

We present a simple way to synthesize FePt and ZnO (wide-band-gap semiconductor) nanoparticle composites. The FePt nanoparticles were fabricated using the method reported by Sun et al. By controlling the heating rate, 3 nm FePt nanoparticles were synthesized. Well-dispersed FePt and ZnO nanoparticle composites were prepared by further adding zinc acetate and oleyl amine into the 3 nm FePt nanoparticle dispersion. By controlling the molar ratio of the FePt and zinc acetate, FePt and ZnO nanoparticle composites with different FePt particle fractions were obtained. The intensity of photo luminescence spectra of the nanoparticle composites increases very much with decreasing FePt particle fraction, whereas the peak position shifts a little. After annealing at 550 °C for half an hour, the nanoparticle composites become magnetically hard or semi-hard with coercivity much dependent on the FePt particle volume fraction. The coercivity of the composites increases with annealing temperature. The composites hold the promise of applications in new generation recording and/or optical devices.     

Desorption of surfactant and sintering of surface-modified PdxNi1 − x nanoparticles

A series of Pd_xNi_1 − x nanoparticles in a diameter of 6-7 nm were prepared by wet chemical reduction. They were then modified with two surfactants, stearic acid (SA) and polyethylene glycol (PEG). Desorption of the surfactant was studied using a temperature programmed desorption technique, and the sintering behavior of surface-modified Pd_xNi_1 − x nanoparticles was examined. Since surface energy of the nanoparticles depends on the alloy composition, it can be correlated with the desorption temperature of surfactant from the nanoparticle surface. Because Ni has a higher surface energy, the surfactant desorption temperature increases as the Ni content increases. With the same stoichiometry, the desorption temperature of SA is always higher than that of PEG. The SA-modified nanoparticles have higher thermal stability and are less sintered than PEG-modified nanoparticles. The sintering and growth behavior of the nanoparticles can be correlated with variation of surface energy due to different surface modification.     

Physical fabrication of colloidal ZnO nanoparticles combining wet-grinding and laser fragmentation

Combination of wet-grinding and laser fragmentation is a promising approach to advance both methods: Laser fragmentation will be more efficient when combined with mechanical treatment and wet-grinding may take advance of the abrasion-free laser process to achieve fabrication of smaller particles. By mechanical pre-treatment of zinc oxide microparticles in a stirred-media mill, the starting material is activated by generation of crystallographic defects, which strongly enhance the efficiency of subsequent laser fragmentation. Picosecond-laser irradiation of mechanically treated and untreated microparticles suspended in water yielded in colloidal zinc oxide nanoparticles. Furthermore, nanoparticle productivity and properties can be controlled by variation of anionic surfactant concentration.     

Optimization of Preparation Techniques for Poly(Lactic Acid-Co-Glycolic Acid) Nanoparticles

Microparticles and nanoparticles of poly(lactic acid-co-glycolic acid) (PLAGA) are excellent candidates for the controlled release of many pharmaceutical compounds because of their biodegradable nature. The preparation of submicron PLAGA particles poses serious challenges that are not necessarily present when preparing microparticles. We have evaluated several combinations of organic solvents and surfactants used in the formulation of PLAGA nanoparticles. Critical factors such as the ability to separate the nanoparticles from the surfactant, the ability to re-suspend the nanoparticles after freeze-drying, formulation yield and nanoparticle size were studied. The smallest particles were obtained using the surfactant/solvent combination of sodium dodecyl sulfate and ethyl acetate (65 nm) and the largest particles were obtained using poly(vinyl alcohol) and dichloromethane (466 nm). However, the optimal nanoparticles were produced using either acetone or ethyl acetate as the organic solvent and poly(vinyl alcohol) or human serum albumin as the surfactant. This is because the most critical measure of performance of these nanoparticles proved to be their ability to re-suspend after freeze-drying.     

Physical properties of magnetic alloy (Nd–Fe–B–C) nanoparticles generated in distilled water using Nd:YAG LASER

In this work, (Nd?CFe?CB?CC) magnetic nanoparticles are generated by pulses of Nd:YAG laser irradiation on the (Nd?CFe?CB?CC) magnetic target in distilled water. Exposure times were 1, 5, and 10 min. Percentages of elements in a bulk sample and nanoparticles are investigated by energy-dispersive X rays (EDX). Mean particle sizes of the nanosamples are analyzed by a transmission electron microscope (TEM). The average size of the nanoparticles is 6.23 nm. A typical selected-area electron-diffraction (SAED) ring pattern from the nanocrystals shows a tetragonal structure in (Nd?CFe?CB?CC) nanoparticles similar to the bulk sample. In order to investigate the nanoparticle stability, in two weeks after nanoparticle generation, the size distribution of nanoparticles is measured using dynamic light scattering (DLS). Using an atomic force microscope (AFM) and a magnetic force microscope (MFM), we show different aspects of generated nanoparticles.     

Laser synthesis of aluminium nanoparticles in biocompatible polymer solutions

Pulsed laser ablation of Aluminium (Al) in pure water rapidly forms a thin alumina (Al₂O₃) layer which drastically modifies surface plasmon resonance (SPR) absorption characteristics in deep-UV region. Initially, pure aluminium nanoparticles (NPs) are generated in water without any stabilizers or surfactants at low laser fluence which gradually transform to stable Al-Al₂O₃ core-shell nanostructure with increasing either residency time or fluence. The role of laser wavelength and fluence on the SPR properties and oxidation characteristics of Al NPs has been investigated in detail. We also present a one-step in situ synthesis of oxide-free stable Al NPs in biocompatible polymer solutions using laser ablation in liquid method. We have used nonionic polymers (PVP, PVA and PEG) and anionic surfactant (SDS) stabilizer to suppress the Al₂O₃ formation and studied the effect of polymer functional group, polymeric chain length, polymer concentration and anionic surfactant on the incipient embryonic aluminium particles and their sizes. The different functional groups of polymers resulted in different oxidation states of Al. PVP and PVA polymers resulted in pure Al NPs; however, PEG and SDS resulted in alumina-modified Al NPs. The Al nanoparticles capped with PVP, PVA, and PEG show a good correlation between nanoparticle stability and monomeric length of the polymer chain.     

Pulsed-laser generation of gold nanoparticles with on-line surface plasmon resonance detection

Size of nanoparticles is an important parameter for their applications. The real-time monitoring is required for reliable and reproducible production of nanoparticles with controllable size. We present results of our research on development of the system for the online nanoparticle characterization during their production by a laser. The laser ablation chamber which allows measurements of surface plasmon resonance spectra during the nanoparticle generation process has been designed and fabricated. The online characterization system was tested by producing and modification of gold nanoparticles. Nanoparticles were generated by nanosecond-laser (wavelength 1064 nm) ablation of gold target in deionized water, and optimal conditions for the highest nanoparticle productivity were estimated. The mean diameter of nanoparticles was determined using their absorption spectra measured in the real-time during the ablation experiments and from the TEM images analysis, and it varied from 20 to 45 nm. The mismatch between nanoparticle diameters, estimated using these two methods, is due to the polydispersity of the generated nanoparticles. The further experiments of laser-induced modification of colloidal gold nanoparticles were carried out using second harmonic (wavelength 532 nm) of nanosecond Nd:YAG laser and alteration in nanoparticle size were acquired by the online measurement system.     

Nanoparticles by Laser Ablation

This review concerns nanoparticles collected in the form of nanopowder or a colloidal solution by laser ablating a solid target that lies in a gaseous or a liquid environment. The paper discusses the advantages of the method as compared with other methods for nanoparticle synthesis, outlines the factors on which the properties of the produced nanoparticles depend, explains the mechanisms and models involved in the generation of nanoparticles by laser ablation, clarifies the differences between nanoparticle generation in gaseous and liquid environments, presents some experimental desigins and equipment used by the several groups for nanoparticle generation by laser ablation, describes the techniques used for “tuning” the width of the nanoparticles size distribution, and finally presents a few interesting examples of nanoparticles generated by laser ablation.     

Hot electrons and laser optoacoustics in metal nanoparticles

The theory of sound generation and heat transfer in matrix-embedded metal nanoparticles under ultra-short laser irradiation has been developed. The shape and time dependence of acoustic waves generated by a sharp change in the pressure of electrons have been investigated for a single nanoparticle and for the group of nanoparticles located on a 2-D flat matrix plane. The dependence of the electronic temperature and the temperature of the interface between the dielectric matrix and nanoparticle as a function of time has been derived.     

Characteristics of the capillary motions of surfactant solutions with a charged free surface

Abastract A dispersion relation is derived and analyzed for the spectrum of capillary motions on the charged plane surface of a liquid in which a surfactant is dissolved. It is shown that two additional wave motions are generated in this kind of system by bulk diffusion and surface diffusion of the surfactant and are sensitive to the diffusion coefficients and elastic properties of the surfactant films and to the viscosity of the solution and the presence of a surface charge. In solutions of inactive surfactants the growth rate of Tonks-Frenkel instability increases as the surfactant concentration increases. Zh. Tekh. Fiz. 68, 22–29 (February 1998)     

Preparation of AgBr Nanoparticles in Microemulsions Via Reaction of AgNO<Subscript>3</Subscript> with CTAB Counterion

Nanoparticles of AgBr were prepared by precipitating AgBr in the water pools of microemulsions consisting of CTAB, n-butanol, isooctane and water. An aqueous solution of AgNO₃ added to the microemulsion was the source of Ag⁺ ions. The formation of AgBr nanoparticles in microemulsions through direct reaction with the surfactant counterion is a novel approach aimed at decreasing the role of intermicellar nucleation on nanoparticle formation for rapid reactions. The availability of the surfactant counterion in every reverse micelle and the rapidity of the reaction with the counterion trigger nucleation within individual reverse micelles. The effect of the following variables on the particle size and size distribution was investigated: the surfactant and cosurfactant concentrations, moles of AgNO₃ added, and water to surfactant mole ratio, R. High concentration of the surfactant or cosurfactant, or high water content of the microemulsion favored intermicellar nucleation and resulted in the formation of large particles with broad size distribution, while high amounts of AgNO₃ favored nucleation within individual micelles and resulted in small nanoparticles with narrow size distribution. A blue shift in the UV absorption threshold corresponding to a decrease in the particle size was generally observed. Notably, the variation of the absorption peak size with the nanoparticle size was opposite to those reported by us in previous studies using different surfactants.     

温度和雷诺数对表面活性剂溶液传热的影响

对不同温度和雷诺数下阳性离子表面活性剂十六烷基三甲基氯化铵(CTAC)溶液在循环回路中的传热特性进行了实验研究。在水中加入表面活性剂后溶液的传热特性明显降低,在不同的温度工况下均存在一个临界雷诺数,随着溶液温度的改变而发生变化。在不同的实验浓度条件下均存在一个临界温度,在临界温度以下时,临界雷诺数随温度升高而增加;在临界温度以上时,临界雷诺数随温度升高而急剧下降。分析该表面活性剂溶液阻力减小和传热性能降低之间的关系,提出了通过对溶液温度的控制来改变减阻流体传热特性的方法。     

A molecular dynamics study on interfacial heat transport of alkanethiol surfactant coated nanofluids-effect of chain length and stiffness

The thermal transport across the alkanethiol surfactant layer at the nanoparticle/base fluid interface in nanofluids was investigated by molecular dynamics simulation, with consideration of the conformation of the surfactant layer with different surfactant chain lengths and backbone stiffness. The variation of temperature drop at nanoparticle-surfactant interface reveals that the interfacial thermal conductance was mediated by the chain length, possibly due to the difference in the adsorption density of surfactant on the surface of the nanoparticles, because of the blocking effect from the bending of the long alkyl chains. The intrinsic thermal conductivity of the surfactant layer increased with decreasing chain length and increasing chain stiffness because of the phonon scattering effect from the bending and cross-linking of the alkyl chains. We quantified the modes of heat flow across the surfactant layer and found that the contribution of intramolecular bonded interaction was much higher than that of atomic translation and nonbonded interaction separately. By analysing the variation of bonded interaction contrition with chain length and stiffness, it is demonstrated that the increased thermal conductivities benefited from the enhanced thermal transfer through the covalent bonds of surfactant molecules. The results can provide insights into the design of thermally conductive surfactants.     

Laser ablation of microparticles for nanostructure generation

The process of laser ablation of microparticles has been shown to generate nanoparticles from microparticles; but the generation of nanoparticle networks from microparticles has never been reported before. We report a unique approach for the generation of nanoparticle networks through ablation of microparticles. Using this approach, two samples containing microparticles of lead oxide (Pb₃O₄) and nickel oxide (NiO), respectively, were ablated under ambient conditions using a femtosecond laser operating in the MHz repetition rate regime. Nanoparticle networks with particle diameter ranging from 60 to 90 nm were obtained by ablation of microparticles without use of any specialized equipment, catalysts or external stimulants. The formation of finer nanoparticle networks has been explained by considering the low pressure region created by the shockwave, causing rapid condensation of microparticles into finer nanoparticles. A comparison between the nanostructures generated by ablating microparticle and those by ablating bulk substrate was carried out; and a considerable reduction in size and narrowed size distribution was observed. Our nanostructure fabrication technique will be a unique process for nanoparticle network generation from a vast array of materials.     

Light-assisted synthesis and functionalization of silver nanoparticles with thiol derivative thioxanthones: new insights into the engineering of metal/chromophore nanoassemblies

Nanofluids are suspensions of nanometer-sized particles which significantly modify the properties of the base fluids. Nanofluids exhibit attractive properties, such as high thermal conductivity, tunable surface tension, viscosity, and rheology. Various attempts have been made to understand the mechanisms for these property modifications caused by adding nanoparticles; however, due to the lack of direct nanoscale evidence, these explanations are still controversial. This work calculated the surface tension, viscosity, and rheology of gold–water nanofluids using molecular dynamics simulations which provide a microscopic interpretation for the modified properties on the molecular level. The gold–water interaction potential parameters were changed to mimic various nanoparticle types. The results show that the nanoparticle wettability is responsible for the modified surface tension. Hydrophobic nanoparticles always tend to stay on the free surface so they behave like a surfactant to reduce the surface tension. Hydrophilic nanoparticles immersed into the bulk fluid impose strong attractive forces on the water molecules at the free surface which reduces the free surface thickness and increases the surface tension of the nanofluid. Solid-like absorbed water layers were observed around the nanoparticles which increase the equivalent nanoparticle radius and reduce the mobility of the nanoparticles within the base fluid which increases the nanofluid viscosity. The results show the water molecule solidification between two or many nanoparticles at high nanoparticle loadings, but the solidification effect is suppressed for shear rates greater than a critical shear rate; thus Newtonian nanofluids can present shear-thinning non-Newtonian behavior.