Adarsh D. Radadia

Surface functionalization of thin-film diamond for highly stable and selective biological interfaces

Carbon is an extremely versatile family of materials with a wide range of mechanical, optical, and mechanical properties, but many similarities in surface chemistry. As one of the most chemically stable materials known, carbon provides an outstanding platform for the development of highly tunable molecular and biomolecular interfaces. Photochemical grafting of alkenes has emerged as an attractive method for functionalizing surfaces of diamond, but many aspects of the surface chemistry and impact on biological recognition processes remain unexplored. Here we report investigations of the interaction of functionalized diamond surfaces with proteins and biological cells using X-ray photoelectron spectroscopy (XPS), atomic force microscopy, and fluorescence methods. XPS data show that functionalization of diamond with short ethylene glycol oligomers reduces the nonspecific binding of fibrinogen below the detection limit of XPS, estimated as > 97% reduction over H-terminated diamond. Measurements of different forms of diamond with different roughness are used to explore the influence of roughness on nonspecific binding onto H-terminated and ethylene glycol (EG)-terminated surfaces. Finally, we use XPS to characterize the chemical stability of Escherichia coli K12 antibodies on the surfaces of diamond and amine-functionalized glass. Our results show that antibody-modified diamond surfaces exhibit increased stability in XPS and that this is accompanied by retention of biological activity in cell-capture measurements. Our results demonstrate that surface chemistry on diamond and other carbon-based materials provides an excellent platform for biomolecular interfaces with high stability and high selectivity.

Micromachined GC columns for fast separation of organophosphonate and organosulfur compounds.

This article demonstrates how to prepare microfabricated columns (microcolumns) for organophosphonate and organosulfur compound separation that rival the performance of commercial capillary columns. Approximately 16,500 theoretical plates were generated with a 3 m long OV-5-coated microcolumn with a 0.25 microm phase thickness using helium as the carrier gas at 20 cm/s. Key to the advance was the development of deactivation procedures appropriate for silicon microcolumns with Pyrex tops. Active sites in a silicon-Pyrex microcolumn cause peak tailing and unwanted adsorption. Experimentally, we found that organosilicon hydride deactivation lowers adsorption activity in microcolumns more than silazane and silane treatments. But without further treatment, the phosphonate peaks continue to tail after the coating process. We found that heat treatment with pinacolyl methylphosphonic acid (PMP) eliminated the phosphonate peak tailing. In contrast, conventional resilylation employing N, O-bis(trimethylsilyl)acetamide, hexamethyldisilazane, and 1-(trimethylsilyl)imidazole does not eliminate peak tailing. Column activity tests show that the PMP treatment also improves the peaks for 2,6-dimethyl aniline, 1-octanol, and 1-decanol implying a decrease in the columns hydrogen bonding sites with the PMP treatment. FT-IR analysis shows that exposure to PMP forms a bond to the stationary phase that deactivates the active sites responsible for organophosphonate peak tailing.

Partially Buried Microcolumns for Micro Gas Analyzers

This article demonstrates the feasibility of making a partially buried micro gas chromatography (micro-GC) column with a rounded channel wall profile, which enables coating the stationary phase more uniformly and shows better separation characteristics than a square deep reactive ion etched (DRIE) wall profile. A buried structure fabrication method was adapted to fabricate 34 cm long, 165 microm wide, and 65 microm deep partially buried microcolumns, which had a unique rounded microcolumn wall profile similar to that of a flattened circular tube. The separation characteristics were compared to that of a 34 cm long, 100 microm x 100 microm square DRIE microcolumn, which had a similar hydraulic diameter. Minimum height equivalent to a theoretical plate (HETP) and reduced HETP of 0.39 mm and 6.02, respectively, with a retention factor of 6.3 were obtained on the coated partially buried microcolumn compared to 0.66 mm and 6.73, respectively, on the coated square DRIE microcolumn with a similar retention factor. The partially buried microcolumn was found to perform closer to the theoretical approximation and this could be attributed to the uniform phase deposition in the partially buried microcolumn compared to the square DRIE microcolumn. A 10 component mix was separated on the partially buried microcolumn in 3.8 s with the maximum peak width at half-height equal to 0.2 s, while a similar mix separated at higher pressure and temperature conditions on the square DRIE microcolumn in 4.6 s. The rounded corners allowed depositing thinner stationary phase, which was reflected in the faster elution of n-C(12) on the partially buried microcolumn compared to the square DRIE microcolumn. The better performance of the partially buried microcolumn may be attributed to either the rounded channel wall profile, the clean channel structures produced by the fabrication process, or the double-etched wall profile, which lowers the Taylor-Aris dispersion.

Rapid thermal lysis of cells using silicon–diamond microcantilever heaters

This paper presents the design and application of microcantilever heaters for biochemical applications. Thermal lysis of biological cells was demonstrated as a specific example. The microcantilever heaters, fabricated from selectively doped single crystal silicon, provide local resistive heating with highly uniform temperature distribution across the cantilevers. Very importantly, the microcantilever heaters were coated with a layer of 100 nm thick electrically insulating ultrananocrystalline diamond (UNCD) layer used for cell immobilization on the cantilever surface. Fibroblast cells or bacterial cells were immobilized on the UNCD/cantilever surfaces and thermal lysis was demonstrated via optical fluorescence microscopy. Upon electrical heating of the cantilever structures to 93 degrees C for 30 seconds, fibroblast cell and nuclear membrane were compromised and the cells were lysed. Over 90% of viable bacteria were also lysed after 15 seconds of heating at 93 degrees C. This work demonstrates the utility of silicon-UNCD heated microcantilevers for rapid cell lysis and forms the basis for other rapid and localized temperature-regulated microbiological experiments in cantilever-based lab on chip applications.

Nano/Micro and Spectroscopic Approaches to Food Pathogen Detection

Despite continuing research efforts, timely and simple pathogen detection with a high degree of sensitivity and specificity remains an elusive goal. Given the recent explosion of sensor technologies, significant strides have been made in addressing the various nuances of this important global challenge that affects not only the food industry but also human health. In this review, we provide a summary of the various ongoing efforts in pathogen detection and sample preparation in areas related to Fourier transform infrared and Raman spectroscopy, light scattering, phage display, micro/nanodevices, and nanoparticle biosensors. We also discuss the advantages and potential limitations of the detection methods and suggest next steps for further consideration.

The fabrication of all-silicon micro gas chromatography columns using gold diffusion eutectic bonding

Temperature programming of gas chromatography (GC) separation columns accelerates the elution rate of chemical species through the column, increasing the speed of analysis, and hence making it a favorable technique to speedup separations in microfabricated GCs (micro-GC). Temperature-programmed separations would be preferred in an all-silicon micro-column compared to a silicon-Pyrex® micro-column given that the thermal conductivity and diffusivity of silicon is 2 orders of magnitude higher than Pyrex®. This paper demonstrates how to fabricate all-silicon micro-columns that can withstand the temperature cycling required for temperature-programmed separations. The columns were sealed using a novel bonding process where they were first bonded using a gold eutectic bond, then annealed at 1100 °C to allow gold diffusion into silicon and form what we call a gold diffusion eutectic bond. The gold diffusion eutectic-bonded micro-columns when examined using scanning electron microscopy (SEM), scanning acoustic microscopy (SAM) and blade insertion techniques showed bonding strength comparable to the previously reported anodic-bonded columns. Gas chromatography-based methane injections were also used as a novel way to investigate proper sealing between channels. A unique methane elution peak at various carrier gas inlet pressures demonstrated the suitability of gold diffusion eutectic-bonded channels as micro-GC columns. The application of gold diffusion eutectic-bonded all-silicon micro-columns to temperature-programmed separations (120 °C min−1) was demonstrated with the near-baseline separation of n-C6 to n-C12 alkanes in 35 s.

A Fully-Integrated MEMS Preconcentrator for Rapid Gas Sampling

In this paper, we present a new type of MEMS gaseous species preconcentrator (muPC) that has been fabricated and tested as a front end for a flame ionization detector (FID). A one microliter muPC filled with microposts is integrated with microvalves (response time < 50 mus) and a resistive microheater (ramping to 200degC in 0.5 seconds). The integrated muPC can sample a cubic centimeter of gas in 0.2 second at 49 kPa, adsorb targeted species, heat and desorb, and inject concentrated gaseous species with 50 microsecond pulses into separation columns and/or detectors. The unprecedented speed of this muPC is enabled by MEMS sizing and fabrication, allowing sniffing of phosphonates, toxic industrial chemicals (TICs), and other volatile compounds in seconds, rather than tens of minutes with conventional systems.

New Column Designs for MicroGC

In this paper, we present some new column designs for micro-gas chromatography (muGC) columns. Serpentine columns are compared to commonly used spiral columns and are found to give relatively lower height equivalent to theoretical plate (HETP) values. Turns are a major dispersion source for serpentine configuration. We found that sinusoidal compensation structures following the turns give lowest dispersion amongst the several tested turn geometries for serpentine configuration.

Synthesis, Characterization, and Photoactivity of Ta2O5‐Grafted SiO2 Nanoparticles

Herein, we discuss the synthesis as well as material and photochemical characterization of nanometer-sized Ta(2)O(5) decorated, in a controlled fashion, on top of 20 nm diameter SiO(2) particles to yield a composite oxide with a tunable band-gap width. Particular emphasis is paid to control of particle size, and control of the distribution of the overlying oxide. The nanoscale dimension imparts a high surface area and introduces quantum confinement effects that displace the conduction band more negatively and the valence band more positively on the electrochemical scale of potentials. This band shift results in an increase of the number of possible participants in photocatalytic reactions. The band shift is shown to result in an increase in driving force for thermodynamically feasible reactions. By decorating SiO(2) with smaller-sized Ta(2)O(5), the interplay of the Lewis acidity of SiO(2) and the contact area between Ta(2)O(5) and SiO(2) is utilized to develop a photocatalyst with higher photoactivity than pure Ta(2)O(5).

Enhanced toxic gas detection using a MEMS preconcentrator coated with the metal organic framework absorber

Widespread and timely sensing of explosives, toxic chemicals and industrial compounds needs fast, sensitive detection technology that is affordable and portable. Many gas detectors developed for portable applications are based on sensing a change in resistivity or other non-selective material properties, often leading to low sensitivity and selectivity. In this paper, we report a new generation of the UIUC MEMS gas preconcentrator (muGPC) and its integration into a microfluidic M-8 (muM8) detector to demonstrate an enhanced overall detection limit and selectivity in detecting a toxic gas simulant. The integration creates a portable sensor to sniff an analyte of interest at concentration of 10 ppb or below.