Total Capture, Convection-Limited Nanofluidic Immunoassays Exhibiting Nanoconfinement Effects.

Understanding nanoconfinement phenomena is necessary to develop nanofluidic technology platforms. One example of nanoconfinement phenomena is shifts in reaction equilibria toward reaction products in nanoconfined systems, which have been predicted theoretically and observed experimentally in DNA hybridization. Here we demonstrate a convection-limited nanofluidic immunoassay that achieves total capture of a target analyte and an apparent shift in the antibody-antigen reaction equilibrium due to nanoconfinement.

Plasma-Assisted Large-Scale Nanoassembly of Metal-Insulator Bioplasmonic Mushrooms.

Large-scale plasmonic substrates consisting of metal-insulator nanostructures coated with a biorecognition layer can be exploited for enhanced label-free sensing by utilizing the principle of localized surface plasmon resonance (LSPR). Most often, the uniformity and thickness of the biorecognition layer determine the sensitivity of plasmonic resonances as the inherent LSPR sensitivity of nanomaterials is limited to 10-20 nm from the surface. However, because of time-consuming nanofabrication processes, there is limited work on both the development of large-scale plasmonic materials and the subsequent surface functionalizing with biorecognition layers.

Microfluidic device flow field characterization around tumor spheroids with tunable necrosis produced in an optimized off-chip process.

Tumor spheroids are a 3-D tumor model that holds promise for testing cancer therapies in vitro using microfluidic devices. Tailoring the properties of a tumor spheroid is critical for evaluating therapies over a broad range of possible indications. Using human colon cancer cells (HCT-116), we demonstrate controlled tumor spheroid growth rates by varying the number of cells initially seeded into microwell chambers.

Light-Induced Reversible Change of Roughness and Thickness of Photosensitive Polymer Brushes.

We investigate light-induced changes in thickness and roughness of photosensitive polymer brushes containing azobenzene cationic surfactants by atomic force microscopy (AFM) in real time during light irradiation. Because the cis-state of azobenzene unit requires more free volume than its trans counterpart, the UV light-induced expansion of polymer thin films associated with the trans-to-cis isomerism of azobenzene groups is expected to occur. This phenomenon is well documented in physisorbed polymer films containing azobenzene groups.

Swelling of polyelectrolyte and polyzwitterion brushes by humid vapors.

Swelling behavior of polyelectrolyte and polyzwitterion brushes derived from poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) in water vapor is investigated using a combination of neutron and X-ray reflectivity and spectroscopic ellipsometry over a wide range of relative humidity (RH) levels. The extent of swelling depends strongly on the nature of the side-chain chemistry. For parent PDMAEMA, there is an apparent enrichment of water vapor at the polymer/air interface.

Opto-mechanical scission of polymer chains in photosensitive diblock-copolymer brushes.

In this paper we report on an opto-mechanical scission of polymer chains within photosensitive diblock-copolymer brushes grafted to flat solid substrates. We employ surface-initiated polymerization of methylmethacrylate (MMA) and t-butyl methacrylate (tBMA) to grow diblock-copolymer brushes of poly(methylmethacrylate-b-t-butyl methacrylate) following the atom transfer polymerization (ATRP) scheme. After the synthesis, deprotection of the PtBMA block yields poly(methacrylic acid) (PMAA).

Separation and molecular-level segregation of complex alkane mixtures in metal-organic frameworks.

In this computational work we explore metal-organic frameworks (MOFs) for separating alkanes according to the degree of branching. We show that the structure MOF-1 shows an adsorption hierarchy for a 13-component light naphtha mixture precisely as desired for increasing the research octane number of gasoline. In addition we report an unusual molecular-level segregation of molecules based on their degree of branching.