Lab-on-a-chip sensor for detection of highly electronegative heavy metals by anodic stripping voltammetry.

This work describes development of a lab-on-a-chip sensor for electrochemical detection of highly electronegative heavy metals such as manganese and zinc by anodic stripping voltammetry. The sensor consists of a three-electrode system, with a bismuth working electrode, a Ag/AgCl reference electrode, and a Au auxiliary electrode. Hydrolysis at the auxiliary electrode is a critical challenge in such electrochemical sensors as its onset severely limits the ability to detect electronegative metals. The bismuth working electrode is used due to its comparable negative detection window and reduced toxicity with respect to a conventional mercury electrode. Through optimization of the sensor layout and the working electrode surface, effects of hydrolysis were substantially reduced and the potential window was extended to the -0.3 to -1.9 V range (vs. Ag/AgCl reference electrode), which is far more negative than what is possible with conventional Au, Pt, or carbon electrodes. The described lab-on-a-chip sensor for the first time permits reliable and sensitive detection of the highly electronegative manganese. The favorable performance of the bismuth electrode coupled with its environmentally-friendly nature make the described sensor attractive for applications where disposable chips are desirable. With further development and integrated sample preparation, the lab-on-a-chip may be converted into a point-of-care platform for monitoring heavy metals in blood (e.g., assessment of manganese exposure).

PEG/Dextran Double Layer Influences Fe Ion Release and Colloidal Stability of Iron Oxide Nanoparticles.

Despite preliminary confidence on biosafety of polymer coated iron oxide nanoparticles (SPIONs), toxicity concerns have hampered their clinical translation. SPIONs toxicity is known to be due to catalytic activity of their surface and release of toxic Fe ions originating from the core biodegradation, leading to the generation of reactive oxygen species (ROS). Here, we hypothesized that a double-layer polymeric corona comprising of dextran as an interior, and polyethylene glycol (PEG) as an exterior layer better shields the core SPIONs. We found that ROS generation was cell specific and depended on SPIONs concentration, although it was reduced by sufficient PEG immobilization or 100 µM deferoxamine. 24 h following injection, PEGylated samples showed reduction of biodistribution in liver, heterogenous biodistribution profile in spleen, and no influence on NPs blood retention. Sufficient surface masking or administration of deferoxamine could be beneficial strategies in designing and clinical translation of future biomedical SPIONs.

Photodefinable polydimethylsiloxane (PDMS) for rapid lab-on-a-chip prototyping.

In this paper, we introduce a new and simple method of patterning polydimethylsiloxane (PDMS) directly using benzophenone as a photoinitiator. The photodefinable PDMS mixture (photoPDMS) is positive-acting and only sensitive to light below 365 nm, permitting processing under normal ambient light. Features of the order of 100 microm, which are sufficiently small for most microfluidic applications, were successfully fabricated using this novel process. A parametric study of process parameters was performed to optimize the fabrication. As a demonstration, microfluidic channels of varying dimensions were successfully fabricated using this process and experimentally characterized using fluorescence microscopy. To further demonstrate photoPDMS potential, thin (<30 microm) free-standing films with through patterns were fabricated and successfully used as shadow masks. The photoPDMS process completely eliminates the need for a master, permits processing under normal ambient light conditions, and makes fabrication fast and simple. This process for rapid prototyping of low-cost, disposable LOCs can be accomplished without cleanroom facilities and thus can be employed for a wide range of applications.

Enhanced Electrochemical Sensing with Carbon Nanotubes Modified with Bismuth and Magnetic Nanoparticles in a Lab-on-a-Chip.

Iron plays an especially important role in human physiological functions and pathological impairments. The superior properties of carbon nanotubes (CNTs) and their modification with bismuth and magnetic nanoparticles as developed in this work have led to an extraordinary and novel material to facilitate ultrasensitive detection in the nanomolar range. Here, we present the development of an electrochemical sensor for detection of ferrous (Fe2+) and ferric (Fe3+) iron by means of CNTs modified with bismuth and magnetic nanoparticles for higher sensitivity of detection. The sensor fabrication includes microfabrication methodologies, soft lithography, and electrodeposition. Cyclic voltammetry and differential pulse voltammetry are used for the electroanalytical studies and detection of the ions in samples. The sensor has a dynamic range of detection from 0.01 nm to 10 mm. The performance of the sensor with modified CNTs was explored for sensitivity and specificity. CNTs, modified with bismuth and magnetic nanoparticles by means of electrodeposition, enhanced the detection limit significantly down to 0.01 nm.

Zinc Detection in Serum by Anodic Stripping Voltammetry on Microfabricated Bismuth Electrodes.

Zinc (Zn) homeostasis is required for a functional immune system. Critically ill patients often exhibit decreased Zn serum concentrations and could potentially benefit from Zn supplementation as a therapeutic strategy. However, the conventional approaches to monitoring Zn are time consuming and costly. This work reports on detection of Zn by anodic stripping voltammetry (ASV) on bismuth electrodes in a microfabricated electrochemical cell. The working potential window of the electrodeposited bismuth film electrode was investigated by cyclic voltammetry, while square wave ASV was used for measuring Zn in acetate buffer and blood serum. Conditions critical to sensing, such as preconcentration potential, preconcentration time, and buffer pH, were optimized for Zn detection. The sensor was successfully calibrated with pH 6 acetate buffer in the physiologically-relevant range of 5 µM to 50µM Zn and exhibited well-defined and highly repeatable peaks. The sensor was used to demonstrate measurement of Zn in blood serum digested in HCl. The results of this work show that Zn detection in serum is possible with smaller sample volumes (µL vs. µL) and faster turnaround time (hours vs. days) as compared with the conventional spectroscopic methods.