Shen, M. - Y. ; Yuran, S. ; Aviv, Y. ; Ayalew, H. ; Luo, C. - H. ; Tsai, Y. - H. ; Reches, M. ; Yu, H. - H. ; Shenhar, R. Electrically Responsive, Nanopatterned Surfaces for Triggered Delivery of Biologically Active Molecules into Cells. ACS Applied Materials & Interfaces 2019, 11, 1201-1208.Abstract

Polyelectrolyte multilayers (PEMs) assembled layer-by-layer have emerged as functional polymer films that are both stable and capable of containing drug molecules for controlled release applications. Most of these applications concentrate on sustained release, where the concentration of the released molecules remains rather constant with time. However, high-efficiency delivery requires obtaining high local concentrations at the vicinity of the cells, which is achieved by triggered release. Here, we show that a nanopatterned PEM platform demonstrates superior properties with respect to drug retention and triggered delivery. A chemically modified block copolymer film was used as a template for the selective deposition of poly(ethylene imine) and a charged derivative of the electroactive poly(3,4-ethylenedioxythiophene) together with a drug molecule. This nanopatterned PEM shows the following advantages: (1) high drug loading; (2) enhanced retention of the bioactive molecule; (3) release triggered by an electrochemical stimulus; (4) high efficacy of drug delivery to cells adsorbed on the surface compared to the delivery efficacy of a similar concentration of drug to cells suspended in a solution.

53. Triggered drug release from nano-patterned substrates

Aviv, Y. ; Altay, E. ; Fink, L. ; Raviv, U. ; Rzayev, J. ; Shenhar, R. Quasi-Two-Dimensional Assembly of Bottlebrush Block Copolymers with Nanoparticles in Ultrathin Films: Combined Effect of Graft Asymmetry and Nanoparticle Size. Macromolecules 2019, 52, 196-207.Abstract

Block copolymer guided assembly of nanoparticles leads to the formation of nanocomposites with periodic arrangement of nanoparticles, which are important for applications such as photonic devices and sensors. However, linear block copolymers offer limited control over the internal arrangement of nanoparticles inside their hosting domains. In contrast, bottlebrush block copolymers possess unique architectural attributes that enable additional ways to control the local organization of nanoparticles. In this work, we studied the coassembly of 8 and 13 nm gold nanoparticles with three bottlebrush block copolymers differing in the asymmetry of their graft lengths. Assembly was performed in ultraconfined films, where it occurs quasi-two-dimensionally. Our results indicate that graft asymmetry could be used as an additional tool to enhance nanoparticle ordering by forcing them to localize at the center of the domain regardless of their size. This behavior is analyzed in terms of the influence of the graft asymmetry on the average conformations of the blocks.

54. Bottlebrush block copolymers nanoparticle assembly

Michman, E. ; Shenhar, R. Directed self-assembly of block copolymer-based nanocomposites in thin films. Polymers for Advanced Technologies 2017, 28, 613-622.Abstract

Exploiting the full potential of metal and semiconductor nanoparticles for advanced nanotechnological applications requires their organization into predefined structures with high orientational control. Nanofabrication approaches that combine high resolution lithography and self-assembly afford the advantages of accurate placement, compositional diversity, and reduced production costs. This review concentrates on the creation of organized nanoparticle superstructures assisted by recent developments in the directed self-assembly of block copolymers, and delineates possible applications. Copyright (C) 2016 John Wiley & Sons, Ltd.

Asor, L. ; Nir, S. ; Oded, M. ; Reches, M. ; Shenhar, R. Nano-patterned polyelectrolyte multilayers assembled using block copolymer templates: The combined effect of ionic strength and nano-confinement. Polymer 2017, 126, 56-64.Abstract

Polyelectrolyte multilayers gain their importance from their applicability to a wide variety of functional building blocks. The ability to create these multilayers as laterally nano-patterned films, which has only been scarcely investigated so far, augments the functionality of the multilayer and makes it valuable for applications that require nanoscale features or periodic arrangement, such as photonic devices, catalytic surfaces, and biomedical applications. In this study we reveal how the lateral confinement imposed by block copolymer nano-domains in thin film templates affects the assembly of the deposited poly electrolyte layers at different ionic strengths, and how the combined effects of nano-confinement and ionic strength dictate the final structure of the multilayer. These fundamental insights provide the basis for successful construction of nano-patterned, functional coatings. (C) 2017 Elsevier Ltd. All rights reserved.

52. nano-confinement effects in nano-patterned PEMs

Wagner, T. ; Oded, M. ; Shenhar, R. ; Böker, A. Two-dimensionally ordered AuNP array formation via microcontact printing on lamellar diblock copolymer films. Polymers for Advanced Technologies 2017, 28, 623-628.Abstract

The construction of nano-sized, two-dimensionally ordered nanoparticle (NP) superstructures is important for various advanced applications such as photonics, sensing, catalysis, or nano-circuitry. Currently, such structures are fabricated using the templated organization approach, in which the templates are mainly created by photo-lithography or laser-lithography and other invasive top-down etching procedures. In this work, we present an alternative bottom-up preparation method for the controlled deposition of NPs into hierarchical structures. Lamellar polystyrene-block-poly(2-vinylpyridinium) thin films featuring alternating stripes of neutral PS and positively charged P2VP domains serve as templates, allowing for the selective adsorption of negatively charged gold NPs. Dense NP assembly is achieved by a simple immersion process, whereas two-dimensionally ordered arrays of NPs are realized by microcontact printing (mu CP), utilizing periodic polydimethylsiloxane wrinkle grooves loaded with gold NPs. This approach enables the facile construction of hierarchical NP arrays with variable geometries. Copyright (C) 2016 John Wiley & Sons, Ltd.

51. Crossbar nanoparticle transfer

Chandaluri, C. G. ; Pelossof, G. ; Tel-Vered, R. ; Shenhar, R. ; Willner, I. Block Copolymer Patterns as Templates for the Electrocatalyzed Deposition of Nanostructures on Electrodes and for the Generation of Surfaces of Controlled Wettability. ACS Applied Materials & Interfaces 2016, 8 1440-1446.Abstract

ITO electrodes modified with a nanopatterned film of polystyrene-block-poly(2-vinylpyridine), PS-b-P2VP, where the P2VP domains are quaternized with iodomethane, are used for selective deposition of redox-active materials. Electrochemical studies (cyclic voltammetry, Faradaic impedance measurements) indicate that the PS domains insulate the conductive surface toward redox labels in solution. In turn, the quaternized P2VP domains electrostatically attract negatively charged redox labels solubilized in the electrolyte solution, resulting in an effective electron transfer between the electrode and the redox label. This phenomenon is implemented for the selective deposition of the electroactive Prussian blue on the nanopatterned surface and for the electrochemical deposition of Au nanoparticles, modified with a monolayer of p-aminothiophenol/2-mercaptoethanesulfonic acid, on the quaternized P2VP domains. The patterned Prussian blue-modified surface enables controlling the wettability properties by the content of the electrochemically deposited Prussian blue. Controlled wettability is unattainable with the homopolymer-modified surface, attesting to the role of the nanopattern.

44. Electrocatalyzed deposition on block copolymer substrates

Oded, M. ; Müller, A. H. E. ; Shenhar, R. A block copolymer-templated construction approach for the creation of nano-patterned polyelectrolyte multilayers and nanoscale objects. Soft Matter 2016, 12, 8098-8103.Abstract

A block copolymer-based assembly approach for the creation of nano-patterned polyelectrolyte multilayers over cm2-scale areas is presented. Up to 5 bi-layers were selectively assembled on top of specific nanodomains featuring different morphologies. The successful isolation of nanoscale objects corresponding in shape to the template features is also demonstrated. This methodology is applicable to different types of polyelectrolytes, and opens up a new dimension for layer-by-layer construction.

49. nano-objects from nanopatterned PEMs  

Metzger, T. S. ; Chandaluri, C. G. ; Tel-Vered, R. ; Shenhar, R. ; Willner, I. Donor/Acceptor-Modified Electrodes for Photoelectrochemical and Photobioelectrochemical Applications. Advanced Functional Materials 2016, 26, 7148-7155.Abstract

A 7-pyrrolidino-7-benzylamino-8,8-dicyanoquinodimethane, PBEDQ, (1), donor-acceptor-modified electrode yields, in the presence of hydroquinone, (2), an anodic photocurrent with quantum efficiency of 1.5%. The PBEDQ-functionalized electrode yields, in the presence of the electron acceptor diquat, (3), a cathodic photocurrent with a quantum efficiency corresponding to 2.1%. The electron transfer cascades leading to the anodic or cathodic photo currents in the different systems are discussed. It is further demonstrated that the integration of 1,4-dihydronicotinamide adenine dinucleotide, NADH, as electron donor, with the PBEDQ-modified electrode leads to an anodic photocurrent. This allowed the assembly of a photobioelectrochemical integrated electrode composed of the photoactive PBEDQ donor-acceptor compound, NAD(+) as cofactor, and the NAD(+)-dependent glucose dehydrogenase, GDH. Irradiation of the integrated electrode in the presence of glucose results in the GDH-biocatalyzed oxidation of glucose to gluconic acid with the concomitant generation of NADH that acts as electron donor for the photo active donor-acceptor PBEDQ units, leading to the generation of steady-state anodic photocurrent. The photocurrent intensities are controlled by the concentrations of glucose. The integrated PBEDQ/NAD(+)/GDH electrodes introduces a functional photobioelectrochemical electrode for the detection of glucose, and demonstrates the assembly of a functional photo-biofuel cell that uses light and a biomass product (glucose) for the generation of electric power.

47. modified electrodes

Oded, M. ; Kelly, S. T. ; Gilles, M. K. ; Müller, A. H. E. ; Shenhar, R. From dots to doughnuts: Two-dimensionally confined deposition of polyelectrolytes on block copolymer templates. Polymer 2016, 107, 406-414.Abstract

The combination of block copolymer templating with electrostatic self-assembly provides a simple and robust method for creating nano-patterned polyelectrolyte multilayers over large areas. The deposition of the first polyelectrolyte layer provides important insights on the initial stages of multilayer buildup. Here, we focus on two-dimensionally confined ``dots'' patterns afforded by block copolymer films featuring hexagonally-packed cylinders that are oriented normal to the substrate. Rendering the cylinder caps positively charged enables the selective deposition of negatively charged polyelectrolytes on them under salt-free conditions. The initially formed polyelectrolyte nanostructures adopt a toroidal (''doughnut'') shape, which results from retraction of dangling polyelectrolyte segments into the ``dots'' upon drying. With increasing exposure time to the polyelectrolyte solution, the final shape of the deposited polyelectrolyte transitions from a doughnut to a hemisphere. These insights would enable the creation of patterned polyelectrolyte multilayers with increased control over adsorption selectivity of the additional incoming polyelectrolytes. (C) 2016 Elsevier Ltd. All rights reserved.

48. from dots to doughnuts

Oded, M. ; Kelly, S. T. ; Gilles, M. K. ; Muller, A. H. E. ; Shenhar, R. Periodic nanoscale patterning of polyelectrolytes over square centimeter areas using block copolymer templates. Soft Matter 2016, 12, 4595-4602.Abstract

Nano-patterned materials are beneficial for applications such as solar cells, opto- electronics, and sensing owing to their periodic structure and high interfacial area. Here, we present a non-lithographic approach for assembling polyelectrolytes into periodic nanoscale patterns over cm(2)-scale areas. Chemically modified block copolymer thin films featuring alternating charged and neutral domains are used as patterned substrates for electrostatic self-assembly. In-depth characterization of the deposition process using spectroscopy and microscopy techniques, including the state-of-the-art scanning transmission X-ray microscopy (STXM), reveals both the selective deposition of the polyelectrolyte on the charged copolymer domains as well as gradual changes in the film topography that arise from further penetration of the solvent molecules and possibly also the polyelectrolyte into these domains. Our results demonstrate the feasibility of creating nano-patterned polyelectrolyte layers, which opens up new opportunities for structured functional coating fabrication.

45. striped nano-patterned PEMs

Sanguramath, R. A. ; Nealey, P. F. ; Shenhar, R. Quasi-Block Copolymers Based on a General Polymeric Chain Stopper. Chemistry-A European Journal 2016, 22, 10203-10210.Abstract

Quasi-block copolymers (q-BCPs) are block copolymers consisting of conventional and supramolecular blocks, in which the conventional block is end-terminated by a functionality that interacts with the supramolecular monomer (a ``chain stopper'' functionality). A new design of q-BCPs based on a general polymeric chain stopper, which consists of polystyrene end-terminated with a sulfonate group (PS-SO3Li), is described. Through viscosity measurements and a detailed diffusion-ordered NMR spectroscopy study, it is shown that PS-SO3Li can effectively cap two types of model supramolecular monomers to form q-BCPs in solution. Furthermore, differential scanning calorimetry data and structural characterization of thin films by scanning force microscopy suggests the existence of the q-BCP architecture in the melt. The new design considerably simplifies the synthesis of polymeric chain stoppers; thus promoting the utilization of q-BCPs as smart, nanostructured materials.

46. universal quasi-block copolymers

Davidi, I. ; Shenhar, R. Synthesis of disk-shaped nanoparticle aggregates organized in hierarchical structures in block copolymer matrixes. Polymer 2015, 64, 39-45.Abstract

Disk-shaped nanoparticle aggregates organized in a hierarchical structure in a microphase separated block copolymer were prepared in a two-step process. First, a system comprising of polystyrene-block-poly(2-vinyl pyridine) and a palladium-pincer based surfactant was let to thermally equilibrate, resulting in the formation of structured material with hierarchically distributed concentrations of the palladium precursors. Then, in-situ reduction of the palladium precursors yielded the hierarchically organized nanocomposite. The importance of using an amphiphilic molecule for obtaining the hierarchical arrangement of the nanoparticle aggregates is demonstrated. Hierarchically arranged nanocomposites consisting of shape-controlled nanoparticle aggregates can potentially be useful as photonic materials with unique anisotropic optical response. (C) 2015 Elsevier Ltd. All rights reserved.

43. disk-shaped aggregates

Halevi, A. ; Halivni, S. ; Oded, M. ; Müller, A. H. E. ; Banin, U. ; Shenhar, R. Co-Assembly of A-B Diblock Copolymers with B'-type Nanoparticles in Thin Films: Effect of Copolymer Composition and Nanoparticle Shape. Macromolecules 2014, 47, 3022-3032.Abstract

The coassembly of A B diblock copolymers with B'-type nanoparticles (i.e., nanoparticles that are slightly incompatible with the B domain) leads to hierarchical structures, where the block copolymer phase separates first and the nanoparticles create close-packed arrays within the B domains due to a slower, secondary phase separation process. Here we report the results of a comprehensive study, which focused on two aspects: the influence of the nanoparticle shape (spherical vs rod-like) and the effect of the volume composition of the blocks. Three polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) copolymers featuring similar molecular weights but differing in PS volume fraction were mixed with spherical and rod-shaped poly(ethylene oxide)- (PEO-) capped CdS nanoparticles at different filling fractions and cast as thin films. Our results highlight the mutual influence between the block copolymer and the nanoparticles on the resulting morphology, demonstrating the ability to control the film morphology by the filling fraction of the nanoparticles and their tendency to localize at the film surface, and by confinement-induced nanoparticle aggregation. Most importantly, the results reveal the influence of the nanoparticle shape on the structure of the film.

41. co-assembly of B'-type nanorods in A-B block copolymers

This paper was highlighted in Advances in Engineering!

Davidi, I. ; Hermida-Merino, D. ; Keinan-Adamsky, K. ; Portale, G. ; Goobes, G. ; Shenhar, R. Dynamic Behavior of Supramolecular Comb Polymers Consisting of Poly(2-Vinyl Pyridine) and Palladium-Pincer Surfactants in the Solid State. Chemistry-A European Journal 2014, 20, 6951-6959.Abstract

When poly(2-vinyl pyridine) is combined with Pd-pincer-based organometallic surfactants, a mesomorphic structure forms due to weak stacking interactions between the pyridine units and the Pd-pincer headgroups. The weak binding between the surfactant and the polymer competes with the tendency of the aliphatic tails of the surfactant to crystallize. Here, we demonstrate that over extended periods of incubation, the crystallization tendency of the surfactant tails causes the surfactant molecules to detach from the polymer and gives rise to additional packing modes of the alkyl tails featuring higher crystalline order. The dynamic behavior of these aged structures was investigated by variable-temperature small-angle X-ray scattering (SAXS) and solid-state 13CNMR, and revealed the influence of thermal changes on the molecular level, and how these changes propagate to the mesoscale structure.

40. dynamic behavior of pi-stacked amphiphile-block copolymer system

Davidi, I. ; Patra, D. ; Herrnida-Merino, D. ; Portale, G. ; Rotello, V. M. ; Raviv, U. ; Shenhar, R. Hierarchical Structures of Polystyrene-block-poly(2-vinylpyridine)/Palladium-Pincer Surfactants: Effect of Weak Surfactant-Polymer Interactions on the Morphological Behavior. Macromolecules 2014, 47, 5774-5783.Abstract

Selective segregation of surfactant molecules to one domain type of block copolymers in the melt leads to the formation of hierarchical structures. Here we show that combining an organometallic, Pd-pincer-based surfactant (Pd-SCS) with a polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) diblock copolymer leads to hierarchical structures due to weak stacking interactions between the Pd-pincer complex and the pyridine units. These structures feature a different morphological behavior than analogous systems, including the formation of perforated lamellae (PL) over a wide range of surfactant filling fractions and a distinct swelling anisotropy behavior of the copolymer chains by the added surfactant molecules. The results suggest that the strength of interaction between the surfactant and the compatible block influences the degree of segregation between the blocks. This study lays the foundations for the creation of organized, hierarchical arrays of inorganic nanoclusters that are periodic on two different length scales.

42. hierarchical structures of Pd-pincer-block copolymer system

Eisenberg, D. ; Quimby, J. M. ; Scott, L. T. ; Shenhar, R. 1,3,5-tricorannulenylbenzene: stereochemistry, reduction and supramolecular dimerization of a branched oligocorannulene. Journal of Physical Organic Chemistry 2013, 26, 124-130.Abstract

Oligocorannulenes are polyarenes composed of several corannulene units that are covalently linked. Their behavior arises both from the diverse properties of each corannulenyl unit and from the interactions between them. In this paper, we present the synthesis, stereochemistry, reduction, and self-assembly properties of a novel type of oligocorannulene: branched 1,3,5-tricorannulenylbenzene. Several stereodynamical elements combine to give rich stereochemistry: bowl-to-bowl inversion, rotation about the aryl-aryl single bonds, and residual stereoisomerism of molecular propellers. Reduction with lithium metal yields an intermediate hexaanion and ultimately produces a highly charged dodecaanion. Self-diffusion NMR demonstrates that the dodecaanion undergoes supramolecular dimerization through charged polyarene stacking, wherein two molecules are linked at all three contact points. The preference for dimerization over dendrimerization is attributed to an entropic effect. The dimer is found to undergo complex structural dynamics, as well as ion-pairing dynamics, as revealed by variable-temperature 1H- and 7Li-NMR. Copyright (C) 2012 John Wiley & Sons, Ltd.

35. tricorannulenyl benzene anions

Liedel, C. ; Pester, C. W. ; Ruppel, M. ; Lewin, C. ; Pavan, M. J. ; Urban, V. S. ; Shenhar, R. ; Bösecke, P. ; Böker, A. Block Copolymer Nanocomposites in Electric Fields: Kinetics of Alignment. ACS Macro Letters 2013, 2 53-58.Abstract

We investigate the kinetics of block copolymer/nanoparticle composite alignment in an electric field using in situ transmission small-angle X-ray scattering. As a model system, we employ a lamellae forming polystyrene-block-poly(2-vinyl pyridine) block copolymer with different contents of gold nanoparticles in thick films under solvent vapor annealing. While the alignment improves with increasing nanoparticle fraction, the kinetics slows down. This is explained by changes in the degree of phase separation and viscosity. Our findings provide extended insights into the basics of nanocomposite alignment.

36. kinetics of nanocomposite alignment under E-field

Pavan, M. J. ; Shenhar, R. Effect of Channel Confinement on the Coarsening Kinetics of Nanoparticles Deposited on Semicrystalline Polymer Templates. ChemPlusChem 2013, 78, 1015-1023.Abstract

Dodecanethiol-capped gold nanoparticles (NPs) deposited onto a poly(ethylene glycol) substrate quickly coarsen over a timescale of days when stored under ambient conditions. The NP coarsening was studied at different surface coverages and temperatures. The coarsening of NPs depended on their location on the film; NPs located inside the channels coarsened in a different fashion than NPs deposited on the plateaus. Size distributions studied by image analysis and comparison to theoretical distribution functions shed light on the coarsening mechanism in each case, revealing the role of dimensionality.

39. effect of channel confinement

This paper was highlighted in Chemistry Views!

Liedel, C. ; Schindler, K. A. ; Pavan, M. J. ; Lewin, C. ; Pester, C. W. ; Ruppel, M. ; Urban, V. S. ; Shenhar, R. ; Böker, A. Electric-Field-Induced Alignment of Block Copolymer/Nanoparticle Blends. Small 2013, 9 3276-3281.Abstract

External electric fields readily align birefringent block-copolymer mesophases. In this study the effect of gold nanoparticles on the electric-field-induced alignment of a lamellae-forming polystyrene-block-poly(2-vinylpyridine) copolymer is assessed. Nanoparticles are homogeneously dispersed in the styrenic phase and promote the quantitative alignment of lamellar domains by substantially lowering the critical field strength above which alignment proceeds. The results suggest that the electric-field-assisted alignment of nanostructured block copolymer/nanoparticle composites may offer a simple way to greatly mitigate structural and orientational defects of such films under benign experimental conditions.

37. E-field induced alignment of nanocomposites

Ploshnik, E. ; Langner, K. M. ; Halevi, A. ; Ben-Lulu, M. ; Müller, A. H. E. ; Fraaije, J. G. E. M. ; Agur Sevink, G. J. ; Shenhar, R. Hierarchical Structuring in Block Copolymer Nanocomposites through Two Phase-Separation Processes Operating on Different Time Scales. Advanced Functional Materials 2013, 23, 4215-4226.Abstract

Tailoring the size and surface chemistry of nanoparticles allows one to control their position in a block copolymer, but this is usually limited to one-dimensional distribution across domains. Here, the hierarchical assembly of poly(ethylene oxide)-stabilized gold nanoparticles (Au-PEO) into hexagonally packed clusters inside mesostructured ultrathin films of polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) is described. A close examination of the structural evolution at different nanoparticle filling fractions and PEO ligand molecular weights suggests that the mechanism leading to this structure-within-structure is the existence of two phase separation processes operating on different time scales. The length of the PEO ligand is shown to influence not only the interparticle distances but also the phase separation processes. These conclusions are supported by novel mesoscopic simulations, which provide additional insight into the kinetic and thermodynamic factors that are responsible for this behavior.

38. co-assembly of B'-nanoparticles with A-B block copolymers