Synthesis of hafnium oxide-gold core-shell nanoparticles.

Developing cheap composite nanoparticle systems that combines a high dielectric constant with good conductivity is important for the future of the electronic industry. In this study, two different sizes, 7.3 ± 2.2 and 5.6 ± 1.9 nm, of HfO(2)@Au core-shell nanoparticles are prepared by using a high-temperature reduction method. The core-shell nanoparticles are characterized by powder X-ray diffraction, high-resolution transmission electron microscopy (HRTEM), energy dispersive X-ray analysis (EDX), and UV-visible absorption spectroscopy. HfO(2) exhibits no absorption in the visible region, but the HfO(2)@Au core-shell nanoparticles show a plasmon absorption band at 555 nm that is 25 nm red-shifted as compared to pure gold nanoparticles. According to transmission electron microscopy and energy dispersive X-ray analysis, the HfO(2) particles are coated with approximately three atomic layers of gold.

Direct synthesis of aqueous quantum dots through 4,4'-bipyridine-based twin ligand strategy.

We report a new class of derivatized 4,4'-bipyridinium ligands for use in synthesizing highly fluorescent, extremely stable, water-soluble CdSe and CdTe quantum dots (QDs) for bioconjugation. We employed an evaporation-condensation technique, also known as solvated metal atom dispersion (SMAD), followed by a digestive ripening procedure. This method has been used to synthesize both metal nanoparticles and semiconductors in the gram scale with several stabilizing ligands in various solvents. The SMAD technique comprised evaporation condensation and stabilization of CdSe or CdTe in tetrahydrofuran. The as-prepared product was then digestively ripened in both water and dimethyl formamide, leading to narrowing of the particle size distributions. The ligands were synthesized by nucleophilic substitution (S(N)2) reactions using 4,4'-bipyridine as a nucleophile. Confocal microscopy images revealed the orange color of the nanocrystalline QDs with diameters of ~5 nm. The size has been confirmed by using transmission electron microscopy. As a part of our strategy, 85% of the 4,4'-bipyridinium salt was synthesized as propionic acid derivative and used to both stabilize the QDs in water and label basic amino acids and different biomarkers utilizing the carboxylic acid functional group. Fifteen percent of the 4,4'-bipyridinium salt was synthesized as N-propyl maleimide and used as a second ligand to label any protein containing the amino acid cysteine by means of a 1,4-Michael addition.

Exciton Dynamics in MoS2-Pentacene and WSe2-Pentacene Heterojunctions.

We measured the exciton dynamics in van der Waals heterojunctions of transition metal dichalcogenides (TMDCs) and organic semiconductors (OSs). TMDCs and OSs are semiconducting materials with rich and highly diverse optical and electronic properties. Their heterostructures, exhibiting van der Waals bonding at their interfaces, can be utilized in the field of optoelectronics and photovoltaics. Two types of heterojunctions, MoS2-pentacene and WSe2-pentacene, were prepared by layer transfer of 20 nm pentacene thin films as well as MoS2 and WSe2 monolayer crystals onto Au surfaces. The samples were studied by means of transient absorption spectroscopy in the reflectance mode. We found that A-exciton decay by hole transfer from MoS2 to pentacene occurs with a characteristic time of 21 ± 3 ps. This is slow compared to previously reported hole transfer times of 6.7 ps in MoS2-pentacene junctions formed by vapor deposition of pentacene molecules onto MoS2 on SiO2. The B-exciton decay in WSe2 shows faster hole transfer rates for WSe2-pentacene heterojunctions, with a characteristic time of 7 ± 1 ps. The A-exciton in WSe2 also decays faster due to the presence of a pentacene overlayer; however, fitting the decay traces did not allow for the unambiguous assignment of the associated decay time. Our work provides important insights into excitonic dynamics in the growing field of TMDC-OS heterojunctions.

Faraday rotation enhancement of gold coated Fe2O3 nanoparticles: comparison of experiment and theory.

Understanding plasmonic enhancement of nanoscale magnetic materials is important to evaluate their potential for application. In this study, the Faraday rotation (FR) enhancement of gold coated Fe(2)O(3) nanoparticles (NP) is investigated experimentally and theoretically. The experiment shows that the Faraday rotation of a Fe(2)O(3) NP solution changes from approximately 3 rad/Tm to 10 rad/Tm as 5 nm gold shell is coated on a 9.7 nm Fe(2)O(3) core at 632 nm. The results also show how the volume fraction normalized Faraday rotation varies with the gold shell thickness. From the comparison of experiment and calculated Faraday rotation based on the Maxwell-Garnett theory, it is concluded that the enhancement and shell dependence of Faraday rotation of Fe(2)O(3) NPs is a result of the shifting plasmon resonance of the composite NP. In addition, the clustering of the NPs induces a different phase lag on the Faraday signal, which suggests that the collective response of the magnetic NP aggregates needs to be considered even in solution. From the Faraday phase lag, the estimated time of the full alignment of the magnetic spins of bare (cluster size 160 nm) and gold coated NPs (cluster size 90 nm) are found to be 0.65 and 0.17 µs. The calculation includes a simple theoretical approach based on the Bruggeman theory to account for the aggregation and its effect on the Faraday rotation. The Bruggeman model provides a qualitatively better agreement with the experimentally observed Faraday rotation and points out the importance of making a connection between component properties and the average "effective" optical behavior of the Faraday medium containing magnetic nanoparticles.

Activation of N2 on Manganese Nitride-Supported Ni3 and Fe3 Clusters and Relevance to Ammonia Formation.

Dual-site models were constructed to represent manganese nitride (Mn4N)-supported Ni3 and Fe3 clusters for NH3 synthesis. Density functional theory calculations produced an energy barrier of approximately 0.55 eV for N-N bond activation at the interfacial nitrogen vacancy sites (Nv); also, the hydrogenation and removal of interfacial N is promoted by earth-abundant Ni and Fe metals. Steady-state microkinetic modeling revealed that the turnover frequencies of NH3 production follow an order of Fe3@Mn4N ≈ Ni3@Mn4N > Mn4N > Fe ≫ Ni. Moreover, we present clear evidence that, before NH3 formation, NH migrates from Nv onto the metallic sites. Using N binding energy (BEN) and the transition-state energy of N2 activation (ETS) as descriptors, we concluded that the beneficial effects owing to interfacial Nv sites are the most pronounced when BEN is either too strong or too weak while ETS is high; otherwise, excessive Nv sites may hinder catalyst performance.

A/C magnetic hyperthermia of melanoma mediated by iron(0)/iron oxide core/shell magnetic nanoparticles: a mouse study.

BACKGROUND: There is renewed interest in magnetic hyperthermia as a treatment modality for cancer, especially when it is combined with other more traditional therapeutic approaches, such as the co-delivery of anticancer drugs or photodynamic therapy. METHODS: The influence of bimagnetic nanoparticles (MNPs) combined with short external alternating magnetic field (AMF) exposure on the growth of subcutaneous mouse melanomas (B16-F10) was evaluated. Bimagnetic Fe/Fe3O4 core/shell nanoparticles were designed for cancer targeting after intratumoral or intravenous administration. Their inorganic center was protected against rapid biocorrosion by organic dopamine-oligoethylene glycol ligands. TCPP (4-tetracarboxyphenyl porphyrin) units were attached to the dopamine-oligoethylene glycol ligands. RESULTS: The magnetic hyperthermia results obtained after intratumoral injection indicated that micromolar concentrations of iron given within the modified core-shell Fe/Fe3O4 nanoparticles caused a significant anti-tumor effect on murine B16-F10 melanoma with three short 10-minute AMF exposures. We also observed a decrease in tumor size after intravenous administration of the MNPs followed by three consecutive days of AMF exposure 24 hrs after the MNPs injection. CONCLUSIONS: These results indicate that intratumoral administration of surface modified MNPs can attenuate mouse melanoma after AMF exposure. Moreover, we have found that after intravenous administration of micromolar concentrations, these MNPs are capable of causing an anti-tumor effect in a mouse melanoma model after only a short AMF exposure time. This is a clear improvement to state of the art.

Size-Controlled Synthesis of Iron and Iron Oxide Nanoparticles by the Rapid Inductive Heating Method.

Inductive heating synthesis is an emerging technique with the potential to displace the hot-injection synthesis method to prepare colloidal particles very rapidly with a narrow size distribution, controlled size, and high crystallinity. In this work, the inductive heating synthesis is applied to produce a short-temperature jump to mimic conditions like the hot-injection method to prepare traditional iron and iron oxide nanoparticles (IONPs) in the 3-11 nm size range within various solvents, precursors, and reaction time conditions. Moreover, this inductive heating technique can be used under unique experimental conditions not available for hot-injection reactions. These conditions include the use of very high initial monomer concentrations. Considering benefits over conventional methods, the inductive heating technique has the potential to provide an industrial level scale-up synthesis. The magnetization of these particles is consistent with the magnetization of the particles from the literature.

Effect of Cd/Te ratio on the formation of CdTe magic-sized quantum dots during aggregation.

In this study, the aggregation dynamics of magic-sized CdTe quantum dots is investigated. The experiments show that the growth kinetics of the quantum dots is very sensitive to the Cd/Te ratio. The crossover from tellurium-rich to cadmium-rich conditions produces a very different aggregation pattern, which can be explained by the lack of formation of magic-sized nanoparticles during the reaction conditions. A simple simulation that includes both monomer-induced growth and aggregation growth is presented to reproduce the experimentally observed aggregation patterns. The simulation results strongly suggest that the experimental aggregation pattern can be reproduced if initially a double magic-sized distribution is assumed. The numerical data clearly show that the aggregation is enhanced by the dipole-dipole interaction. Simulations also suggest that the neck formation of the CdTe quantum dot aggregates is unlikely under the experimental conditions. The absence of neck formation is in agreement with the expectations during high-temperature synthesis.

Rapid Induction and Microwave Heat-Up Syntheses of CdSe Quantum Dots.

The production of nanoparticles on an industrial scale requires an approach other than the widely used hot-injection method. In this work, two heat-up methods are applied to nanoparticle synthesis. The induction heating method produces CdSe quantum dots with ultrasmall properties in seconds. Initial flow-through experiments demonstrate that induction heating continuously produces quantum dots. These results are compared with those from microwave synthesis, which produces quantum dots on a longer timescale but provides fast, continuous heating. Both methods can produce quantum dots within seconds because of rapid heating. In addition, different precursors, single source and separate source, give different results, ultimately providing a handle to control quantum dot properties.

Rapid Nanoparticle Synthesis by Magnetic and Microwave Heating.

Traditional hot-injection (HI) syntheses of colloidal nanoparticles (NPs) allows good separation of the nucleation and growth stages of the reaction, a key limitation in obtaining monodisperse NPs, but with limited scalability. Here, two methods are presented for obtaining NPs via rapid heating: magnetic and microwave-assisted. Both of these techniques provide improved engineering control over the separation of nucleation and growth stages of nanomaterial synthesis when the reaction is initiated from room temperature. The advantages of these techniques with preliminary data are presented in this prospective article. It is shown here that microwave assisted heating could possibly provide some selectivity in activating the nanomaterial precursor materials, while magnetic heating can produce very tiny particles in a very short time (even on the millisecond timescale), which is important for scalability. The fast magnetic heating also allows for synthesizing larger particles with improved size distribution, therefore impacting, not only the quantity, but the quality of the nanomaterials.

Graphene/GaSe-Nanosheet Hybrid: Towards High Gain and Fast Photoresponse.

While high photoconductive gain has been recently achieved in graphene-based hybrid phototransistors using semiconductor two-dimensional transition/post-transition metal dichalcogenides or quantum dots sensitizers, obtaining fast photoresponse simutaneously remains a challenge that must be addressed for practical applications. In this paper we report a graphene/GaSe nanosheets hybrid photodetector, in which GaSe nanosheets provide a favorable geometric link to graphene conductive layer through van Der Waals force. After a vacuum annealing process, a high gain in exceeding 10(7) has been obtained simitaneously with a dynamic response time of around 10 ms for both light on and off. We attribute the high performance to the elimination of possible deep charge traps, most probably at the graphene/GaSe nanosheets interface. This result demonstrates high photoconductive gain and fast photoresponse can be achieved simultaneously and a clean interface is the key to the high performance of these hybrid devices.

Nested Helmholtz coil design for producing homogeneous transient rotating magnetic fields.

Electromagnets that can produce strong rotating magnetic fields at kHz frequencies are potentially very useful to exert rotating force on magnetic nanoparticles as small as few nanometers in size. In this article, the construction of a pulsed high-voltage rotating electromagnet is demonstrated based on a nested Helmholtz coil design. The energy for the coils is provided by two high-voltage discharge capacitors. The triggered spark gaps used in the experiments show sufficient accuracy to achieve the high frequency rotating magnetic field. The measured strength of the rotating magnetic field is 200 mT. This magnetic field is scalable by increasing the number of turns on the coils, by reducing the dimensions of the coils and by increasing the discharge current/voltage of the capacitors.

Combining hard and soft magnetism into a single core-shell nanoparticle to achieve both hyperthermia and image contrast.

BACKGROUND: A biocompatible core/shell structured magnetic nanoparticles (MNPs) was developed to mediate simultaneous cancer therapy and imaging. METHODS & RESULTS: A 22-nm MNP was first synthesized via magnetically coupling hard (FePt) and soft (Fe3O4) materials to produce high relative energy transfer. Colloidal stability of the FePt@Fe3O4 MNPs was achieved through surface modification with silane-polyethylene glycol (PEG). Intravenous administration of PEG-MNPs into tumor-bearing mice resulted in a sustained particle accumulation in the tumor region, and the tumor burden of treated mice was a third that of the mice in control groups 2 weeks after a local hyperthermia treatment. In vivo magnetic resonance imaging exhibited enhanced T2 contrast in the tumor region. CONCLUSION: This work has demonstrated the feasibility of cancer theranostics with PEG-MNPs.

Pulsed magnetic field induced fast drug release from magneto liposomes via ultrasound generation.

Fast drug delivery is very important to utilize drug molecules that are short-lived under physiological conditions. Techniques that can release model molecules under physiological conditions could play an important role to discover the pharmacokinetics of short-lived substances in the body. Here an experimental method is developed for the fast release of the liposomes' payload without a significant increase in (local) temperatures. This goal is achieved by using short magnetic pulses to disrupt the lipid bilayer of liposomes loaded with magnetic nanoparticles. The drug release has been tested by two independent assays. The first assay relies on the AC impedance measurements of MgSO4 released from the magnetic liposomes. The second standard release assay is based on the increase of the fluorescence signal from 5(6)-carboxyfluorescein dye when the dye is released from the magneto liposomes. The efficiency of drug release ranges from a few percent to up to 40% in the case of the MgSO4. The experiments also indicate that the magnetic nanoparticles generate ultrasound, which is assumed to have a role in the release of the model drugs from the magneto liposomes.

Effects of interband transitions on Faraday rotation in metallic nanoparticles.

The Faraday rotation in metallic nanoparticles is considered based on a quantum model for the dielectric function ϵ(ω) in the presence of a DC magnetic field B. We focus on effects in ϵ(ω) due to interband transitions (IBTs), which are important in the blue and ultraviolet for noble metals used in plasmonics. The dielectric function is found using the perturbation of the electron density matrix due to the optical field of the incident electromagnetic radiation. The calculation is applied to transitions between two bands (d and p, for example) separated by a gap, as one finds in gold at the L-point of the Fermi surface. The result of the DC magnetic field is a shift in the effective optical frequency causing IBTs by ±µBB/h, where opposite signs are associated with left/right circular polarizations. The Faraday rotation for a dilute solution of 17 nm diameter gold nanoparticles is measured and compared with both the IBT theory and a simpler Drude model for the bound electron response. Effects of the plasmon resonance mode on Faraday rotation in nanoparticles are also discussed.

Magnetic-Fe/Fe(3)O(4)-nanoparticle-bound SN38 as carboxylesterase-cleavable prodrug for the delivery to tumors within monocytes/macrophages.

The targeted delivery of therapeutics to the tumor site is highly desirable in cancer treatment, because it is capable of minimizing collateral damage. Herein, we report the synthesis of a nanoplatform, which is composed of a 15 ± 1 nm diameter core/shell Fe/Fe(3)O(4) magnetic nanoparticles (MNPs) and the topoisomerase I blocker SN38 bound to the surface of the MNPs via a carboxylesterase cleavable linker. This nanoplatform demonstrated high heating ability (SAR = 522 ± 40 W/g) in an AC-magnetic field. For the purpose of targeted delivery, this nanoplatform was loaded into tumor-homing double-stable RAW264.7 cells (mouse monocyte/macrophage-like cells (Mo/Ma)), which have been engineered to express intracellular carboxylesterase (InCE) upon addition of doxycycline by a Tet-On Advanced system. The nanoplatform was taken up efficiently by these tumor-homing cells. They showed low toxicity even at high nanoplatform concentration. SN38 was released successfully by switching on the Tet-On Advanced system. We have demonstrated that this nanoplatform can be potentially used for thermochemotherapy. We will be able to achieve the following goals: (1) Specifically deliver the SN38 prodrug and magnetic nanoparticles to the cancer site as the payload of tumor-homing double-stable RAW264.7 cells; (2) Release of chemotherapeutic SN38 at the cancer site by means of the self-containing Tet-On Advanced system; (3) Provide localized magnetic hyperthermia to enhance the cancer treatment, both by killing cancer cells through magnetic heating and by activating the immune system.

Cell-delivered magnetic nanoparticles caused hyperthermia-mediated increased survival in a murine pancreatic cancer model.

Using magnetic nanoparticles to absorb alternating magnetic field energy as a method of generating localized hyperthermia has been shown to be a potential cancer treatment. This report demonstrates a system that uses tumor homing cells to actively carry iron/iron oxide nanoparticles into tumor tissue for alternating magnetic field treatment. Paramagnetic iron/ iron oxide nanoparticles were synthesized and loaded into RAW264.7 cells (mouse monocyte/ macrophage-like cells), which have been shown to be tumor homing cells. A murine model of disseminated peritoneal pancreatic cancer was then generated by intraperitoneal injection of Pan02 cells. After tumor development, monocyte/macrophage-like cells loaded with iron/ iron oxide nanoparticles were injected intraperitoneally and allowed to migrate into the tumor. Three days after injection, mice were exposed to an alternating magnetic field for 20 minutes to cause the cell-delivered nanoparticles to generate heat. This treatment regimen was repeated three times. A survival study demonstrated that this system can significantly increase survival in a murine pancreatic cancer model, with an average post-tumor insertion life expectancy increase of 31%. This system has the potential to become a useful method for specifically and actively delivering nanoparticles for local hyperthermia treatment of cancer.

Preparation of iron and gold silicide nanodomains on silicon (111) by the reaction of gold, iron-gold core-shell, and alloy nanoparticles with triethylsilane.

This study describes a strategy to use composite colloidal nanoparticles and triethylsilane as precursors to synthesize nanometer size structures on single-crystal silicon substrate. The concept is demonstrated by depositing gold, iron-gold alloy, and iron-gold core-shell nanoparticles on silicon (111). Upon heating, the nanoparticles form new crystalline phases on the Si (111) surface. Atomic force microscope (AFM) data show the collapse of the iron gold core-shell and alloy nanoparticles at temperatures 100-200 degrees C higher than gold nanoparticles, indicating the efficient tethering of iron containing nanoparticles on silicon (111). Both structural analysis and X-ray spectroscopy show that the iron-gold alloy and iron-gold core-shell nanoparticles successfully form the semiconducting beta-FeSi(2) phase at relatively low temperature. The stabilities of the silicide are assessed at elevated temperatures. Silicon successfully nucleates on the created nanostructures, which suggests strong catalytic activity towards producing further nanostructures on the surface.

Attenuation of mouse melanoma by A/C magnetic field after delivery of bi-magnetic nanoparticles by neural progenitor cells.

Localized magnetic hyperthermia as a treatment modality for cancer has generated renewed interest, particularly if it can be targeted to the tumor site. We examined whether tumor-tropic neural progenitor cells (NPCs) could be utilized as cell delivery vehicles for achieving preferential accumulation of core/shell iron/iron oxide magnetic nanoparticles (MNPs) within a mouse model of melanoma. We developed aminosiloxane-porphyrin functionalized MNPs, evaluated cell viability and loading efficiency, and transplanted neural progenitor cells loaded with this cargo into mice with melanoma. NPCs were efficiently loaded with core/shell Fe/Fe(3)O(4) MNPs with minimal cytotoxicity; the MNPs accumulated as aggregates in the cytosol. The NPCs loaded with MNPs could travel to subcutaneous melanomas, and after A/C (alternating current) magnetic field (AMF) exposure, the targeted delivery of MNPs by the cells resulted in a measurable regression of the tumors. The tumor attenuation was significant (p < 0.05) a short time (24 h) after the last of three AMF exposures.

Direct observation of gold nanoparticle assemblies with the porin MspA on mica.

The octameric porin MspA from Mycobacterium smegmatis is sufficiently stable to form a nonmembrane-supported stand-alone porin on mica surfaces. About 98% of all MspA octamers were found to stand upright on mica, with their periplasmic loop regions bound to the hydrophilic mica surface. Both, small (d = 3.7 nm) and large (d = 17 nm) gold nanoparticles bind to MspA, however, in different positions: small gold nanoparticles bind within the MspA pore, whereas the large gold nanoparticles bind to the upper region of MspA. These experiments demonstrate that gold nanoparticles can be positioned at different, well-defined distances from the underlying surface using the MspA pore as a template. These findings represent a significant step toward the use of electrically insulating stable proteins in combination with metal nanoparticles in nanodevices.