Daniel Mandler

Institute of Chemistry
Faculty of Science
The Hebrew University, Jerusalem 91904, Israel
Tel: +972-2-6585831; Fax: +972-2- 6585319
E-mail: mandler@vms.huji.ac.il
Website:http://chem.ch.huji.ac.il/mandler/

Electrochemically Functionalized Coatings

Our research focuses on different aspects of patterning and deposition of nanostructures by electrochemistry. Specifically, we have focused on the following topics:

Electrochemical codeposition of sol-gel nanocomposites

We have developed a novel electrochemical method for the formation of nanocomposite thin films made of carbon nanotubes (CNTs) and a sol-gel matrix.

Figure 1: SEM image of PhMOS/CNTs-CO2H nanocomposite film electrochemically codeposited on ITO by applying -0.8 V for 10 min.

Growth of the films is driven by altering the pH on the electrode surface which catalyzes the condensation of the sol-gel precursors and the incorporation of the CNTs. The nanocomposite films were characterized by a wide variety of techniques including SEM, tunneling AFM, Nano Scratch Test, etc, which enabled to study the effect of different parameters, such as the potential of deposition, on the interface, morphology and phase composition as well as the effect of the CNTs on the resulting nanocomposite films. Finally, we have demonstrated the generic nature of this approach by using different types of CNTs and sol-gel precursors. Figure 1 shows the surface of ITO on which a layer composed of sol-gel and CNT was deposited electrochemically

Electrochemically coating of biomedical implants by nanoparticles

Biodegradable nanoparticles represent a promising platform for controlled release and other applications in medicine. To alter the interface of the medical device with the living tissue successfully, a thin coating needs to be applied onto the surface. The traits and functionality of the coating depends on its components, which in the presented work are sol-gel and biodegradable nanoparticles (NPs) deposited onto the substrate using the electrochemical sol-gel method. Aspects affecting the deposition process were investigated such as the applied potential and its duration. The properties of the deposits with emphasis on the biodegradable NPs within the deposited films were characterized and studied. Another element examined was the loading ability of the NPs. A fluorescent organic molecule was incorporated in the biodegradable NPs as a drug model, to demonstrate loading capability.

Figure 2: Top - schematics of the approach for the deposition of nanoparticles on biomedical implants. Bottom -

Preparation and Characterization of Mono and Multilayer Films of Polymerizable 1,2 Polybutadiene Using the Langmuir-Blodgett Technique

The essence of this part was to apply the Langmuir Blodgett (LB) technique for assembling asymmetric membranes. Accordingly, Langmuir films of a (further) polymerizable polymer; 1,2 polybutadiene (1,2-pbd), were studied and transferred onto different solid supports, such as gold, indium tin oxide (ITO) and silicon. The layers were characterized both at the air-water interface as well as on different substrates using numerous methods including cyclic voltammetry, impedance spectroscopy, spectroscopic ellipsometry, AFM, XPS and reflection-absorption FTIR. The Langmuir films were stable at the air-water interface as long as they were not exposed to UV irradiation. The LB films formed disorganized layers, which gradually blocked the permeation of different species with increasing the number of deposited layers. The thickness was ca. 4-7 A per layer. Irradiating the Langmuir films caused their cross-linking at the water-air interface. Furthermore, we took advantage of the reactivity of the double bo nd of the LB films on the solid supports and graft polymerized acrylic acid on top of the 1,2-pbd layers. This approach is the basis of the formation of an asymmetric membrane that requires different porosity on its both sides.

Figure 3: Left - schematics of the system studied, right - AFM images (height and phase imaging) of Si after deposition of partially polymerized 1,2-pbd Langmuir films: A - one layer, B - three layers of partially polymerized 1,2-pbd.

Specific research topics related to Nanoscience and Nanotechnology:

• Electrochemically codeposition of carbon nanotubes and sol-gel
• Design of asymmetric membranes by nanometric films
• Visualization of fingerprints using nanotechnology
• Coating medical implants by nanoparticles

List of publications in Nanoscience and Nanotechnology (2009-2011)

• R. Okner, M. Oron, N. Tal, A. Nyska, N. Kumar, D. Mandler, A. J. Domb, Electrocoating of stainless steel coronary stents for extended release of paclitaxel, J. Biomed. Mater. Res. Part A, 2009, 88, 510-513.
• M. Sheffer and D. Mandler, Control of Locally Deposited Gold Nanoparticle on Polyaniline Films, Electrochim. Acta, 2009, 54, 2951-2956.
• J. Zhang, D. P. Burt, A. L. Whitworth, D. Mandler and P. R. Unwin, Polyaniline Langmuir-Blodgett films: formation and properties, Phys. Chem. Chem. Phys. 2009, 11, 3490-3496. 
• R. Okner, Y. Shaulov, N. Tal, G. Favaro, A. J. Domb and D. Mandler, Electropolymerized Tricopolymer Based on N-Pyrrole Derivatives as a Primer Coating for Improving the Performance of a Drug Eluting Stent, J. Appl. Mater. Interfaces, 2009, 1, 758-767.
• R. Okner, A. J. Domb and D. Mandler, Electrochemically Deposited Poly(ethylene glycol)-Based Sol-Gel Thin Films on Stainless Steel Stents, New J. Chem., 2009, 33, 1596-1604.
• Y. Levy, N. Tal, J. Weinberger, A. J. Domb and D. Mandler, Evaluation of Drug-Eluting Stents' Coating Durability--Clinical and Regulatory Implications, Journal of Biomedical Materials Research: Part B - Applied Biomaterials, 2009, 91, 441-451.
• Y. Levi, N. Tal, J. Weinberger, A. J. Domb and D. Mandler, Drug-Eluting Stent with Improved Durability and Controllability Properties, Obtained via Electrocoated Adhesive Promotion Layer, Journal of Biomedical Materials Research: Part B - Applied Biomaterials, 2009, 91B, 819-830.
• A. Becker, H. Tobias and D. Mandler, Electrochemical Determination of Uranyl Ions Using a Self-Assembled Monolayer, Anal. Chem. 2009, 81, 8629-8631.
• Y. Shaulov, R. Okner, Y. Levi, N. Tal, V. Gutkin, D. Mandler, and A. J. Domb, Poly(methyl methacrylate) Grafting onto Stainless Steel Surfaces: Application to Drug-Eluting Stents, Appl. Mater Interfaces, 2009, 1, 2519-2528.
• R. Shacham, D. Mandler and D. Avnir, Pattern recognition in oxides thin-film electrodeposition: Printed circuits, C. R. Chimie, 2010, 13, 237-241.
• Gofberg and D. Mandler, Preparation and Comparison between Different Thiol-Protected Au Nanoparticles, J. Nanoparticle Res., 2010, 12, 1807-1811.
• G. Tanami, V. Gutkin and D. Mandler, Thin Nanocomposite Films of Polyaniline/Au-Nanoparticles by the Langmuir-Blodgett Technique, Langmuir, 2010, 26, 4239-45.
• S. Kraus-Ophir, J. Almog and D. Mandler, Selective Complexation between a Novel Bowl-Shaped Molecule and Fe3+ or PdCl42- Ions, Inorg. Chim. Acta, 2010, 363, 2677-2681. http://dx.doi.org/10.1016/j.ica.2010.04.032
• R. Toledano and D. Mandler, Electrochemical Codeposition of Gold Nanoparticles/Sol-Gel Thin Films, Chem. Mater., 2010, 22, 3943-3951.
• R. Ginzburg-Turgeman and D. Mandler, Nanometric Thin Polymeric Films Based on Molecularly Imprinted Technology: towards Electrochemical Sensing Applications, Phys. Chem. Chem. Phys., 2010, 12, 11041-11050.
• I. Levy, S. Magdassi and D. Mandler, Potential Induced pH Change: towards Electrochemical Coating of Medical Implants by Organic Nanoparticles, Electrochim. Acta, in press 2010, http://dx.doi.org/10.1016/j.electacta.2010.07.067
• E. Malel, R. Ludwig, L. Gorton and D. Mandler, Local Bio-catalyzed Deposition of Au Nanoparticles by Cellobiose Dehydrogenase and, Chem. Eur. J., 2010, 16, 11697-11706. http://dx.doi.org/10.1002/chem.201000453
• R. Okner, G. Favaro, A. Radko,A. J. Domb and D. Mandler, Electrochemical Codeposition of Sol-Gel Films on Stainless Steel: Controlling the Chemical and Physical Coating Properties of Biomedical Implants, Phys. Chem. Chem. Phys., 2010, in press, http://dx.doi.org/10.1016/j.electacta.2010.07.067
• D. Mandler, Formation, Characterization, and Applications of Organic and Inorganic Nanometric Films, Isr. J. Chem. 2010, in press.
• T. Noyhouzer and D. Mandler, Determination of Low Levels of Cadmium Ions by the Under Potential Deposition on a Self-Assembled Monolayer on Gold Electrode, Anal. Chim. Acta 2010, in press.
• L. Liu, R. Toledano, T. Danieli, J.-Q. Zhang, J.-M. Hu and D. Mandler, Electrochemically Patterning Sol-Gel Structures on Conducting and Insulating Surfaces, Chem. Comm. 2011, 47, 6909-6911.
• E. Malel, J. Colleran and D. Mandler, Studying the Localized Deposition of Ag Nanoparticles on Self-Assembled Monolayers by Scanning Electrochemical Microscopy (SECM), Electrochim. Acta, 2011, 56, 6954-6961.
• D. Mandler and S. Kraus-Ophir, Self-Assembled Monolayers (SAMs) for Electrochemical Sensing, J. Solid State Electrochem., 2011, 15, 1535-1558.
• E. Gdor and D. Mandler, Electrochemical Assisted Deposition of Biodegradable Polymer Nanoparticles/Sol Gel Thin Films, J. Mater. Chem., 2011, 21, 12145-12150
• S. Kraus-Ophir, I. Jerman, B. Orel and D. Mandler, Symmetrical thiol functionalized polyhedral oligomeric silsesquioxanes as building blocks for LB films, Soft Matter, 2011, in press.
• T. Danieli, J. Colleran and D. Mandler, Deposition of Au and Ag Nanoparticles on PEDOT, Phys. Chem. Chem. Phys. 2011, in press.
• M. Hitrik, V. Gutkin, O. Lev and D. Mandler, Preparation and Characterization of Mono and Multilayer Films of Polymerizable 1,2 Polybutadiene Using the Langmuir-Blodgett Technique, Langmuir, 2011, in press.

Five most significant publications and number of citations:

• G. Tanami, V. Gutkin and D. Mandler, Thin Nanocomposite Films of Polyaniline/Au-Nanoparticles by the Langmuir-Blodgett Technique, Langmuir, 2010, 26, 4239-45.
• R. Toledano and D. Mandler, Electrochemical Codeposition of Gold Nanoparticles/Sol-Gel Thin Films, Chem. Mater., 2010, 22, 3943-3951.
• E. Malel, R. Ludwig, L. Gorton and D. Mandler, Localized Deposition of Au Nanoparticles by Direct Electron Transfer through Cellobiose Dehydrogenase, Chem. Eur. J., 2010, 16, 11697-11706.
• L. Liu, R. Toledano, T. Danieli, J.-Q. Zhang, J.-M. Hu and D. Mandler, Electrochemically Patterning Sol-Gel Structures on Conducting and Insulating Surfaces, Chem. Comm. 2011, 47, 6909-6911.
• M. Hitrik, V. Gutkin, O. Lev and D. Mandler, Preparation and Characterization of Mono and Multilayer Films of Polymerizable 1,2 Polybutadiene Using the Langmuir-Blodgett Technique, Langmuir, 2011, in press.

New patents and patents utilization (2009-2011):

• Process for Electrochemical Coating of Conductive Surfaces by Organic Nanoparticles, with Shlomo Magdassi.
• Solar-Radiation-Absorbing Formulation and Related Apparatus and Methods, with Shlomo Magdassi.

Cooperation with industries and defense projects (2010-2011):

• Magnet SES - solar energy systems
• Magnet NES - nano empowerment systems
• Project with BrightSource on Photothermal Solar Conversion

Success stories:

Cooperation with Industry and Academia

• Collaboration with Shlomo Magdassi (different projects).
• Collaboration with Joseph Almog (visualization of fingerprints by nanotechnology).
• Collaboration with Avi Domb on coating of stents by electrochemistry.
• Collaboration with Uri Banin on organizing nanorods using the LB method.

• Collaboration with Moshe Lalouche from Bar Ilan University.
• Collaboration with Rachel Yerushalmi from Ben Gurion University.

Research grants:

• ISF
• GIF
• BSF
• Magnet SES
• Magnet NES
• Magneton
• Ministry of Science - Tashtiot
• European project
• Office of Naval Research - Technical Support Working Group (TSWG)

List of Students:

Staff scientists:Dr. Camille Zwiker
Postdocs: Dr. Adam Lesniewski, Dr. Liang Liu
PhD students: (present and graduated) Shlomit Kraus, Tomer Noyhouzer, Esteban Malel, Tamar Danieli, Maria Hitrik, Efrat Gdor, Reut Toledano, Itamar Gofberg
MSc students: Rachel Assa, Moran Rave, Dani Tulchinski, Tehila Shahar, Elena Krent

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