Electrochemical gating enhances nearfield trapping of single metalloprotein junctions

Metalloprotein based junctions are widely used as model systems in the field of molecular bioelectronics to miniaturise electronic circuitry with help of biomolecular device components. To further progress in the field, new approaches are sought to form junctions with longer lifetimes than the current limit of hundreds of milliseconds, ideally approaching timescales sufficient for detailed junction characterization or even relevant for device operation. Here, we present an electrochemically gated plasmon-supported break-junction (EC-PBJ) platform that prolongs the lifetime of single-molecule junctions of Azurin (Azu) under strict electrochemical control and physiological conditions. EC-PBJ efficiently combines nearfield and electrochemical gating effects that stabilise the formed metalloprotein junction while maintaining the native structure of the biomolecule. For moderate far-field power densities of ca. 9.49 mW mu m(-2), the lifetime of individual oxidised Azu junctions is increased by a factor of 40 compared to laser-OFF conditions, which equals a nearfield trapping efficiency increase close to three orders of magnitude compared with reduced Azu junctions at the lowest used power density. We ascribe the lifetime tuning through EC-PBJ to two synergistic parameters: (i) the control of the redox state of trapped Azu that affects its resonant state and polarisability, and (ii) the steering of the localised surface plasmon resonance (LSPR) of the junction nanogap through electrode potential control. At the used laser mid-power range, the Azu redox state and polarisability have a more significant effect on the nearfield trapping efficiency than the LSPR shift. Non-invasively increased junction lifetimes pave the way for the development of improved biomolecular sensing and recognition platforms

Electric fields as actuators in unimolecular contacts

Single-molecule detection is essential for investigating individual molecules and (electro)chemical processes at the molecular level. Often, interrogation of individual molecules is achieved by fixating them in nanogaps to minimise the masking effect of surrounding molecular ensembles common to bulk analysis. Electrical detection methods are reliable options for single-molecule studies as they are label-free and provide a robust real-time readout easy to monitor. Here we review how the electric field generated in the nanogap between two electrodes can be employed to achieve active control over the target molecule beyond simple molecular sensing. First, we describe the use of electric fields to build the interelectrode nanogap, to orient the molecular contact, to steer molecule-electrode interaction, and to promote reactivity of the trapped molecule. Second, we focus on the use of the electric field as a contact stabilising agent, to address the main drawbacks of single-molecule sensing, such as detection rate and timescales

Elevated O-GlcNAc levels activate epigenetically repressed genes and delay mouse ES cell differentiation without affecting naive to primed cell transition

The differentiation of mouse embryonic stem (ES) cells is controlled by the interaction of multiple signaling pathways, typically mediated by post-translational protein modifications. The addition of O-linked N-acetylglucosamine (O-GlcNAc) to serine and threonine residues of nuclear and cytoplasmic proteins is one such modification (O-GlcNAcylation), whose function in ES cells is only now beginning to be elucidated. Here we demonstrate that the specific inhibition of O-GlcNAc hydrolase (Oga) causes increased levels of protein O-GlcNAcylation and impairs differentiation of mouse ES cells both in serum-free monolayer and in embryoid bodies (EBs). Use of reporter cell lines demonstrates that Oga inhibition leads to a reduction in the number of Sox1-expressing neural progenitors generated following induction of neural differentiation, as well as maintained expression of the ES cell marker Oct4 (Pou5f1). In EBs expression of mesodermal and endodermal markers is also delayed. However, the transition of naïve cells to primed pluripotency indicated by Rex1 (Zfp42), Nanog, Esrrb and Dppa3 downregulation and Fgf5 upregulation remains unchanged. Finally, we demonstrate that increased O-GlcNAcylation results in upregulation of genes normally epigenetically silenced in ES cells, supporting the emerging role for this protein modification in the regulation of histone modifications and DNA methylation. Stem Cells 2014

Intermanifold similarities in partial photoionization cross sections of helium

Using the eigenchannel R-matrix method we calculate partial photoionization cross sections from the ground state of the helium atom for incident photon energies up to the N=9 manifold. The wide energy range covered by our calculations permits a thorough investigation of general patterns in the cross sections which were first discussed by Menzel and co-workers [Phys. Rev. A {\bf 54}, 2080 (1996)]. The existence of these patterns can easily be understood in terms of propensity rules for autoionization. As the photon energy is increased the regular patterns are locally interrupted by perturber states until they fade out indicating the progressive break-down of the propensity rules and the underlying approximate quantum numbers. We demonstrate that the destructive influence of isolated perturbers can be compensated with an energy-dependent quantum defect.Comment: 10 pages, 10 figures, replacement with some typos correcte

Robust Bayes-Like Estimation: Rho-Bayes estimation

We consider the problem of estimating the joint distribution $P$ of $n$ independent random variables within the Bayes paradigm from a non-asymptotic point of view. Assuming that $P$ admits some density $s$ with respect to a given reference measure, we consider a density model $\overline S$ for $s$ that we endow with a prior distribution $\pi$ (with support $\overline S$) and we build a robust alternative to the classical Bayes posterior distribution which possesses similar concentration properties around $s$ whenever it belongs to the model $\overline S$. Furthermore, in density estimation, the Hellinger distance between the classical and the robust posterior distributions tends to 0, as the number of observations tends to infinity, under suitable assumptions on the model and the prior, provided that the model $\overline S$ contains the true density $s$. However, unlike what happens with the classical Bayes posterior distribution, we show that the concentration properties of this new posterior distribution are still preserved in the case of a misspecification of the model, that is when $s$ does not belong to $\overline S$ but is close enough to it with respect to the Hellinger distance.Comment: 68 page

Tuning Single-Molecule Conductance by Controlled Electric Field-Induced trans-to-cis Isomerisation

External electric fields (EEFs) have proven to be very efficient in catalysing chemical reactions, even those inaccessible via wet-chemical synthesis. At the single-molecule level, oriented EEFs have been successfully used to promote in situ single-molecule reactions in the absence of chemical catalysts. Here, we elucidate the effect of an EEFs on the structure and conductance of a molecular junction. Employing scanning tunnelling microscopy break junction (STM-BJ) experiments, we form and electrically characterize single-molecule junctions of two tetramethyl carotene isomers. Two discrete conductance signatures show up more prominently at low and high applied voltages which are univocally ascribed to the trans and cis isomers of the carotenoid, respectively. The difference in conductance between both cis-/trans- isomers is in concordance with previous predictions considering pi-quantum interference due to the presence of a single gauche defect in the trans isomer. Electronic structure calculations suggest that the electric field polarizes the molecule and mixes the excited states. The mixed states have a (spectroscopically) allowed transition and, therefore, can both promote the cis-isomerization of the molecule and participate in electron transport. Our work opens new routes for the in situ control of isomerisation reactions in single-molecule contacts

Investigation of Single Boron Acceptors at the Cleaved Si:B (111) Surface

The cleaved and (2 x 1) reconstructed (111) surface of p-type Si is investigated by scanning tunneling microscopy (STM). Single B acceptors are identified due to their characteristic voltage-dependent contrast which is explained by a local energetic shift of the electronic density of states caused by the Coulomb potential of the negatively charged acceptor. In addition, detailed analysis of the STM images shows that apparently one orbital is missing at the B site at sample voltages of 0.4 - 0.6 V, corresponding to the absence of a localized dangling-bond state. Scanning tunneling spectroscopy confirms a strongly altered density of states at the B atom due to the different electronic structure of B compared to Si.Comment: 6 pages, 7 figure

Resonance structure in the Li^- photodetachment cross section

We report on the first observation of resonance structure in the total cross section for the photodetachment of Li^-. The structure arises from the autodetaching decay of doubly excited ^1P states of Li^- that are bound with respect to the 3p state of the Li atom. Calculations have been performed for both Li^- and H^- to assist in the identification of these resonances. The lowest lying resonance is a symmetrically excited intrashell resonance. Higher lying asymmetrically excited intershell states are observed which converge on the Li(3p) limit.Comment: 4 pages, 2 figure, 19 references, RevTeX, figures in ep

Atomic Force Microscopy of height fluctuations of fibroblast cells

We investigated the nanometer scale height fluctuations of 3T3 fibroblast cells with the atomic force microscope (AFM) under physiological conditions. Correlation between these fluctuations and lateral cellular motility can be observed. Fluctuations measured on leading edges appear to be predominantly related to actin polymerization-depolymerization processes. We found fast (5 Hz) pulsatory behavior with 1--2 nm amplitude on a cell with low motility showing emphasized structure of stress fibres. Myosin driven contractions of stress fibres are thought to induce this pulsation.Comment: 6 pages, 5 figures, 1 tabl