We drive reversible photoinduced switching of single azobenzene-functionalized molecules isolated in tailored alkanethiolate monolayer matrices on Au{111}. We designed molecular tethers to suppress excited-state quenching from the metal substrate and formed rigid assemblies of single tethered azobenezene molecules in the domains of monolayer to limit steric constraints and tip-induced and stochastic switching effects. Single molecules were reversibly photoisomerized between trans and cis conformations by cycling exposure to visible and UV light. Trans and cis conformations were imaged as high (2.1 +/- 0.3 A) and low (0.7 +/- 0.2 A) protrusions in STM images and were assigned to the on and off states of the molecule, respectively.

A microcantilever, coated with a monolayer of redox-controllable, bistable [3]rotaxane molecules (artificial molecular muscles), undergoes reversible deflections when subjected to alternating oxidizing and reducing electrochemical potentials. The microcantilever devices were prepared by precoating one surface with a gold film and allowing the palindromic [3]rotaxane molecules to adsorb selectively onto one side of the microcantilevers, utilizing thiol-gold chemistry. An electrochemical cell was employed in the experiments, and deflections were monitored both as a function of (i) the scan rate (< or =20 mV s(-1)) and (ii) the time for potential step experiments at oxidizing (>+0.4 V) and reducing (<+0.2 V) potentials. The different directions and magnitudes of the deflections for the microcantilevers, which were coated with artificial molecular muscles, were compared with (i) data from nominally bare microcantilevers precoated with gold and (ii) those coated with two types of control compounds, namely, dumbbell molecules to simulate the redox activity of the palindromic bistable [3]rotaxane molecules and inactive 1-dodecanethiol molecules. The comparisons demonstrate that the artificial molecular muscles are responsible for the deflections, which can be repeated over many cycles. The microcantilevers deflect in one direction following oxidation and in the opposite direction upon reduction. The approximately 550 nm deflections were calculated to be commensurate with forces per molecule of approximately 650 pN. The thermal relaxation that characterizes the device's deflection is consistent with the double bistability associated with the palindromic [3]rotaxane and reflects a metastable contracted state. The use of the cooperative forces generated by these self-assembled, nanometer-scale artificial molecular muscles that are electrically wired to an external power supply constitutes a seminal step toward molecular-machine-based nanoelectromechanical systems (NEMS).

The self-assembly of 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine (TPyP) on Au(111) electrodes was investigated. The adlayer structure was found to depend on the electrode potential. At positive potentials (>0.5V(SCE)), a disordered layer of TPyP is formed on the Au(111) electrode. STM images showed that the disordered molecules are immobile. At negative potentials (-0.2V(SCE)), however, the molecules are highly mobile and can no longer be imaged by STM, though they remain on the surface. At intermediate potentials (-0.2 to +0.2V(SCE)), the TPyP formed a highly ordered adlayer. Once the ordered adlayer is formed, it persists even after the potential is stepped to higher values (0.5-0.8 V(SCE)). These results can be explained by the role of potential modulated adsorbate-substrate interaction and surface mobility. This suggests the intriguing prospect of using electrode potential to tune surface interactions and to drive surface processes, e.g., molecular self-assembly, in electrochemical systems.

The nanoscale arrangement of the DNA probe molecules on sensor surfaces has a profound impact on molecular recognition and signaling reactions on DNA biosensors and microarrays. Using electrochemical atomic force microscopy, we have directly determined the nanoscale spatial distribution of thiolated DNA that are attached to gold via different methods. We discovered significant heterogeneity in the probe density and limited stability for DNA monolayers prepared by the backfilling method, that is, first exposing the surface to thiolated DNA then "backfilling" with a passivating alkanethiol. On the other hand, the monolayers prepared by "inserting" thiolated DNA into a preformed alkanethiol monolayer lead to a more uniformly distributed layer of DNA. With high-resolution images of single DNA molecules on the surface, we have introduced spatial statistics to characterize the nanoscale arrangement of DNA probes. The randomness of the spatial distribution has been characterized. By determining the local densities surrounding individual molecules, we observed subpopulations of probes with dramatically different levels of "probe crowding". We anticipate that the novel application of spatial statistics to DNA monolayers can enable a framework to understand heterogeneity in probe spatial distributions, interprobe interactions, and ultimately probe activity on sensor surfaces.

Background: Left bundle branch pacing (LBBP) has been suggested as an alternative means to deliver cardiac resynchronization therapy (CRT). Hypothesis: LBBP may deliver resynchronization therapy along with an advantage over traditional biventricular (BiV) pacing in clinical outcomes. Methods: Heart failure patients who presented LBBB morphology according to Strauss's criteria and received successful CRT procedure were enrolled in the present study. Propensity score matching was applied to match patients into LBBP-CRT group and BiV-CRT group. Then, the electrographic data, the echocardiographic data and New York heart association (NYHA) class were compared between the groups. Results: Twenty-one patients with successful LBBP procedure and another 21 matched patients with successful BiV-CRT procedure were finally enrolled in the study. The QRS duration (QRSd) was narrowed from 167.7 ± 14.9 ms to 111.7 ± 12.3 ms (P < .0001) in the LBBP-CRT group and from 163.6 ± 13.8 ms to 130.1 ± 14.0 ms (P < .0001) in the BiV-CRT group. A trend toward better left ventricular ejection fraction (LVEF) was recorded in the LBBP-CRT group (50.9 ± 10.7% vs 44.4 ± 13.3%, P = .12) compared to that in the BiV-CRT group at the 6-month follow-up. A trend toward better echocardiographic response was documented in patients receiving LBBP-CRT procedure (90.5% vs 80.9%, P = .43) and more super CRT response was documented in the LBBP-CRT group (80.9% vs 57.1%, P = .09) compared to that in the BiV-CRT group. Conclusions: LBBP-CRT can dramatically improve the electrical synchrony in heart failure patients with LBBB. Meanwhile, compared with the traditional BiV-CRT, it has Jincun Guo and Linlin Li contributed equally to this work.

We have directly observed electrochemically driven single-molecule station changes within bistable rotaxane molecules anchored laterally on gold surfaces. These observations were achieved by employing molecular designs that significantly reduced the mobility and enhanced the assembly of molecules in orientations conducive to direct measurement using scanning tunneling microscopy. The results reveal molecular-level details of the station changes of surface-bound bistable rotaxane molecules, correlated with their different redox states. The mechanical motions within these mechanically interlocked molecules are influenced by their interactions with the surface and with neighboring molecules, as well as by the conformations of the dumbbell component.

Surfaces that can actively regulate binding affinities or catalytic properties in response to external stimuli are a powerful means to probe and control the dynamic interactions between the cell and its microenvironment. Active surfaces also enable novel functionalities in biosensors and biomolecular separation technologies. Although electrical stimuli are often appealing due to their speed and localization, the operation of these electrically activated surfaces has mostly been characterized with techniques averaging over many molecules. Without a molecular-scale understanding of how biomolecules respond to electric fields, achieving the ultimate detection sensitivity or localized biological perturbation with the ultimate resolution would be difficult. Using electrochemical atomic force microscopy, we are able to follow the conformational changes of individual, short DNA molecules tethered to a gold electrode in response to an applied potential. Our study reveals conformations and dynamics that are difficult to infer from ensemble measurements: defects in the self-assembled monolayer (SAM) significantly perturb conformations and adsorption/desorption kinetics of surface-tethered DNA; on the other hand, the SAM may be actively molded by the DNA at different potentials. These results underscore the importance of characterizing the systems at the relevant length scale in the development of electrically switchable biofunctional surfaces.

We have combined contact angle measurements, Fourier transform infrared spectroscopy (FT-IR), and atomic force microscopy (AFM) to investigate the UV photoreactivity of octadecylsiloxane (ODS) SAMs (self-assembled monolayers) in air. Contact angle measurements present evidence that ozone is not the active agent in alkylsiloxane SAM degradation under UV illumination in air. A combination of UV and oxygen is necessary for monolayer degradation to proceed. AFM measurements on submonolayer coverage SAMs provide direct evidence of the photodegradation of ODS SAMs and reveal the role of defects in the degradation process. FT-IR and AFM results suggest that the hydrocarbon chain is the reactive site of the monolayers. A microscopic mechanism of the photoreactivity involving hydrogen abstraction is suggested based on the mechanism of gas-phase oxidation of alkanes. Our results have implications in clarifying the contribution from the reactivity of alkyl chains during the photomodification of SAMs. This clarification may provide insight into optimization of the SAM photopatterning processes.