Journal Article

2014
Tivony R, Larush L, Sela-Tavor O, Magdassi S. Biomedical Imaging of Colorectal Cancer by Near Infrared Fluorescent Nanoparticles. Journal of biomedical nanotechnology. 2014;10 (6) :1041 - 1048.Abstract

In this paper we describe the preparation of novel Near Infrared (NIR) fluorescent nanoparticles for application in medical imaging of colorectal tumors. The nanoparticles are prepared by using only non-covalent binding processes of molecules which are approved for clinical use. The preparation process is based on the precipitation of a polycation, Eudragit-RS, followed by sequential adsorption of a blocking protein, sodium caseinate, NIR fluorescent dye, Indocyanine Green (ICG) and optionally, a targeting molecule, anti-CEA antibody. Fluorescence measurements have shown that these nanoparticles have higher resistance to photobleaching and higher quantum yield relatively to free ICG. Imaging experiments in orthotopic colorectal cancer mice models have shown that these fluorescent nanoparticles are capable of binding to LS174T human colon tumors in vivo with high specificity, even without the targeting molecule. These nanoparticles, composed of all FDA approved materials, open the way to clinical bioimaging and diagnostics of colon cancer.

Cao X, Wang N, Magdassi S, Mandler D, Long Y. Europium Doped Vanadium Dioxide Material: Reduced Phase Transition Temperature, Enhanced Luminous Transmittance and Solar Modulation. [Internet]. 2014;6 (3) :558 - 561. Publisher's VersionAbstract

Vanadium dioxide is a well-known near room temperature phase transition material with a transition temperature (tau(C)) at 68 degrees C. In this paper, Eu3+ dopant with different doping levels was introduced into the crystal lattice of VO2. The thermochromic properties, including the integrated visible transmittance (T-lum) and the solar modulating ability (Delta T-sol) were favorably affected by the Eu-doping. It is of great interest that the substitution of V4+ by Eu3+ in the VO2 crystal structure reduced the tau(C) from 68 degrees C to 47.5 degrees C with an approximate decreasing rate of 6.5 degrees C/at% up to 4 at%. More importantly, the Eu dopant helped in improving the properties of luminous transmittance and solar modulating ability, which were difficult to be achieved by other dopants.

Meker S, Margulis-Goshen K, Magdassi S, Tshuva EY. Hydrolysis Resistant Salan Titanium(IV) Anti-cancer Agents in Nanoparticles. [Internet]. 2014;19 :S650 - S650. Publisher's Version
Grouchko M, Roitman P, Zhu X, Popov I, Kamyshny A, Su HB, Magdassi S. Merging of metal nanoparticles driven by selective wettability of silver nanostructures. Nature communications. 2014;5.Abstract

The welding and sintering of nanomaterials is relevant, for example, to form electrical contacts between metallic particles in printed electronic devices. Usually the welding of nanoparticles is achieved at high temperatures. Here we find that merging of two different metals, silver and gold nanoparticles, occurs on contact at room temperature. The merging process was investigated by experimental and molecular dynamics simulations. We discovered that the merging of these particles is driven by selective wettability of silver nanoparticles, independent of their size and shape (spheres or rods); silver behaves as a soft matter, whereas gold as a hard surface being wetted and retaining its original morphology. During that process, the silver atoms move towards the surface of the Au nanoparticles and wrap the Au nanoparticles in a pulling up-like process, leading to the wetting of Au nanoparticles.

Cao X, Wang N, Law JY, Loo SCJ, Magdassi S, Long Y. Nanoporous Thermochromic VO2 (M) Thin Films: Controlled Porosity, Largely Enhanced Luminous Transmittance and Solar Modulating Ability. [Internet]. 2014;30 (6) :1710 - 1715. Publisher's VersionAbstract

Vanadium dioxide is the most widely researched thermochromic material with a phase transition temperature (tau(c)) of around 68 degrees C, and its thermochromic performance can be enhanced by adding nanoporosity. Freeze-drying has been employed to fabricate nanostructures with different porosities from 16 to 45% by varying the prefreezing temperature and precursor concentration. The luminous transmittance (T-lum) and solar modulating ability (Delta T-sol) are greatly enhanced as a result of increasing pore size and pore density. The freeze-dried sample with 7.5 mL of H2O2 precursor dip-coated at 300 mm/min gives the best combination of thermochromic properties (T-lum approximate to 50%, Delta T-sol = 14.7%), which Surpasses the best combined thermochromic performance reported to date that we are aware of (T-lum approximate to 41%, Delta T-sol = 14.1%).

2013
Lim HM, Batabyal SK, Pramana SS, Wong LH, Magdassi S, Mhaisalkar SG. Chemical welding of binary nanoparticles: room temperature sintering of CuSe and In2S3 nanoparticles for solution-processed CuInSxSe1-x solar cells. [Internet]. 2013;49 (47) :5351 - 5353. Publisher's VersionAbstract

Chemical welding of oppositely charged dissimilar metal chalcogenide nanomaterials is reported to produce a quaternary metal chalcogenide. CuSe and In2S3 nanoparticles were synthesized with opposite surface charges by stabilizing with polyacrylic acid and polydiallyldimethylammonium chloride. Upon mixing these nanoparticles at room temperature, the electrostatic attraction induced coalescence of these nanoparticles and led to the formation of CuInSxSe1-x nanoparticles.

Kumar RSS, Shiny PJ, Anjali CH, Jerobin J, Goshen KM, Magdassi S, Mukherjee A, Chandrasekaran N. Distinctive effects of nano-sized permethrin in the environment. [Internet]. 2013;20 (4) :2593 - 2602. Publisher's VersionAbstract

Pesticides are an essential tool in integrated pest management. Nanopermethrin was prepared by solvent evaporation from an oil-in-water volatile microemulsion. The efficacy of the formulated nanopermethrin was tested against Aedes aegypti and the results compared to those of regular, microparticular permethrin. The 24 h LC50 for nanopermethrin and permethrin was found to be 0.0063 and 0.0199 mg/L, respectively. The formulated nanopermethrin was tested for toxicity against non-target organisms. Nanopermethrin did not show antibacterial activity against Escherichia coli (ATCC 13534 and 25922) or against Bacillus subtilis. Phytotoxicity studies of nanopermethrin to the seeds of Lycopersicum esculentum, Cucumis sativus, and Zea mays showed no restraint in root length and germination percentage. In the Allium cepa test, regular microparticular permethrin treatment of 0.13 mg/L showed a mitotic index (MI) of 46.8 % and chromosomal aberration of 0.6 %, which was statistically significant (p < 0.05) compared to control. No significant differences were observed in 0.13 mg/L nanopermethrin exposure as compared to control (MI of 52.0 and 55.03 % and chromosomal aberration of 0.2 and 0 %, respectively). It was concluded that formulated nanopermethrin can be used as a safe and effectual alternative to commercially available permethrin formulation in agricultural practices.

Margulis-Goshen K, di Gregorio MC, Pavel NV, Abezgauz L, Danino D, Tato JV, Tellini VHS, Magdassi S, Galantini L. Drug-loaded nanoparticles and supramolecular nanotubes formed from a volatile microemulsion with bile salt derivatives. [Internet]. 2013;15 (16) :6016 - 6024. Publisher's VersionAbstract

The main objective of this study was to form nanoparticles of a model hydrophobic drug, celecoxib, from a volatile microemulsion stabilized by a bile salt derivative. Nanoparticles were obtained by conversion of the microemulsion nanodroplets with the dissolved drug into solid nanometric particles. The use of bile salt derivatives as the surfactants for the formation of a microemulsion enabled significantly higher loading of the drug in both the microemulsion and nanoparticles, compared with the native bile salt. In addition, superior stability of the particles was achieved with the bile salt derivatives, and drug crystallization was inhibited. Interestingly, differences in particle stability and crystallization inhibition were observed between two bile salt derivatives differing only by one hydroxyl group on the bile salt backbone, indicating the delicate balance of interactions in the system. For one of the derivatives, upon dispersion of the nanoparticles in water, they spontaneously arranged into well-defined elongated nanometric tubules as detected and attested by cryo-TEM. It was found that the drug present in nanoparticles induces formation of the nanotubes.

Ning W, Huang YZ, Magdassi S, Mandler D, Hai L, Yi L. Formation of VO2 zero-dimensional/nanoporous layers with large supercooling effects and enhanced thermochromic properties. [Internet]. 2013;3 (19) :7124 - 7128. Publisher's VersionAbstract

Vanadium dioxide is an intriguing candidate for use in intelligent devices such as sensors, magnetic refrigeration and particularly as solar modulating smart window materials. A facile sol-gel route is developed to produce pure VO2 with different nanostructures in a CO2 atmosphere. It was found that the nanoporous structures demonstrated a 16% increase in the luminous transmittance (T-lum) (from 20% to 36%) compared with the vacuum results, while large supercooling effects of up to 30 degrees C have been observed in zero-dimensional structures.

Lu YX, Liu L, Foo W, Magdassi S, Mandler D, Lee PS. Self-assembled polymer layers of linear polyethylenimine for enhancing electrochromic cycling stability. [Internet]. 2013;1 (23) :3651 - 3654. Publisher's VersionAbstract

A self-assembled polymer of linear polyethylenimine (LPEI) on indium tin oxide (ITO) is found to stabilize the titanium-doped vanadium oxide film. After modification by LPEI, the oxide film shows good cycling stability, and sustains over 1500 cycles in a three-electrode system, a remarkable improvement compared to that without LPEI modification.

Layani M, Cooperstein I, Magdassi S. UV crosslinkable emulsions with silver nanoparticles for inkjet printing of conductive 3D structures. Journal of Materials Chemistry C. 2013;1 (19) :3244-3249.Abstract

3D conductors are developed by inkjet printing a UV curable ink composed of oil-in-water emulsion combined with a dispersion of silver nanoparticles. Upon UV radiation by LED light the droplets immediately polymerize and form solid structures with embedded silver nanoparticles. The unique composition of the new ink enables sintering of the silver nanoparticles at room temperature by contact with NaCl solution, leading to a conductivity of 1.9 × 106 S m−1 while maintaining the 3D structure. The aspect ratio for photo-polymerized printed lines is more than 10 times larger than that of non-irradiated lines. The emulsion–dispersion new inks are potential materials for 3D fabrication of conductors and other functional materials in printed electronics

Wang JX, Yan CY, Magdassi S, Lee PS. Zn2GeO4 Nanowires As Efficient Electron Injection Material for Electroluminescent Devices. [Internet]. 2013;5 (15) :6793 - 6796. Publisher's VersionAbstract

Pure phase Zn2GeO4 nanowires (NWs) were grown by the chemical vapor transport method on p-GaN: Mg/Al2O3 substrate. The as grown Zn2GeO4 NWs exhibited n-type characteristic due to native defects and formed a p-n heterojunction with the p-GaN substrate. The unique energy level of Zn2GeO4 NWs promotes electron injection into GaN active region while suppressing hole injection into Zn2GeO4 NWs. The device exhibited an emission centered at 426 nm and a low turn-on voltage around 4 V. Zn2GeO4 NWs are first reported in this paper as promising electron transport and injection material for electroluminescent devices.

2012
Portnoy E, Gurina M, Magdassi S, Eyal S. Evaluation of the Near Infrared Compound Indocyanine Green as a Probe Substrate of P-Glycoprotein. [Internet]. 2012;9 (12) :3595 - 3601. Publisher's VersionAbstract

The efflux transporter P-glycoprotein (P-gp) affects the pharmacokinetics of many drugs. Currently used methods for characterization of P-gp's functional activity in vivo involve the use of radiolabeled substrates, are costly, and are technically demanding. Our objective was to evaluate whether the FDA-approved near-infrared compound indocyanine green (ICG) can be used as a probe substrate of P-gp. We also characterized the interaction of ICG with another efflux transporter, the breast cancer resistance protein (BCRP). We evaluated ICG accumulation and transport in MDCK cells overexpressing P-gp or BCRP (MDCK-MDRI and MDCK-BCRP, respectively) compared to control MDCK cells, in the presence or the absence of transporter inhibitors. In vivo imaging of ICG biodistribution in mice was conducted over 3.5 h using valspodar as the P-gp inhibitor. The EC50 values for ICG accumulation in control MDCK and MDCK-MDR1 cells were 9.0 x 10(-6) +/- 5.7 x 10(-7) M and 1.5 x 10(-5) +/- 1.1 x 10(-6) M, respectively. The efflux ratio for ICG in MDCK-MDR1 cells was 6.8-fold greater than in control cells. P-gp inhibition attenuated ICG efflux from MDR1-MDCK cells, and their effects in those cells were greater than in control MDCK cells. In contrast, BCRP level of expression or pharmacological inhibition did not significantly affect ICG cellular accumulation. In vivo imaging indicated enhanced cerebral ICG distribution with valspodar (brain - foot area under the concentration-time curves of 3.0 x 10(10), 5.6 x 10(10) and 3.7 x 10(19) h.[p/s/sr]/mu W in valspodar-treated mice vs 9.0 x 10(9) and 5.3 x 10(9) h.[p/s/sr]/mu W in controls). The findings from this pilot study suggest that near-infrared imaging using ICG as the probe substrate should be further characterized as a methodology for in vivo evaluation of P-gp activity.

Azoubel S, Shemesh S, Magdassi S. Flexible electroluminescent device with inkjet-printed carbon nanotube electrodes. [Internet]. 2012;23 (34). Publisher's VersionAbstract

Carbon nanotube (CNTs) inks may provide an effective route for producing flexible electronic devices by digital printing. In this paper we report on the formulation of highly concentrated aqueous CNT inks and demonstrate the fabrication of flexible electroluminescent (EL) devices by inkjet printing combined with wet coating. We also report, for the first time, on the formation of flexible EL devices in which all the electrodes are formed by inkjet printing of low-cost multi-walled carbon nanotubes (MWCNTs). Several flexible EL devices were fabricated by using different materials for the production of back and counter electrodes: ITO/MWCNT and MWCNT/MWCNT. Transparent electrodes were obtained either by coating a thin layer of the CNTs or by inkjet printing a grid which is composed of empty cells surrounded by MWCNTs. It was found that the conductivity and transparency of the electrodes are mainly controlled by the MWCNT film thickness, and that the dominant factor in the luminance intensity is the transparency of the electrode.

Dvores MP, Marom G, Magdassi S. Formation of Organic Nanoparticles by Electrospinning of Volatile Microemulsions. [Internet]. 2012;28 (17) :6978 - 6984. Publisher's VersionAbstract

This study presents a method for one-step formation of poly(ethylene oxide) nanofibers incorporating, nanoparticles of a poorly water-soluble compound. Using the new method reported here, nanofiber-nanoparticle composites are fabricated in one step by electrospinning of an oil-in-water microemulsion, in which a model material, propylparaben, has been dissolved within the volatile dispersed phase in the presence of a high-molecular-weight polymer. The approach is based on nanoscale confinement to the dispersed phase of an oil-in-water microemulsion with a volatile oil phase, in which the poorly water-soluble materials are dissolved. Thus, when the thermodynamically stable oil-in-water microemulsion is combined with the rapid evaporation of solvent inherent in the electrospinning process, the droplets are converted into organic nanoparticles embedded within a polymeric nanofiber. In addition to possessing process simplicity, this method exhibits a very high percentage of nanopartide loading with desirable active material properties. Specifically, the diameter of the nanofibers is in the range of 60-185 nm, and propylparaben exists within the nanofiber as nanocrystals of 30-120 nm. These dimensions suggest that the nanofiber nanocrystal composites could serve as a delivery system for water-insoluble materials.

Frusic-Zlotkin M, Soroka Y, Tivony R, Larush L, Verkhovsky L, Bregegere FM, Neuman R, Magdassi S, Milner Y. Penetration and biological effects of topically applied cyclosporin A nanoparticles in a human skin organ culture inflammatory model. [Internet]. 2012;21 (12) :938 - 943. Publisher's VersionAbstract

Systemic antipsoriatic therapies have potentially life-threatening, long-term side effects. The efficacy of topical drugs is poor, but may be improved by the use of delivery systems based on drug nanoparticles. To produce nanoparticles (NP) composed of cyclosporin A, a classical antipsoriatic drug, and to investigate their penetration and biological effects in human skin affected by psoriatic symptoms, poly-e-caprolactone (PCL) and cyclosporin A (CsA) NP were prepared by the solvent evaporation method. Skin penetration was followed using fluorescently labeled NP in human skin organ cultures (hSOC). Psoriatic symptoms were mimicked in hSOC by the treatment with epidermal growth factor (EGF) and bacterial lipopolysaccharide (LPS). Cell viability in hSOC was evaluated by the resazurin test, and cytokine secretion into the growth medium was measured by immunodetection. We showed that topically applied NP diffused throughout the epidermis within two hours and through the dermis within the following day. They significantly reduced the secretion of inflammatory cytokines IL1 beta, IL6, IL8, IL20 and IL23. At active doses, no cytotoxicity was detected. This type of NP display relevant properties for the use as topical anti-inflammatory agents and may help to resorb psoriatic lesions.

Perelaer J, Jani R, Grouchko M, Kamyshny A, Magdassi S, Schubert US. Plasma and Microwave Flash Sintering of a Tailored Silver Nanoparticle Ink, Yielding 60% Bulk Conductivity on Cost- Effective Polymer Foils. [Internet]. 2012;24 (29) :3993 - 3998. Publisher's Version
2011
Grouchko M, Kamyshny A, Mihailescu CF, Anghel DF, Magdassi S. Conductive Inks with a "Built-In" Mechanism That Enables Sintering at Room Temperature. ACS nano 5.4. 2011;5 (4) :3354 - 3359.Abstract

At present there is no metallic ink that enables formation of conductive patterns at room temperature by a single printing step. Printing conductive features by metallic nanoparticle-based inks must be followed by sintering while heating to elevated temperatures, thus preventing their utilization on most plastic substrates used in plastic electronics. In this report we present a new silver nanoparticle-based conductive ink, having a built-in sintering mechanism, which is triggered during drying of the printed pattern. The nanoparticles that are stabilized by a polymer undergo self-sintering spontaneously, due to the presence of a destabilizing agent, which comes into action only during drying of the printed pattern. The destabilizing-agent, which contains Cl- ions, causes detachment of the anchoring groups' of the stabilizer from the nanoparticles surface and thus enables their coalescence and sintering. It was found that the new metallic ink leads to very high conductivities, by a single printing step: up to 41% of the conductivity of bulk silver was achieved, the highest reported conductivity of a printed pattern that is obtained from nanoparticles at room temperature.

Layani M, Magdassi S. Flexible transparent conductive coatings by combining self-assembly with sintering of silver nanoparticles performed at room temperature. Journal of Materials Chemistry. 2011;21 (39) :15378-15382.Abstract

Transparent conductive coatings are essential for fabrication of a variety of printed electronic devices such as flexible displays and solar cells. We report on a simple method to obtain such coatings by using aqueous dispersions of silver nanoparticles in an evaporative lithography process which is performed directly onto plastic substrates. In essence, a droplet containing silver nanoparticles is placed on top of a metallic mesh, instantaneously spreading over the mesh and the plastic substrate, and after the flow of the dispersion towards the wires of the mesh and drying, a transparent grid composed of the nanoparticles is formed. The silver nanoparticles are tailored to self-sinter upon short exposure to HCl vapors, due to the presence of polyacrylic acid salt on the surface of the particles. Therefore, immediate sintering of the silver nanoparticles in the thin lines of the grid occurs even at room temperature, enabling formation of transparent, flexible conductive grid on heat-sensitive substrates. The process yielded a conductive array having a very low sheet resistance, 9 ± 0.8 Ω/□, and a transparency above 75%. The application of the flexible conductive grid, which can replace conventional and expensive ITO, is demonstrated in an electroluminescent (EL) device.

Margulis-Goshen K, Silva BFB, Marques EF, Magdassi S. Formation of solid organic nanoparticles from a volatile catanionic microemulsion. SOFT MATTER [Internet]. 2011;7 (19) :9359 - 9365. Publisher's VersionAbstract

A novel volatile microemulsion formed by the catanionic surfactant hexadecyltrimethylammonium octylsulfonate (TA(16)So(8)), heptane and water has been explored as a template for producing nanoparticles of hydrophobic organic materials. Butylated hydroxytoluene (BHT) was employed as the model hydrophobic substance. First, the oil-in-water microemulsion was formed, containing TA16So8 as the single emulsifier and BHT dispersed in the volatile microphase. Microstructure characterization by self-diffusion NMR revealed that BHT was indeed incorporated into the oil droplets and that the mean diameter of the main droplet population was 30 nm, larger than in the BHT-free microemulsion. Next, a rapid solvent and water removal by freeze drying allowed converting the microemulsion droplets into nanoparticles in the form of a dry, fine powder. This powder was freely dispersible in water to yield a stable suspension of amorphous BHT particles with a mean size of 19 nm and zeta-potential of +37 mV. The solid nanoparticles in the aqueous dispersion were thus smaller than the initial microemulsion droplets. For comparison, a conventional o/w microemulsion composed of CTAB and sec-butanol was also tested as a template for BHT particle formation by the same process, and it was found that it yielded crystalline particles of micrometre size. On the basis of our results, we anticipate the catanionic microemulsion method to be an efficient one for producing size-controlled, water-dispersible nanoparticles of other hydrophobic organic materials.

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