Lighting-up the dynamics of telomerization and DNA replication by CdSe-ZnS quantum dots

CdSe-ZnS core-shell quantum dots (QDs) act as photochemical centers for lighting-up the dynamics of telomerization or DNA replication.     

Magneto-mechanical detection of nucleic acids and telomerase activity in cancer cells

The ultra-sensitive magneto-mechanical detection of DNA, single-base-mismatches in nucleic acids, and the assay of telomerase activity are accomplished by monitoring the magnetically induced deflection of a cantilever functionalized with magnetic beads associated with the biosensing interface. The analyzed M13phi DNA hybridized with the nucleic acid-functionalized magnetic beads is replicated in the presence of dNTPs that include biotin-labeled dUTP. The resulting beads are attached to an avidin-coated cantilever, and the modified cantilever is deflected by an external magnetic field. Similarly, telomerization of nucleic acid-modified magnetic beads in the presence of dNTPs, biotin-labeled dUTP, and telomerase from cancer cell extracts and the subsequent association of the magnetic beads to the cantilever surface results in the lever deflection by an external magnetic field. M13phi DNA is sensed with a sensitivity limit of 7.1 x 10(-20) M by the magneto-mechanical detection method.     

Biased random walks

How much can an imperfect source of randomness affect an algorithm? We examine several simple questions of this type concerning the long-term behavior of a random walk on a finite graph. In our setup, at each step of the random walk a “controller” can, with a certain small probability, fix the next step, thus introducing a bias. We analyze the extent to which the bias can affect the limit behavior of the walk. The controller is assumed to associate a real, nonnegative, “benefit” with each state, and to strive to maximize the long-term expected benefit. We derive tight bounds on the maximum of this objective function over all controller's strategies, and present polynomial time algorithms for computing the optimal controller strategy.     

Decoherence in an anharmonic oscillator coupled to a thermal environment: a semiclassical forward-backward approach

The decoherence of an anharmonic oscillator in a thermal harmonic bath is examined via a semiclassical approach. A computational strategy is presented and exploited to calculate the time dependence of the purity and the decay of individual matrix elements in the energy representation for a variety of initial states. The time dependence of the decoherence is found to depend on the temperature of the bath, the coupling strength, the initial state of the oscillator, and the choice of quantity measuring the decoherence. Recurrences in the purity and in the off-diagonal matrix elements are observed, as well as the collapse of these matrix elements to the diagonal, providing evidence for the retention of quantum coherence for time scales longer than that indicated by the purity. The results are used to analyze the utility of the Caldeira-Leggett and Redfield models of decoherence and to assess the dependence of dephasing rates on the degree of structure in phase space. In several cases we find that the dephasing dynamics can be described as an initial Zeno-effect regime, followed by a Caldeira-Leggett region, followed by recurrences.     

Structural analysis of electrolyte solutions for rechargeable Mg batteries by stereoscopic means and DFT calculations

We present a rigorous analysis of unique, wide electrochemical window solutions for rechargeable magnesium batteries, based on aromatic ligands containing organometallic complexes. These solutions are comprised of the transmetalation reaction products of Ph(x)MgCl(2-x) and Ph(y)AlCl(3-y) in different proportions, in THF. In principle, these reactions involve the exchange of ligands between the magnesium and the aluminum based compounds, forming ionic species and neutral molecules, such as Mg(2)Cl(3)(+)·6THF, MgCl(2)·4THF, and Ph(y)AlCl(4-y)(-) (y = 0-4). The identification of the equilibrium species in the solutions is carried out by a combination of Raman spectroscopy, multinuclear NMR, and single-crystal XRD analyses. The association of the spectroscopic results with explicit identifiable species is supported by spectral analyses of specially synthesized reference compounds and DFT quantum-mechanical calculations. The correlation between the identified solution equilibrium species and the electrochemical anodic stability window is investigated. This study advances both development of new nonaqueous solution chemistry and possible development of high-energy density rechargeable Mg batteries.     

Effect of fluoroethylene carbonate (FEC) on the performance and surface chemistry of Si-nanowire Li-ion battery anodes

The effect of FEC as a co-solvent on the electrochemical performance and surface chemistry of silicon nanowire (SiNW) anodes was thoroughly investigated. Enhanced electrochemical performance was observed for SiNW anodes in alkyl carbonates electrolyte solutions containing fluoroethylene carbonate (FEC). Reduced irreversible capacity losses accompanied by enhanced and stable reversible capacities over prolonged cycling were achieved with FEC-containing electrolyte solutions. TEM studies provided evidence for the complete and incomplete lithiation of SiNW's in FEC-containing and FEC-free electrolyte solutions, respectively. Scanning electron microscopy (SEM) results proved the formation of much thinner and compact surface films on SiNW's in FEC-containing solutions. However, thicker surface films were identified for SiNW electrodes cycled in FEC-free solutions. SiNW electrodes develop lower impedance in electrolyte solutions containing FEC in contrast to standard (FEC-free) solutions. The surface chemistry of SiNW electrodes cycled in FEC-modified and standard electrolytes were investigated using X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy. The impact of FEC as a co-solvent on the electrochemical behavior of SiNW electrodes is discussed herein in light of the spectroscopic and microscopic studies.     

Electrocatalytic intercalator-induced winding of double-stranded DNA with polyaniline

The intercalation of doxorubicin into double-stranded DNA stimulates the electocatalyzed oxidation of aniline to polyaniline and its winding on the DNA template.     

Redox-active nucleic-acid replica for the amplified bioelectrocatalytic detection of viral DNA

A new concept for the amplified electrochemical detection of the 7229-base viral DNA of M13phi is developed. A thiolated 27-base nucleic acid (1) is assembled on an Au-electrode. Hybridization between the sensing interface and the M13phi DNA is followed by the polymerase-induced replication of the analyte DNA in the presence of dCTP, dGTP, dATP, and ferrocene-tethered-dUTP (2). The generated redox-active replica mediates electron transfer between the enzyme glucose oxidase (GOx) and the electrode and activates the bioelectrocatalyzed oxidation of glucose. The bioelectrocatalyzed oxidation of glucose provides a biocatalytic amplification path for the formation of the redox-active replica. The electrochemical techniques to follow the replication and the bioelectrocatalytic amplification are differential pulse voltammetry and cyclic voltammetry. The electrical responses from the system relate to the bulk concentration of the M13phi DNA, thus enabling the quantitative analysis of the viral gene.