Amplified surface plasmon resonance and electrochemical detection of Pb2+ ions using the Pb2+-dependent DNAzyme and hemin/G-quadruplex as a label

The hemin/G-quadruplex nanostructure and the Pb(2+)-dependent DNAzyme are implemented to develop sensitive surface plasmon resonance (SPR) and electrochemical sensing platforms for Pb(2+) ions. A complex consisting of the Pb(2+)-dependent DNAzyme sequence and a ribonuclease-containing nucleic acid sequence (corresponding to the substrate of the DNAzyme) linked to a G-rich domain, which is "caged" in the complex structure, is assembled on Au-coated glass surfaces or Au electrodes. In the presence of Pb(2+) ions, the Pb(2+)-dependent DNAzyme cleaves the substrate, leading to the separation of the complex and to the self-assembly of the hemin/G-quadruplex on the Au support. In one sensing platform, the Pb(2+) ions are analyzed by following the dielectric changes at the surface as a result of the formation of the hemin/G-quadruplex label using SPR. This sensing platform is further amplified by the immobilization of the sensing complex on Au NPs (13 nm) and using the electronic coupling between the NPs and the surface plasmon wave as an amplification mechanism. This method enables the sensing of Pb(2+) ions with a detection limit that corresponds to 5 fM. The second sensing platform implements the resulting hemin/G-quadruplex as an electrocatalytic label that catalyzes the electrochemical reduction of H(2)O(2). This method enables the detection of Pb(2+) with a detection limit of 1 pM. Both sensing platforms reveal selectivity toward the detection of Pb(2+) ions.     

Thermo‐Switchable Charge Transport and Electrocatalysis Using Metal‐Ion‐Modified pNIPAM‐Functionalized Electrodes

Metal ions (Ag⁺, Cu²⁺, Hg²⁺) are incorporated into an electropolymerized, poly(N‐isopropyl acrylamide), pNIPAM, thermosensitive polymer associated with an electrode using the “breathing‐in” method. The ion‐functionalized pNIPAM matrices reveal ion‐dependent gel‐to‐solid phase‐transition temperatures (28 ± 1 °C, 25 ± 1 °C, 40 ± 1 °C for the Ag⁺, Cu²⁺, and Hg²⁺‐modified pNIPAM, respectively). Furthermore, the ion‐functionalized polymers exhibit quasi‐reversible redox properties, and the ions are reduced to the respective Ag⁰, Cu⁰, and Hg⁰ nanocluster‐modified polymers. The metal‐nanocluster‐functionalized pNIPAM matrices enhance the electron transfer (they exhibit lower electron‐transfer resistances) in the compacted states. The electron‐transfer resistances of the metal‐nanocluster‐modified pNIPAM can be cycled between low and high values by temperature‐induced switching of the polymer between its contracted solid and expanded gel states, respectively. The enhanced electron‐transfer properties of the metal nanocluster‐functionalized polymer are attributed to the contacting of the metal nanoclusters in the contracted state of the polymers. This temperature‐switchable electron transfer across a Ag⁰‐modified pNIPAM was implemented to design a thermo‐switchable electrocatalytic process (the temperature‐switchable electrocatalyzed reduction of H₂O₂ by Ag⁰‐pNIPAM).     

Surface jumping in a harmonic model of trans-octatetraene: Franck—condon factors and accepting vibrational modes in s1→S0 non-vertical radiationless transition

A phase-space method for finding the accepting modes in a non-vertical radiationless vibronic transition and for recognizing the final state with the largest Franck—Condon factor is applied to a harmonic model of the S₁ → S₀ relaxation in trans-octatetraene. Input required for the analysis includes the energy gap between S₁ and S₀, normal mode frequencies, reduced masses, and eigenvectors (including the Duschinsky rotation matrix), and the molecule equilibrium configurations (bond lengths and angles) in S₁ and S₀. Some of these data are taken from published experimental results and some are calculated in this work. The energy gap of 0.132 au is much larger than the energy of a vertical transition, which is only 0.047 au. The phase-space method gives a closed-form analytic solution for how to divide the excess energy between the accepting modes. The final distribution includes a large excitation of the two CH₂ end groups, where the motion of the two hydrogen atoms within each quasilocal CH₂ group is antisymmetric; a symmetric stretch of the two central C-H bonds of the molecule; and small totally symmetric bending of the whole molecule. Comparison of Franck-Condon factors (exact within the harmonic model) of the final state obtained by the phase-space analysis and of other similar isoenergetic states shows that the phase-space method indeed chooses the most probable final energy distribution. Possible modifications of these results due to anharmonic effects are discussed.     

An Au nanoparticle/bisbipyridinium cyclophane-functionalized ion-sensitive field-effect transistor for the sensing of adrenaline

A film consisting of polyethyleneimine (PEI), Au nanoparticles (12 +/- 1 nm) and coadsorbed cyclobis(paraquat-p-phenylene) (1) was assembled as a sensing interface on the Al2O3 insulating layer of an ion-sensitive field-effect transistor (ISFET). Adrenaline (2) was sensed by the functionalized ISFET with a detection limit of 1 x 10(-6) M. The sensing ability of the nanostructured device for the analysis of adrenaline originates from the preconcentration of the analyte in the cyclophane by pi-pi donor-acceptor interactions. Analysis of adrenaline is accomplished by the measurement of the source-drain current, Isd, or by the gate-source voltage, Vgs. The sensing device is reusable (at least 100 cycles) and exhibits high stability.     

Surface Imprinting in Layer‐by‐Layer Nanostructured Films

In this Full Paper, we develop a novel approach for the generation of stable molecularly imprinted sites in polymeric films by combining the layer‐by‐layer (LbL) technique and photochemical crosslinking of the layered structure. After photo‐crosslinking, the imprinted films show high reproducibility and rapid loading and unloading of imprinted sites by the template molecules. Moreover, the competitive adsorption of template molecules and redox labels into the imprinted film using electrochemical methods indicates that the imprinted film has higher affinity for template molecules. We believe this approach may have some advantages over traditional ways of preparing imprinted sites in polymer matrices and it may open a new avenue for the functionalization of LbL films.     

Measurement of Q degradation due to polarisation mode dispersion using multiple importance sampling

Multiple importance-sampling (IS) is used to measure the Q degradation due to the polarisation mode dispersion generated by three programmable DGD elements with uniform polarisation coupling between sections. The measured Q-penalty probability distribution extends to <10/sup -17/ with only 1800 experimental samples.     

Evolution of the acousto-optic wavelength routing switch

Through the efforts of many research groups and consortia over the last several years, the acousto-optic tunable filter has evolved into a device capable of high-performance wavelength-selective optical switching and wavelength routing in dense WDM systems. The distinguishing feature of the AO switch is its ability to sustain many independent coexisting passbands, thus allowing in a simple integrated-optic device, the parallel processing capability of much more complex designs. The AOTF has also found a role in active gain equalization of optically amplified networks. In this paper, we review the design of both hybrid and fully integrated AO switches. The theory of operation is reviewed and recent advances in passband engineering are described which have made low-crosstalk, wavelength misalignment-tolerant switches to be possible. Advanced issues such as mechanisms of interchannel crosstalk and its reduction are also discussed. Both device and system issues are covered     

Inhibition of the acetycholine esterase-stimulated growth of Au nanoparticles: nanotechnology-based sensing of nerve gases

The acetylcholine esterase, AChE, mediated hydrolysis of acetylthiocholine (1) yields a reducing agent thiocholine (2) that stimulates the catalytic enlargement of Au NP seeds in the presence of AuCl(4)(-). The reductive enlargement of the Au NPs is controlled by the concentration of the substrate (1) and by the activity of the enzyme. The catalytic growth of the Au NPs is inhibited by 1,5-bis(4-allyldimethylammoniumphenyl)pentane-3-one dibromide (3) or by diethyl p-nitrophenyl phosphate (paraoxon; 4), thus enabling a colorimetric test for AChE inhibitors. The colorimetric assay was also developed on glass supports.