Cu Nanoclusters-Encapsulated Liposomes: Toward Sensitive Liposomal Photoelectrochemical Immunoassay.

Herein we report the strategy of liposome-mediated Cu2+-induced exciton trapping upon CdS quantum dots (QDs) for amplified photoelectrochemical (PEC) bioanalysis application. Specifically, the Cu nanoclusters (NCs)-encapsulated liposomes were first fabricated and then processed with antibodies bound to their external surfaces. After the sandwich immunocomplexing, the confined liposomal labels were subjected to sequential lysis treatments for the release of Cu NCs and numerous Cu2+ ions, which were then directed to interact with the CdS QDs electrode. The interaction of Cu2+ ions with CdS QDs could generate CuxS and form the trapping sites to block the photocurrent generation. Since the photocurrent inhibition is closely related with the Cu NCs-loaded liposomal labels, a novel and general "signal-off" PEC immunoassay could thus be tailored with high sensitivity. Meanwhile, a complementary "signal-on" fluorescent detection could be accomplished by measuring the fluorescence intensity originated from the Cu NCs. This work features the first use of Cu NCs in PEC bioanalysis and also the first NCs-loaded liposomal PEC bioanalysis. More importantly, by using other specific ions/reagents-semiconductors interactions, this protocol could serve as a common basis for the general development of a new class of liposome-mediated PEC bioanalysis.

3D Semiconducting Polymer/Graphene Networks: Toward Sensitive Photocathodic Enzymatic Bioanalysis.

This work reports the development of three-dimensional (3D) semiconducting polymer/graphene (SP/G) networks toward sensitive photocathodic enzymatic bioanalysis. Specifically, the porous 3D graphene was first synthesized via the hydrothermal and freeze-dry processes and then mixed with semiconducting polymer to obtain the designed hierarchical structure with unique porosity and large surface area. Afterward, the as-prepared hybrid was immobilized onto the indium tin oxide (ITO) for further characterizations. Exemplified by sarcosine oxidase (SOx) as a model biocatalyst, an innovative 3D SP/G-based photocathodic bioanalysis capable of sensitive and specific sarcosine detection was achieved. The suppression of cathodic photocurrent was observed in the as-developed photocathodic enzymatic biosystem due to the competition of oxygen consumption between the enzyme-biocatalyst process and O2-dependent photocathodic electrode. This work not only presented a unique protocol for 3D SP/G-based photocathodic enzymatic bioanalysis but also provided a new horizon for the design, development, and utilization of numerous 3D platforms in the broad field of general photoelectrochemical (PEC) bioanalysis.

Donnan potential caused by polyelectrolyte monolayers.

The Donnan potential is successfully isolated from ion pair potential on a ferrocene-labeled polyelectrolyte (DNA) monolayer. The isolated Donnan potential shifts negatively upon the increase in NaClO4 concentration with a slope of -58.8 mV/decade. With the salt concentration grown up to 1 M, the stretched DNA chains in low salt concentration are found to experience a gradual conformation relaxing process. At salt concentrations higher than 2 M, Donnan breakdown occurs where only the ion pair effect modulates the apparent potential. The apparent formal potential also shows strong dependence on solution pH, which reveals that the charge density in the polyelectrolyte monolayer plays an important role in the establishment of Donnan equilibrium.

Multi-parameter detection of diabetes mellitus on multichannel poly(dimethylsiloxane) analytical chips coupled with nanoband microelectrode arrays.

This article demonstrates a novel method for multi-parameter detection of diabetes mellitus. We propose an approach for fabrication of a 3-D metal films array with gold and copper using electroless deposition technique on PDMS substrate. The obtained PDMS slices containing metal films are superimposed layer by layer as a sandwich structure to form 3-D metal films array. The cross-sections of the array could be used as nanoband array electrochemical detectors, which are further integrated with a multichannel microchip for simultaneously detecting multi-parameter of diabetes mellitus, including glucose and metabonomics of diabetes containing aldehyde compounds (glyoxal and methylglyoxal) and short organic acids (lactate, urate and 2-hydroxybutyrate). Under optimized separation and detection conditions, glucose, aldehyde compounds and short organic acids respond linearly in the concentration range of 10-2000, 1-500 and 5-600 µM, with the LODs of 4, 0.5 and 3 µM for glucose, aldehyde compounds and short organic acids, respectively. This system is successfully employed to detect these compounds in serums. This study reveals that the electrochemical array detectors with different materials integrated with multichannel microchip provide a flexible and inexpensive approach for routine, simultaneous and direct detection of some metabolites in metabonomics.

Improvement of heat dissipation for polydimethylsiloxane microchip electrophoresis.

Effective removing of Joule heat in polymer-based microchip system is an important factor for high efficient separation because of lower heat conductivity of polymers than silica or glass. In this paper, a new kind of polydimethylsiloxane (PDMS) microchip electrophoresis system integrated with a laser-induced fluorescence detector has been successfully constructed on the basis of a commercial heat sink for computer CPU (central processor unit). Experimental results on separation current using high concentration running buffers demonstrated that heat dissipation of PDMS/PDMS microchip system was significantly improved. Furthermore, with this integrated system, theoretical plate number of fluorescein using 100 mM phosphate-buffered saline + 1 mM sodium dodecyl sulfate as running buffer was determined to be 2750 (for 2.5-cm separation channel, corresponding to 110,000/m). This high separation efficiency demonstrated that such heat sink-based polymer microchip system could be effectively applied for high-concentration buffers.

Bulk modification of PDMS microchips by an amphiphilic copolymer.

A simple and rapid bulk-modification method based on adding an amphiphilic copolymer during the fabrication process was employed to modify PDMS microchips. Poly(lactic acid)-poly(ethylene glycol) (PLA-PEG) was used as the additive substance. Compared to the native PDMS microchips, both the contact angle and the EOF of the bulk-modified PDMS microchips decreased. The effects of the additive loading and the pH on the EOF were investigated in detail. The bulk-modified PDMS microchips exhibited reproducible and stable EOF behavior. The application of the bulk-modified PDMS microchips was also studied and the results indicated that they could be successfully used to separate amino acids and to suppress protein adsorption.