Bogdan Zdyrko

A Major Constituent of Brown Algae for Use in High-Capacity Li-Ion Batteries

Alginate extracts help stabilize silicon nanoparticles used in a high-capacity lithium-silicon battery. The identification of similarities in the material requirements for applications of interest and those of living organisms provides opportunities to use renewable natural resources to develop better materials and design better devices. In our work, we harness this strategy to build high-capacity silicon (Si) nanopowder–based lithium (Li)–ion batteries with improved performance characteristics. Si offers more than one order of magnitude higher capacity than graphite, but it exhibits dramatic volume changes during electrochemical alloying and de-alloying with Li, which typically leads to rapid anode degradation. We show that mixing Si nanopowder with alginate, a natural polysaccharide extracted from brown algae, yields a stable battery anode possessing reversible capacity eight times higher than that of the state-of-the-art graphitic anodes.

Toward Efficient Binders for Li-Ion Battery Si-Based Anodes: Polyacrylic Acid

Si-based Li-ion battery anodes offer specific capacity an order of magnitude beyond that of conventional graphite. However, the formation of stable Si anodes is a challenge because of significant volume changes occurring during their electrochemical alloying and dealloying with Li. Binder selection and optimization may allow significant improvements in the stability of Si-based anodes. Most studies of Si anodes have involved the use of carboxymethylcellulose (CMC) and poly(vinylidene fluoride) (PVDF) binders. Herein, we show for the first time that pure poly(acrylic acid) (PAA), possessing certain mechanical properties comparable to those of CMC but containing a higher concentration of carboxylic functional groups, may offer superior performance as a binder for Si anodes. We further show the positive impact of carbon coating on the stability of the anode. The carbon-coated Si nanopowder anodes, tested between 0.01 and 1 V vs Li/Li+ and containing as little as 15 wt % of PAA, showed excellent stability during the first hundred cycles. The results obtained open new avenues to explore a novel series of binders from the polyvinyl acids (PVA) family.

Mid-infrared materials and devices on a Si platform for optical sensing

Abstract In this article, we review our recent work on mid-infrared (mid-IR) photonic materials and devices fabricated on silicon for on-chip sensing applications. Pedestal waveguides based on silicon are demonstrated as broadband mid-IR sensors. Our low-loss mid-IR directional couplers demonstrated in SiNx waveguides are useful in differential sensing applications. Photonic crystal cavities and microdisk resonators based on chalcogenide glasses for high sensitivity are also demonstrated as effective mid-IR sensors. Polymer-based functionalization layers, to enhance the sensitivity and selectivity of our sensor devices, are also presented. We discuss the design of mid-IR chalcogenide waveguides integrated with polycrystalline PbTe detectors on a monolithic silicon platform for optical sensing, wherein the use of a low-index spacer layer enables the evanescent coupling of mid-IR light from the waveguides to the detector. Finally, we show the successful fabrication processing of our first prototype mid-IR waveguide-integrated detectors.

Integrated chalcogenide waveguide resonators for mid-IR sensing: leveraging material properties to meet fabrication challenges

In this paper, attributes of chalcogenide glass (ChG) based integrated devices are discussed in detail, including origins of optical loss and processing steps used to reduce their contributions to optical component performance. Specifically, efforts to reduce loss and tailor optical characteristics of planar devices utilizing solution-based glass processing and thermal reflow techniques are presented and their results quantified. Post-fabrication trimming techniques based on the intrinsic photosensitivity of the chalcogenide glass are exploited to compensate for fabrication imperfections of ring resonators. Process parameters and implications on enhancement of device fabrication flexibility are presented.

Multimodal analysis of PEI-mediated endocytosis of nanoparticles in neural cells.

Polymer nanoparticles are widely used as a highly generalizable tool to entrap a range of different drugs for controlled or site-specific release. However, despite numerous studies examining the kinetics of controlled release, the biological behavior of such nanoparticles remains poorly understood, particularly with respect to endocytosis and intracellular trafficking. We synthesized polyethylenimine-decorated polymer nanospheres (ca. 100-250 nm) of the type commonly used for drug release and used correlated electron microscopy, fluorescence spectroscopy and microscopy, and relaxometry to track endocytosis in neural cells. These capabilities provide insight into how polyethylenimine mediates the entry of nanoparticles into neural cells and show that polymer nanosphere uptake involves three distinct steps, namely, plasma membrane attachment, fluid-phase as well as clathrin- and caveolin-independent endocytosis, and progressive accumulation in membrane-bound intracellular vesicles. These findings provide detailed insight into how the intracellular delivery of nanoparticles is mediated by polyethylenimine, which is presently the most commonly used nonviral gene transfer agent. This fundamental knowledge may also assist in the preparation of next-generation nonviral vectors.

Field-Directed Self-Assembly with Locking Nanoparticles

A reversible locking mechanism is established for the generation of anisotropic nanostructures by a magnetic field pulse in liquid matrices by balancing the thermal energy, short-range attractive and long-range repulsive forces, and dipole-dipole interactions using a specially tailored polymer shell of nanoparticles. The locking mechanism is used to precisely regulate the dimensions of self-assembled magnetic nanoparticle chains and to generate and disintegrate three-dimensional (3D) nanostructured materials in solvents and polymers.

In vivo Imaging and Biodistribution of Multimodal Polymeric Nanoparticles Delivered to the Optic Nerve

The use of nanoparticles for targeted delivery of therapeutic agents to sites of injury or disease in the central nervous system (CNS) holds great promise. However, the biodistribution of nanoparticles following in vivo administration is often unknown, and concerns have been raised regarding potential toxicity. Using poly(glycidyl methacrylate) (PGMA) nanoparticles coated with polyethylenimine (PEI) and containing superparamagnetic iron oxide nanoparticles as a magnetic resonance imaging (MRI) contrast agent and rhodamine B as a fluorophore, whole animal MRI and fluorescence analyses are used to demonstrate that these nanoparticles (NP) remain close to the site of injection into a partial injury of the optic nerve, a CNS white matter tract. In addition, some of these NP enter axons and are transported to parent neuronal somata. NP also remain in the eye following intravitreal injection, a non-injury model. Considerable infiltration of activated microglia/macrophages occurs in both models. Using magnetic concentration and fluorescence visualization of tissue homogenates, no dissemination of the NP into peripheral tissues is observed. Histopathological analysis reveals no toxicity in organs other than at the injection sites. Multifunctional nanoparticles may be a useful mechanism to deliver therapeutic agents to the injury site and somata of injured CNS neurons and thus may be of therapeutic value following brain or spinal cord trauma.

PROGRESS ON THE FABRICATION OF ON-CHIP, INTEGRATED CHALCOGENIDE GLASS (CHG)-BASED SENSORS

In this paper, we review ongoing progress in the development of novel on-chip, low loss planar molecular sensors that address the emerging need in the field of biochemical sensing. Chalcogenide glasses were identified as the material of choice for sensing due to their wide infrared transparency window. We report the details of manufacturing processes used to realize novel high-index-contrast, compact micro-disk resonators. Our findings demonstrate that our device can operate in dual modalities, for detection of the infrared optical absorption of a binding event using cavity enhanced spectroscopy, or sensing refractive index change due to surface molecular binding and extracting micro-structural evolution information via cavity enhanced refractometry.

Nano-patterning with polymer brushes viasolvent-assisted polymer grafting

We report surface patterning on the nanolevel with the “grafting to” approach carried out at relatively low temperatures (40 °C). Low grafting temperatures were achieved viasolvent-assisted grafting and allowed the use of the developed approach for surface templating in a variety of ways. Specifically, two examples of the patterning are discussed. A poly-2-vinylpyridine, P2VP surface pattern was created by a combination of capillary force lithography and the solvent-assisted grafting. Silver nanoparticle arrays were created and transferred into a silicon matrix employing the P2VP pattern. Solvent-assisted grafting was also a suitable technique for manipulating thermolabile objects, e.g.proteins. Protein molecules were imprinted via the grafting. Rebinding experiments showed preferential protein adsorption onto the imprinted surface relative to a non-imprinted control sample.

Toward protein imprinting with polymer brushes

The authors described an original approach for a surface protein imprinting employing grafting of polymer brushes. Protein molecules were first chemically bound to an ultrathin (1–3 nm) poly(glycidyl methacrylate) reactive polymer layer and later removed by protease treatment. Residual amino acids became grafted to the surface and to a certain extent imitated the surface chemical composition and shape of the template molecule on a nanolevel. The space surrounding the adsorbed biomolecules was modified with grafted poly(ethylene glycol) layer. This led to the formation of islands of spatial nanosized pockets complementary to the protein shape. The adsorbing protein recognized the surfaces imprinted and was anchored to the substrate.