Jin Lu

Graphene Oxide Amplified Electrogenerated Chemiluminescence of Quantum Dots and Its Selective Sensing for Glutathione from Thiol-Containing Compounds

Here we report a graphene oxide amplified electrogenerated chemiluminescence (ECL) of quantum dots (QDs) platform and its efficient selective sensing for antioxidants. Graphene oxide facilitated the CdTe QDs*+ production and triggered O2*- generation. Then, a high yield of CdTe QDs* was formed due to the combination of CdTe QDs*+ and O2*-, leading to an approximately 5-fold ECL amplification. Glutathione is the most abundant cellular thiol-containing peptide, but its selective sensing is an intractable issue in analytical and biochemical communities because its detection is interfered with by some thiol-containing compounds. This platform showed a detection limit of 8.3 microM (S/N = 3) for glutathione and a selective detection linear dependence from 24 to 214 microM in the presence of 120 muM cysteine and glutathione disulfide. This platform was also successfully used for real sample (eye drug containing glutathione) detection without any pretreatment with a wide linear range from 0.04 to 0.29 microg mL(-1).

Fabrication of polymeric ionic liquid/graphene nanocomposite for glucose oxidase immobilization and direct electrochemistry.

A novel polymeric ionic liquid functionalized graphene, poly(1-vinyl-3-butylimidazolium bromide)-graphene (denoted as poly(ViBuIm(+)Br(-))-G), was synthesized. FTIR, UV-vis spectra and TEM were used to characterize the formation of as synthesized nanocomposites. Due to the modification of the polymeric ionic liquid, poly(ViBuIm(+)Br(-))-G can not only be dispersed well in aqueous solutions to form a homogeneous colloidal suspension of individual nanosheets, but also exhibit a strong positive charge. Based on self-assembly, the negatively charged glucose oxidase (GOD) was immobilized onto the poly(ViBuIm(+)Br(-))-G to form a GOD/poly(ViBuIm(+)Br(-))-G/glassy carbon (GC) electrode under mild conditions. With the advantage of both poly(ViBuIm(+)Br(-)) and graphene, poly(ViBuIm(+)Br(-))-G can provide a favorable and conductive microenvironment for the immobilized GOD and thus promote their direct electron transfer at the GC electrode. Furthermore, the GOD/poly(ViBuIm(+)Br(-))-G/GC electrode displayed an excellent sensitivity, together with a wide linear range and excellent stability for the detection of glucose. Accordingly, these unique properties of such novel nanocomposite generate a promising platform for the construction of mediator-free enzymatic biosensors.

Label-free imaging, detection, and mass measurement of single viruses by surface plasmon resonance

We report on label-free imaging, detection, and mass/size measurement of single viral particles in solution by high-resolution surface plasmon resonance microscopy. Diffraction of propagating plasmon waves along a metal surface by the viral particles creates images of the individual particles, which allow us to detect the binding of the viral particles to surfaces functionalized with and without antibodies. We show that the intensity of the particle image is related to the mass of the particle, from which we determine the mass and mass distribution of influenza viral particles with a mass detection limit of approximately 1 ag (or 0.2 fg/mm2). This work demonstrates a multiplexed method to measure the masses of individual viral particles and to study the binding activity of the viral particles.

A Hybrid Electrochemical−Colorimetric Sensing Platform for Detection of Explosives

A highly selective, sensitive, and low-cost hybrid sensing platform is developed based on extraordinary properties of explosives in an ionic liquid and an integrated electrochemical and colorimetric approach.

Plasmonic-Based Electrochemical Impedance Spectroscopy: Application to Molecular Binding

Plasmonic-based electrochemical impedance spectroscopy (P-EIS) is developed to investigate molecular binding on surfaces. Its basic principle relies on the sensitive dependence of surface plasmon resonance (SPR) signal on surface charge density, which is modulated by applying an ac potential to a SPR chip surface. The ac component of the SPR response gives the electrochemical impedance, and the dc component provides the conventional SPR detection. The plasmonic-based impedance measured over a range of frequency is in quantitative agreement with the conventional electrochemical impedance. Compared to the conventional SPR detection, P-EIS is sensitive to molecular binding taking place on the chip surface and less sensitive to bulk refractive index changes or nonspecific binding. Moreover, this new approach allows for simultaneous SPR and surface impedance analysis of molecular binding processes.

Hybrid mechanoresponsive polymer wires under force activation.

Force activation is triggered in a stretched polymer wire with color changes produced as a consequence of the molecules undergoing structural and conformational changes. A markedly increased efficiency of force activation is achieved by decreasing the diameter of the wires. The hybrid mechanosensitive polymer wire can function as micro- and nanoscale force sensor.

Label‐Free Imaging of Dynamic and Transient Calcium Signaling in Single Cells

Cell signaling consists of diverse events that occur at various temporal and spatial scales, ranging from milliseconds to hours and from single biomolecules to cell populations. The pathway complexities require the development of new techniques that detect the overall signaling activities and are not limited to quantifying a single event. A plasmonic-based electrochemical impedance microscope (P-EIM) that can provide such data with excellent temporal and spatial resolution and does not require the addition of any labels for detection has now been developed. The highly dynamic and transient calcium signaling activities at the early stage of G-protein-coupled receptor (GPCR) stimulation were thus studied. It could be shown that a subpopulation of cells is more responsive towards agonist stimulation, and the heterogeneity of the local distributions and the transient activities of the ion channels during agonist-activated calcium flux in single HeLa cells were investigated.

Single-Molecule Electrochemistry on a Porous Silica-Coated Electrode

Here we report the direct observation and quantitative analysis of single redox events on a modified indium-tin oxide (ITO) electrode. The key in the observation of single redox events are the use of a fluorogenic redox species and the nanoconfinement and hindered redox diffusion inside 3-nm-diameter silica nanochannels. A simple electrochemical process was used to grow an ultrathin silica film (∼100 nm) consisting of highly ordered parallel nanochannels exposing the electrode surface from the bottom. The electrode-supported 3-nm-diameter nanochannels temporally trap fluorescent resorufin molecules resulting in hindered molecular diffusion in the vicinity of the electrode surface. Adsorption, desorption, and heterogeneous redox events of individual resorufin molecules can be studied using total-internal reflection fluorescence (TIRF). The rate constants of adsorption and desorption processes of resorufin were characterized from single-molecule analysis to be (1.73 ± 0.08) × 10-4 cm·s-1 and 15.71 ± 0.76 s-1, respectively. The redox events of resorufin to the non-fluorescent dihydroresorufin were investigated by analyzing the change in surface population of single resorufin molecules with applied potential. The scan-rate-dependent molecular counting results (single-molecule fluorescence voltammetry) indicated a surface-controlled electrochemical kinetics of the resorufin reduction on the modified ITO electrode. This study demonstrates the great potential of mesoporous silica as a useful modification scheme for studying single redox events on a variety of transparent substrates such as ITO electrodes and gold or carbon film coated glass electrodes. The ability to electrochemically grow and transfer mesoporous silica films onto other substrates makes them an attractive material for future studies in spatial heterogeneity of electrocatalytic surfaces.

Tuned chromic process for polydiacetylenes vesicles: the influence of polymer matrices

Thermo-sensitive poly(N-isopropylacrylamide) hydrogel was used as a matrix polymer to immobilize polydiacetylenes (PDAs) vesicles. Blue-red chromic transition of PDAs was observed at lower temperature, compared to PDAs vesicle dispersion. The tuned chromic process was due to the interaction between matrix polymer and PDAs, especially the discontinuous volume phase transitions around the lower critical solution temperature of poly(N-isopropylacrylamide).

Electrostatic Ion Enrichment in an Ultrathin-Layer Cell with a Critical Dimension between 5 and 20 nm

Electrostatic interactions play an essential role in many analytical applications including molecular sensing and transport studies using nanopores and separation of charged species. Here, we report the voltammetric quantification of electrostatic ion enrichment in a 5-20 nm thin electrochemical cell. A simple lithographic micro/nanofabrication process was used to create ultrathin-layer cells (UTLCs) with a critical dimension (i.e., cell thickness) as small as 5 nm. The voltammetric response of a UTLC was found to be largely dominated by the electrostatic interaction between charges on the cell walls and the redox species. We show that the ultrasmall cell dimension yielded a 100-300-fold enrichment for cationic redox species. An interesting surface adsorption effect was also demonstrated.