Nasim Hyder

Layer-by-layer assembled polyaniline nanofiber/multiwall carbon nanotube thin film electrodes for high-power and high-energy storage applications

Thin film electrodes of polyaniline (PANi) nanofibers and functionalized multiwall carbon nanotubes (MWNTs) are created by layer-by-layer (LbL) assembly for microbatteries or -electrochemical capacitors. Highly stable cationic PANi nanofibers, synthesized from the rapid aqueous phase polymerization of aniline, are assembled with carboxylic acid functionalized MWNT into LbL films. The pH-dependent surface charge of PANi nanofibers and MWNTs allows the system to behave like weak polyelectrolytes with controllable LbL film thickness and morphology by varying the number of bilayers. The LbL-PANi/MWNT films consist of a nanoscale interpenetrating network structure with well developed nanopores that yield excellent electrochemical performance for energy storage applications. These LbL-PANi/MWNT films in lithium cell can store high volumetric capacitance (~238 ± 32 F/cm(3)) and high volumetric capacity (~210 mAh/cm(3)). In addition, rate-dependent galvanostatic tests show LbL-PANi/MWNT films can deliver both high power and high energy density (~220 Wh/L(electrode) at ~100 kW/L(electrode)) and could be promising positive electrode materials for thin film microbatteries or electrochemical capacitors.

Drastically Lowered Protein Adsorption on Microbicidal Hydrophobic/Hydrophilic Polyelectrolyte Multilayers

Polyelectrolyte multilayer films assembled from a hydrophobic N-alkylated polyethylenimine and a hydrophilic polyacrylate were discovered to exhibit strong antifouling, as well as antimicrobial, activities. Surfaces coated with these layer-by-layer (LbL) films, which range from 6 to 10 bilayers (up to 45 nm in thickness), adsorbed up to 20 times less protein from blood plasma than the uncoated controls. The dependence of the antifouling activity on the nature of the polycation, as well as on assembly conditions and the number of layers in the LbL films, was investigated. Changing the hydrophobicity of the polycation altered the surface composition and the resistance to protein adsorption of the LbL films. Importantly, this resistance was greater for coated surfaces with the polyanion on top; for these films, the average zeta potential pointed to a near neutral surface charge, thus, presumably minimizing their electrostatic interactions with the protein. The film surface exhibited a large contact angle hysteresis, indicating a heterogeneous topology likely due to the existence of hydrophobic-hydrophilic regions on the surface. Scanning electron micrographs of the film surface revealed the existence of nanoscale domains. We hypothesize that the existence of hydrophobic/hydrophilic nanodomains, as well as surface charge neutrality, contributes to the LbL films resistance to protein adsorption.

Synthesis of Highly Stable Sub-8 nm TiO2 Nanoparticles and Their Multilayer Electrodes of TiO2/MWNT for Electrochemical Applications

Next-generation electrochemical energy storage for integrated microsystems and consumer electronic devices requires novel electrode materials with engineered architectures to meet the requirements of high performance, low cost, and robustness. However, conventional electrode fabrication processes such as doctor blading afford limited control over the electrode thickness and structure at the nanoscale and require the incorporation of insulating binder and other additives, which can promote agglomeration and reduce active surface area, limiting the inherent advantages attainable from nanoscale materials. We have engineered a route for the synthesis of highly stable, sub-8 nm TiO2 nanoparticles and their subsequent incorporation with acid-functionalized multiwalled carbon nanotubes (MWNTs) into nanostructured electrodes using aqueous-based layer-by-layer electrostatic self-assembly. Using this approach, binder-free thin film electrodes with highly controllable thicknesses up to the micrometer scale were developed with well-dispersed, nonagglomerated TiO2 nanoparticles on MWNTs. Upon testing in an Li electrochemical half-cell, these electrodes demonstrate high capacity (>150 mAh/gel(ectrode) at 0.1 A/gel(ectrode)), good rate capability (>100 mAh/gel(ectrode) up to 1 A/g(electrode)) and nearly no capacity loss up to 200 cycles for electrodes with thicknesses up to 1480 nm, indicating their promise as thin-film negative electrodes for future Li storage applications.

Rapid fabrication of thick spray-layer-by-layer carbon nanotube electrodes for high power and energy devices

Rapid fabrication of layer-by-layer (LbL) electrodes is essential to expand their utility in energy storage applications. Herein, we address challenges in developing thick LbL electrodes of multi-wall carbon nanotubes (MWNTs) using conventional dip- and spray-LbL processes, and present a solution to overcome these challenges. The vacuum-assisted spray-LbL process using porous carbon substrates enabled a linear growth of LbL-MWNT electrodes with a 600 time decrease in their fabrication time. This result was attributed to the enhanced surface interactions between MWNTs and substrate via increased surface areas, enhanced capillary forces, physical entrapment in pores, and changes in hydrodynamic drag forces. Scanning electron microscopy (SEM) revealed high surface area carbon nanotube networks comprised of individual MWNTs. The spray MWNT electrodes delivered a high gravimetric energy of 100 W h kg−1 at high gravimetric power of 50 kW kg−1, which is higher than those of most carbon nanotube electrodes reported. Moreover, the spray MWNT electrodes delivered the highest energy capacity per unit area (up to 300 μW h cm−2 at 0.4 mW cm−2 among the LbL electrodes reported, and showed excellent retention of energy capacity up to 100 μW h cm−2 at high power capacity of 200 mW cm−2. These performance values are higher or comparable to the most advanced battery electrodes for high energy capacity per unit area.

Assembly of Viral Hydrogels for Three-Dimensional Conducting Nanocomposites

M13 bacteriophages act as versatile scaffolds capable of organizing single-walled carbon nanotubes and fabricating three-dimensional conducting nanocomposites. The morphological, electrical, and electrochemical properties of the nanocomposites are presented, as well as its ability to disperse and utilize single-walled carbon nanotubes effectively.

Enhancing droplet deposition through in-situ precipitation

Retention of agricultural sprays on plant surfaces is an important challenge. Bouncing of sprayed pesticide droplets from leaves is a major source of soil and groundwater pollution and pesticide overuse. Here we report a method to increase droplet deposition through in-situ formation of hydrophilic surface defects that can arrest droplets during impact. Defects are created by simultaneously spraying oppositely charged polyelectrolytes that induce surface precipitation when two droplets come into contact. Using high-speed imaging, we study the coupled dynamics of drop impact and surface precipitate formation. We develop a physical model to estimate the energy dissipation by the defects and predict the transition from bouncing to sticking. We demonstrate macroscopic enhancements in spray retention and surface coverage for natural and synthetic non-wetting surfaces and provide insights into designing effective agricultural sprays. The extensive use of pesticides in agriculture calls for efficient spraying techniques to reduce pollution of soils and groundwater by toxic chemicals. Damak et al. simultaneously spray liquids containing oppositely charged polyelectrolytes that form defects, pinning droplets on targeted surfaces.

Carbon nanotube–polyaniline core–shell nanostructured hydrogel for electrochemical energy storage

Conductive polymer hydrogels, which synergize the advantageous features of hydrogels and conductive materials, have been utilized in many electrochemical energy storage applications. Here, we introduce phytic acid as (1) a dispersing agent for pristine multi-walled carbon nanotubes (MWNTs) in aqueous solution containing aniline and as (2) a gelator to form polyaniline (PANI)-based hydrogels after polymerization. The PANI-based hydrogels exhibit nanowire-based mesoporous networks with high surface area and electrical conductivity. The nanostructured core (MWNT)–shell (PANI) hydrogels show an improvement on the electrical conductivity from 0.21 to 1.54 S cm−1 as the loading of MWNTs increases from 0 to 5.0 wt%. The conducting nanowire-based networks with MWNT loadings of 3.0 wt% in the hydrogel provide efficient electron transport pathways that exhibit a maximal specific capacity of 609 F g−1. The scalable and facile synthesis demonstrates excellent electrochemical performance, rendering it attractive for sensing, energy conversion, and energy storage applications.

Synthetic nanoscale electrostatic particles as growth factor carriers for cartilage repair

Abstract The efficient transport of biological therapeutic materials to target tissues within the body is critical to their efficacy. In cartilage tissue, the lack of blood vessels prevents the entry of systemically administered drugs at therapeutic levels. Within the articulating joint complex, the dense and highly charged extracellular matrix (ECM) hinders the transport of locally administered therapeutic molecules. Consequently, cartilage injury is difficult to treat and frequently results in debilitating osteoarthritis. Here we show a generalizable approach in which the electrostatic assembly of synthetic polypeptides and a protein, insulin‐like growth factor‐1 (IGF‐1), can be used as an early interventional therapy to treat injury to the cartilage. We demonstrated that poly(glutamic acid) and poly(arginine) associated with the IGF‐1 via electrostatic interactions, forming a net charged nanoscale polyelectrolyte complex (nanoplex). We observed that the nanoplex diffused into cartilage plugs in vitro and stimulated ECM production. In vivo, we monitored the transport, retention and therapeutic efficacy of the nanoplex in an established rat model of cartilage injury. A single therapeutic dose, when administered within 48 hr of the injury, conferred protection against cartilage degradation and controlled interleukin‐1 mediated inflammation. IGF‐1 contained in the nanoplex was detected in the joint space for up to 4 weeks following administration and retained bioactivity. The results indicate the potential of this approach as an early intervention therapy following joint injury to delay or even entirely prevent the onset of osteoarthritis.

Chapter 5:Bioinspired Photocatalytic Nanomaterials

Solar energy is one of the few alternative energy sources that could meet increased future energy demands. Mimicking natural photosynthesis has been a goal for the research community for decades, designing artificial molecular systems for the electrolysis of water. This chapter discusses recent developments and challenges on the rational design and assembly of nanoscale catalysts based on biological principles that are required for the water-splitting reaction – for the production of oxygen and hydrogen gas driven by light. Natural biogenic systems with delicate symmetries and hierarchy vary widely in shape and size with diverse chemical and physical properties. These physical differences allow researchers to design ordered structures and assemblies from biotemplates rendering efficient functional devices. For the development of highly ordered nanostructures for smaller, lightweight flexible solar cells, the design, selection, and assembly of materials are key issues from the organization of disordered components through spontaneous interactions. Rapid advances in nanoscience coupled with the revolution in biology has imparted unprecedented opportunities to design functional nanomaterials based on biological principles. Biological templates, such as bacteriophages, offer environmentally friendly synthesis and organization of nanomaterials to develop functional assemblies for developing complete photoelectrochemical systems.