Magnetic properties of γ-Fe2O3nanoparticles in a porous SiO2shell for drug delivery.

A method is presented for synthesizing core-shell nanoparticles with a magnetic core and a porous shell suitable for drug delivery and other medical applications. The core contains multiple $\gamma$-Fe$_2$O$_3$ nanoparticles ($\sim$15~nm) enclosed in a SiO$_2$ ($\sim$100-200~nm) matrix using either methyl (denoted TMOS-$\gamma$-Fe$_2$O$_3$) or ethyl (TEOS-$\gamma$-Fe$_2$O$_3$) template groups. Low-temperature M{\"o}ssbauer spectroscopy showed that the magnetic nanoparticles have the maghemite structure, $\gamma$-Fe$_2$O$_3$, with all the vacancies in the octahedral sites. Saturation magnetization measurements revealed that the density of $\gamma$-Fe$_2$O$_3$ was greater in the TMOS-$\gamma$-Fe$_2$O$_3$ nanoparticles than TEOS-$\gamma$-Fe$_2$O$_3$ nanoparticles, presumably because of the smaller methyl group. Magnetization measurements showed that the blocking temperature is around room temperature for the TMOS-$\gamma$-Fe$_2$O$_3$ and around 250~K for the TEOS-$\gamma$-Fe$_2$O$_3$. Three dimensional topography analysis shows clearly that the magnetic nanoparticles are not only at the surface but have penetrated deep in the silica to form the core-shell structure.

Dynamic Curvature Nanochannel-Based Membrane with Anomalous Ionic Transport Behaviors and Reversible Rectification Switch.

Biological nanochannels control the movements of different ions through cell membranes depending on not only those channels' static inherent configurations, structures, inner surface's physicochemical properties but also their dynamic shape changes, which are required in various essential functions of life processes. Inspired by ion channels, many artificial nanochannel-based membranes for nanofluidics and biosensing applications have been developed to regulate ionic transport behaviors by using the functional molecular modifications at the inner surface of nanochannel to achieve a stimuli-responsive layer. Here, the concept of a dynamic nanochannel system is further developed, which is a new way to regulate ion transport in nanochannels by using the dynamic change in the curvature of channels to adjust ionic rectification in real time. The dynamic curvature nanochannel-based membrane displays the advanced features of the anomalous effect of voltage, concentration, and ionic size for applying simultaneous control over the curvature-tunable asymmetric and reversible ionic rectification switching properties. This dynamic approach can be used to build smart nanochannel-based systems, which have strong implications for flexible nanofluidics, ionic rectifiers, and power generators.

Molecular Dynamics Modeling of Methylene Blue-DOPC Lipid Bilayer Interactions.

We present a coarse-grained MARTINI model for methylene blue (MB) and investigate the interactions of MB with dioleylphosphatidylcholine (DOPC) lipid bilayers by molecular dynamics simulations. Our results show that the charge state of MB and the oxidation degree of the DOPC bilayer play critical roles on membrane properties. Oxidation of the DOPC bilayer significantly increases permeability of water and MB molecules, irrespective of the charge state of MB. The most significant changes in membrane properties are obtained for peroxidized lipid bilayers in the presence of cationic MB, with ∼11% increase in the membrane area per lipid head group and ∼7 and 44% reduction in membrane thickness and lateral diffusivity, respectively.

Improved controlled release of protein from expanded-pore mesoporous silica nanoparticles modified with co-functionalized poly(n-isopropylacrylamide) and poly(ethylene glycol) (PNIPAM-PEG).

Novel pore-expanded mesoporous silica nanoparticles (MSNs) with pore sizes of approximately 11nm were synthesized and modified with thermoresponsive, poly(n-isopropylacrylamide) (PNIPAM) gating groups on the nanoparticle exterior surface and in addition with poly(ethylene-glycol) (PEG) within the porous interior to minimize protein adsorption. PEG traditionally has been grafted to the nanoparticle exterior to minimize non-specific binding and interactions with the biological environment, but due to the templating mechanism of MSN synthesis, both the pore interior and nanoparticle surface can be separately modified. Here, an improved control release behavior of bovine hemoglobin (BHb) was observed after PEGylating the interior porous framework, compared to the release BHb from unmodified MSNs. This can be attributed to the reduced protein denaturation on PEGylated silica that was observed using circular dichroism spectroscopy.

Response to Extreme Temperatures of Mesoporous Silica MCM-41: Porous Structure Transformation Simulation and Modification of Gas Adsorption Properties.

Molecular dynamics (MD) and Monte Carlo (MC) simulations were applied together for the first time to reveal the porous structure transformation mechanisms of mesoporous silica MCM-41 subjected to temperatures up to 2885 K. Silica was experimentally characterized to inform the models and enable prediction of changes in gas adsorption/separation properties. MD simulations suggest that the pore closure process is activated by a collective diffusion of matrix atoms into the porous region, accompanied by bond reformation at the surface. Degradation is kinetically limited, such that complete pore closure is postponed at high heating rates. We experimentally observe decreased gas adsorption with increasing temperature in mesoporous silica heated at fixed rates, due to pore closure and structural degradation consistent with simulation predictions. Applying the Kissinger equation, we find a strong correlation between the simulated pore collapse temperatures and the experimental values which implies an activation energy of 416 ± 17 kJ/mol for pore closure. MC simulations give the adsorption and selectivity for thermally treated MCM-41, for N2, Ar, Kr, and Xe at room temperature within the 1-10 000 kPa pressure range. Relative to pristine MCM-41, we observe that increased surface roughness due to decreasing pore size amplifies the difference of the absolute adsorption amount differently for different adsorbate molecules. In particular, we find that adsorption of strongly interacting molecules can be enhanced in the low-pressure region while adsorption of weakly interacting molecules is inhibited. This then results in higher selectivity in binary mixture adsorption in mesoporous silica.

Nanowire formation is preceded by nanotube growth in templated electrodeposition of cobalt hybrid nanostructures.

Cobalt fluted nanowires, novel nanostructures with a diameter of 200 nm consisting of a solid nanowire base and a thin, nanotubular flute shape, were grown in track-etched polycarbonate membranes via templated electrodeposition. The structures were characterized electrochemically via cyclic voltammetry, chronoamperometry, and charge stripping, and structurally via  scanning electron microscopy, transmission electron microscopy, and focused ion beam cross-sectioning. Electrochemical and structural analysis reveals details of their deposition kinetics, structure, and morphology, and indicate possible mechanisms for their formation and control. These unique structures provide inspiration for an array of possible applications in electronics, photonics, and other fields.

Understanding the Interaction of Pluronics L61 and L64 with a DOPC Lipid Bilayer: An Atomistic Molecular Dynamics Study.

We investigate the interactions of Pluronics L61 and L64 with a dioleylphosphatidylcholine (DOPC) lipid bilayer by atomistic molecular dynamics simulations using the all-atom OPLS force field. Our results show that the initial configuration of the polymer with respect to the bilayer determines its final conformation within the bilayer. When the polymer is initially placed at the lipid/water interface, we observe partial insertion of the polymer in a U-shaped conformation. On the other hand, when the polymer is centered at the bilayer, it stabilizes to a transmembrane state, which facilitates water transport across the bilayer. We show that membrane thickness decreases while its fluidity increases in the presence of Pluronics. When the polymer concentration inside the bilayer is high, pore formation is initiated with L64. Our results show good agreement with existing experimental data and reveal that the hydrophilic/lipophilic balance of the polymer plays a critical role in the interaction mechanisms as well as in the dynamics of Pluronics with and within the bilayer.

Template-based syntheses for shape controlled nanostructures.

A variety of nanostructured materials are produced through template-based synthesis methods, including zero-dimensional, one-dimensional, and two-dimensional structures. These span different forms such as nanoparticles, nanowires, nanotubes, nanoflakes, and nanosheets. Many physical characteristics of these materials such as the shape and size can be finely controlled through template selection and as a result, their properties as well. Reviewed here are several examples of these nanomaterials, with emphasis specifically on the templates and synthesis routes used to produce the final nanostructures. In the first section, the templates have been discussed while in the second section, their corresponding synthesis methods have been briefly reviewed, and lastly in the third section, applications of the materials themselves are highlighted. Some examples of the templates frequently encountered are organic structure directing agents, surfactants, polymers, carbon frameworks, colloidal sol-gels, inorganic frameworks, and nanoporous membranes. Synthesis methods that adopt these templates include emulsion-based routes and template-filling approaches, such as self-assembly, electrodeposition, electroless deposition, vapor deposition, and other methods including layer-by-layer and lithography. Template-based synthesized nanomaterials are frequently encountered in select fields such as solar energy, thermoelectric materials, catalysis, biomedical applications, and magnetowetting of surfaces.

A novel technique for detoxification of phenol from wastewater: Nanoparticle Assisted Nano Filtration (NANF).

BACKGROUND: Phenol is one of the most versatile and important organic compound. It is also a growing concern as water pollutants due to its high persistence and toxicity. Removal of Phenol from wastewaters was investigated using a novel nanoparticle adsorption and nanofiltration technique named as Nanoparticle Assisted Nano Filtration (NANF). METHODS: The nanoparticle used for NANF study were silver nanoparticles and synthesized to three distinct average particle sizes of 10 nm, 40 nm and 70 nm. The effect of nanoparticle size, their concentrations and their tri and diparticle combinations upon phenol removal were studied. RESULTS: Total surface areas (TSA) for various particle size and concentrations have been calculated and the highest was 4710 × 10(12 )nm(2 )for 10 nm particles and 180 ppm concentration while the lowest was for 2461 × 10(11) for 70 nm and 60 ppm concentrations. Tri and diparticle studies showed more phenol removal % than that of their individual particles, particularly for using small particles on large membrane pore size and large particles at low concentrations. These results have also been confirmed with COD and toxicity removal studies. CONCLUSIONS: The combination of nanoparticles adsorption and nanofiltration results in high phenol removal and mineralization, leading to the conclusion that NANF has very high potential for treating toxic chemical wastewaters.

Measurement of Small Molecular Dopant F4TCNQ and C60F36 Diffusion in Organic Bilayer Architectures.

The diffusion of molecules through and between organic layers is a serious stability concern in organic electronic devices. In this work, the temperature-dependent diffusion of molecular dopants through small molecule hole transport layers is observed. Specifically we investigate bilayer stacks of small molecules used for hole transport (MeO-TPD) and p-type dopants (F4TCNQ and C60F36) used in hole injection layers for organic light emitting diodes and hole collection electrodes for organic photovoltaics. With the use of absorbance spectroscopy, photoluminescence spectroscopy, neutron reflectometry, and near-edge X-ray absorption fine structure spectroscopy, we are able to obtain a comprehensive picture of the diffusion of fluorinated small molecules through MeO-TPD layers. F4TCNQ spontaneously diffuses into the MeO-TPD material even at room temperature, while C60F36, a much bulkier molecule, is shown to have a substantially higher morphological stability. This study highlights that the differences in size/geometry and thermal properties of small molecular dopants can have a significant impact on their diffusion in organic device architectures.

Poly(N-isopropylacrylamide)-gated Fe3O4/SiO2 core shell nanoparticles with expanded mesoporous structures for the temperature triggered release of lysozyme.

Core-shell nanoparticles comprised of Fe3O4 cores and a mesoporous silica shell with an average expanded pore size of 6.07 nm and coated with a poly(N-isopropylacrylamide) (PNIPAM) layer (CS-MSNs-EP-PNIPAM) were prepared and characterized. The nanoparticles was loaded with (Ru(bipy)3(2+)) dye or an antibacterial enzyme, lysozyme, to obtain CS-MSNs-EP-PNIPAM-Ru(bipy)3(2+) and CS-MSNs-EP-PNIPAM-Lys, respectively. The lysozyme loading was determined to be 160 mg/g of nanoparticle. It was seen that Ru(bipy)3(2+) and lysozyme release was minimal at a room temperature of 25 °C while at physiological temperature (37 °C), abrupt release was observed. The applicability of the CS-MSNs-EP-PNIPAM-Lys was further tested with two Gram-positive bacteria samples, Bacillus cereus and Micrococcus luteus. At physiological temperature, the nanoparticles were shown to reduce bacterial growth, indicating a successful release of lysozyme from the nanoparticles. This nanoparticle system shows potential as a nanocarrier for the loading of similarly sized proteins or other species as a drug delivery platform.

Reversible optical control of conjugated polymer solubility with sub-micrometer resolution.

Organic electronics promise to provide flexible, large-area circuitry such as photovoltaics, displays, and light emitting diodes that can be fabricated inexpensively from solutions. A major obstacle to this vision is that most conjugated organic materials are miscible, making solution-based fabrication of multilayer or micro- to nanoscale patterned films problematic. Here we demonstrate that the solubility of prototypical conductive polymer poly(3-hexylthiophene) (P3HT) can be reversibly "switched off" using high electron affinity molecular dopants, then later recovered with light or a suitable dedoping solution. Using this technique, we are able to stack mutually soluble materials and laterally pattern polymer films by evaporation or with light, achieving sub-micrometer, optically limited feature sizes. After forming these structures, the films can be dedoped without disrupting the patterned features; dedoped films have identical optical characteristics, charge carrier mobilities, and NMR spectra as as-cast P3HT films. This method greatly simplifies solution-based device fabrication, is easily adaptable to current manufacturing workflows, and is potentially generalizable to other classes of materials.

Bioelectronic light-gated transistors with biologically tunable performance.

Light-activated bioelectronic silicon nanowire transistor devices are made by fusing proteoliposomes containing a bacteriorhodopsin (bR) proton pump onto the nanowire surface. Under green-light illumination, bR pumps protons toward the nanowire, and the pH gradient developed by the pump changes the transistor output. Furthermore, co-assembly of small biomolecules that alter the bilayer permeability to other ions can upregulate and downregulate the response of field-effect transistor devices.

Protein diffusion through charged nanopores with different radii at low ionic strength.

The diffusion of two similar molecular weight proteins, bovine serum albumin (BSA) and bovine haemoglobin (BHb), through nanoporous charged membranes with a wide range of pore radii is studied at low ionic strength. The effects of the solution pH and the membrane pore diameter on the pore permeability allow quantifying the electrostatic interaction between the charged pore and the protein. Because of the large screening Debye length, both surface and bulk diffusion occur simultaneously. By increasing the pore diameter, the permeability tends to the bulk self-diffusion coefficient for each protein. By decreasing the pore diameter, the charges on the pore surface electrostatically hinder the transport even at the isoelectric point of the protein. Surprisingly, even at pore sizes 100 times larger than the protein, the electrostatic hindrance still plays a major role in the transport. The experimental data are qualitatively explained using a two-region model for the membrane pore and approximated equations for the pH dependence of the protein and pore charges. The experimental and theoretical results should be useful for designing protein separation processes based on nanoporous charged membranes.

Modified release from lipid bilayer coated mesoporous silica nanoparticles using PEO-PPO-PEO triblock copolymers.

Triblock copolymers comprised of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO, or trade name Pluronic) interact with lipid bilayers to increase their permeability. Here we demonstrate a novel application of Pluronic L61 and L64 as modification agents in tailoring the release rate of a molecular indicator species from 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) bilayer-coated superparamagnetic Fe3O4/mesoporous silica core-shell nanoparticles. We show there is a direct relationship between the Pluronics' concentration and the indicator molecule release, suggesting Pluronics may be useful for the controlled release of drugs from lipid bilayer-coated carriers.

Transition and stability of copolymer adsorption morphologies on the surface of carbon nanotubes and implications on their dispersion.

In this study, the adsorption morphologies as well as stability and transitions of a commercial dispersant copolymer (BYK 9076) on the surface of multiwalled carbon nanotubes (MWCNTs) were studied using Fourier transform infrared and UV-vis spectroscopy, dynamic light scattering, and electron microscopy techniques. The results show that the dispersion of carbon nanotubes in ethanol does not increase continuously with increasing copolymer/CNT ratio, which is correlated with the adsorption morphologies of the copolymer on the CNT surface. At a ratio of copolymer/CNT below 0.5, the morphology is random, shifting to a hemimicelle structure at a ratio from 0.5 to 1.0 while at ratios above 1.0, a cylindrical pattern is seen. The hemimicelle morphology is able to prevent the agglomeration of CNTs when the CNT concentration increases to 8.7 mg/mL, while cylindrical morphology is more efficient and stable to provide dispersion of CNTs at higher concentrations of CNTs.

Photoinduced demulsification of emulsions using a photoresponsive gemini surfactant.

This Article reports on the influence of light irradiation on the stability of emulsions prepared using a photoresponsive gemini surfactant (C7-azo-C7) having an azobenzene skeleton as a spacer. When mixtures of trans C7-azo-C7 aqueous solution and n-octane are homogenized, stable emulsions are obtained in a specific region of weight fraction and surfactant concentration. Fluorescence microscopy observations using a small amount of fluorescent probes show that the stable emulsions are oil-in-water (O/W)-type. UV irradiation of stable O/W emulsions promotes the cis isomerization of trans C7-azo-C7 and leads to the coalescence of the oil (octane) droplets in the emulsions, that is, demulsification. While the equilibrated interfacial tension (IFT) between aqueous trans C7-azo-C7 solution and octane is almost the same as that between aqueous cis C7-azo-C7 and octane, the occupied area per molecule for C7-azo-C7 at octane/water interface decreases with the cis photoisomerization of trans isomer. Dynamic IFT measurement shows that UV irradiation to the interface between aqueous trans C7-azo-C7 solution and octane brings about an increase in the interfacial tension, indicating that the Gibbs free energy at the interface increases. From these results, the cis isomerization of trans C7-azo-C7 molecules at the O/W interface due to UV irradiation leads to direct contact between the water and octane phases, because of the reduction of molecular area at the interface, and subsequently makes the emulsions demulsified.

Hybrid response surface methodology-genetic algorithm optimization of ultrasound-assisted transesterification of waste oil catalysed by immobilized lipase on mesoporous silica/iron oxide magnetic core-shell nanoparticles.

The production ofbiodiesel by transesterification of waste cooking oil (WCO) to partially substitute petroleum diesel is one of the measures for solving the twin problems of environment pollution and energy demand. An environmentally benign process for the enzymatic transesterification using immobilized lipase has attracted considerable attention for biodiesel production. Here, a superparamagnetic, high surface area substrate for lipase immobilization is evaluated. These immobilization substrates are composed of mesoporous silica/superparamagnetic iron oxide core-shell nanoparticles. The effects of methanol ratio to WCO, lipase concentration, water content and reaction time on the synthesis of biodiesel were analysed by utilizing the response surface methodology (RSM). A quadratic response surface equation for calculating fatty acid methyl ester (FAME) content as the objective function was established based on experimental data obtained in accordance with the central composite design. The RSM-based model was then used as the fitness function for genetic algorithm (GA) to optimize its input space. Hybrid RSM-GA predicted the maximum FAME content (91%) at the optimum level of medium variables: methanol ratio to WCO, 4.34; lipase content, 43.6%; water content, 10.22%; and reaction time, 6h. Moreover, the immobilized lipase could be used for four times without considerable loss of the activity.

Lipid bilayer composition can influence the orientation of proteorhodopsin in artificial membranes.

Artificial membrane systems allow researchers to study the structure and function of membrane proteins in a matrix that approximates their natural environment and to integrate these proteins in ex vivo devices such as electronic biosensors, thin-film protein arrays, or biofuel cells. Given that most membrane proteins have vectorial functions, both functional studies and applications require effective control over protein orientation within a lipid bilayer. In this work, we explored the role of the bilayer surface charge in determining transmembrane protein orientation and functionality during formation of proteoliposomes. We reconstituted a model vectorial ion pump, proteorhodopsin, in liposomes of opposite charges and varying charge densities and determined the resultant protein orientation. Antibody-binding assay and proteolysis of proteoliposomes showed physical evidence of preferential orientation, and functional assays verified the vectorial nature of ion transport in this system. Our results indicate that the manipulation of lipid composition can indeed control orientation of an asymmetrically charged membrane protein, proteorhodopsin, in liposomes.

Effects of magnetite nanoparticles on soybean chlorophyll.

Nanoparticles (NPs) have emerged as one of the most innovative and promising application in agriculture. Since plants are recognized as essential component of all ecosystems, the effects of NPs on plants may pave a new insight to the ecosystems. Here, uptake and translocation of superparamagnetic iron oxide NPs (SPIONs), with various surface charges, on soybean has been probed; in addition, the effects of SPIONs on variations of chlorophyll, in hydroponic condition, together with their ability for reduction of iron deficiency chlorosis were explored. We find that SPIONs, which were entered and translocated in the soybean, increased chlorophyll levels, with no trace of toxicity. Furthermore, it was found that physicochemical characteristics of the SPIONs had a crucial role on the enhancement of chlorophyll content in subapical leaves of soybean. The equivalent ratio of chlorophyll a to b, in all treatments with conventional growth medium iron chelate and SPIONs (as iron source), indicated no significant difference on the photosynthesis efficiency. Finally, it was observed that the effect of SPIONs on the soybean chlorophyll content may have influence on both biochemical and enzymatic efficiency in different stages of the photosynthesis reactions.