Scanning near-field optical coherent spectroscopy of single molecules at 1.4 K

We present scanning near-field extinction spectra of single molecules embedded in a solid matrix. By varying the tip-molecule separation, we modify the line shape of the spectra, demonstrating the coherent nature of the interaction between the incident laser light and the excited state of the molecule. We compare the measured data with the outcome of numerical calculations and find a very good agreement.     

Oxygen-dependent photochemistry of fluorescent dyes studied at the single molecule level

We perform wide-field microscopy to investigate the photobleaching of organic fluorophores embedded in the polymeric host PMMA. Our experimental arrangement facilitates the comparison between the ensemble and single molecule data. We characterize the photostability of dye molecules of various families by measuring the ‘bleaching number’, defined as the average number of photons a molecule emits until photobleaching occurs. In particular, we have analysed the dependence of the bleaching number on the presence of oxygen. Surprisingly, we find an improvement of photostability in the presence of oxygen for ionic dyes (DiI, TMR, Rh6G, Alexa 546), suggesting that oxygen quenches the photoactive triplet state, but it only indirectly contributes to photochemistry. In contrast, we observe that photobleaching of the aromatic hydrocarbon is strongly enhanced by oxygen.     

Molecular dynamics study of biomembrane/local anesthetics interactions

It is still controversial how local anesthetics (LAs) act upon the nervous system and how the membrane contributes to this process, since probably the most important active site of the LAs is located in the sodium channels, a trans-membrane protein. An important role of the bio-membrane would be the stabilization and orientation of local anesthetics molecules, reducing their translational and rotational degrees of freedom, which could reinforce the mechanisms which interrupt the nervous impulse. This study aims to perform a computational analysis of the LAs behaviour in the membrane, and the effect of the water/membrane interface on their stabilization and orientation. Analysis by molecular dynamics (MD) showed that the charged form of these drugs are oriented at the interface, while the neutral form can easily cross the interface, entering the membrane, in agreement with the most recent experimental results in the literature. In contrast, it is here suggested that benzocaine (BZC), which exists only in its uncharged form in physiological media, behaves like the charged anesthetics, remaining stabilized and oriented at the interface. This could explain the similar anesthetic effect of BZC and the charged forms of tetracaine (TTC) and lidocaine (LDC).     

Structural dependency of optical excitation transfer via optical near-field interactions between semiconductor quantum dots

The distribution dependency of quantum dots was theoretically and experimentally investigated with respect to the basic properties optical excitation transfer via optical near-field interactions between quantum dots. The effects of three-dimensional structure and arraying precision of quantum dots on the signal transfer performance were analyzed. In addition, the quantum dot distribution dependency of the signal transfer performance was experimentally evaluated by using stacked CdSe quantum dots and an optical near-field fiber probe tip laminated with quantum dots serving as an output terminal, showing good agreement with theory. These results demonstrate the basic properties of signal transfer via optical near-field interactions and serve as guidelines for a nanostructure design optimized to attain the desired signal transfer performances.     

Dynamic stability and thermodynamic characterization in an enzymatic reaction at the single molecule level

In this work we study, at the single molecular level, the thermodynamic and dynamic characteristics of an enzymatic reaction comprising a rate limiting step. We investigate how the stability of the enzyme-state stationary probability distribution, the reaction velocity, and its efficiency of energy conversion depend on the system parameters. We employ in this study a recently introduced formalism for performing a multiscale thermodynamic analysis in continuous-time discrete-state stochastic systems.     

Investigation of mechanical interactions between the tips of two scanning near-field optical microscopes

We describe a method to monitor the distance between two tips of a scanning near-field optical microscope setup. The interaction between the two tips, caused by shear forces and air pressure oscillations between the tips, makes each oscillating tip perform an additional oscillation at the frequency of the other tip. The interaction is detected by analyzing one of the tuning fork signals with a lock-in amplifier locked at the oscillation frequency of the other tuning fork. The resulting signal, called crosstalk, increases sharply only when the scanning tip comes into the immediate vicinity of the stationary one. This effect allows us to prevent the tips from colliding during scanning.     

Discrimination of photoblinking and photobleaching on the single molecule level

Wide field observation of individual dye molecules have been performed to study fluorescence intermittency. We demonstrate a data analysis scheme, which enables us to quantify the decay of the ensemble intensity which is due to on/off-blinking of the molecules (photophysical bleaching) by getting rid of the effects of photochemical degradation of the dye (photochemical bleaching). Under the conditions of our experiments, photophysical and thus reversible bleaching is the dominant of the two bleaching mechanisms.     

Measuring local optical properties: near-field polarimetry of photonic block copolymer morphology

Ultrahigh molecular weight polystyrene-b-polyisoprene block copolymers (BCs), noted for their photonic behavior, were imaged using transmission near-field scanning optical microscopy (NSOM) and NSOM polarimetry. Our improved scheme for polarization modulation (PM) polarimetry, which accounts for optical anisotropies of the NSOM aperture probe, enables mapping of the local diattenuation and birefringence (with separately aligned diattenuating and fast axes) in these specimens with subdiffraction limited resolution. PM-NSOM micrographs illuminate the mesoscopic optical nature of these BC specimens by resolving individual microphase domains and defect structures.     

High-resolution imaging of single fluorescent molecules with the optical near-field of a metal tip

We show that a concentration of light at a metal tip allows near-field optical imaging of single fluorescent dye molecules at very high resolution, despite strong quenching effects. Details as small as 10 nm were observed in the fluorescence patterns of single Cy-3 dyes bound to the termini of DNA. Data evaluation by model fitting determines the positions of the dyes to an accuracy even better than 1 nm and also yields their 3D orientation. The metal tip simultaneously provides high-resolution topographic imaging complementing the optical signal for a detailed surface examination.     

Tomography of the near-field optical signal

In near-field optics, measurement of vertical variations of the near field is of great interest for characterizing the efficiency of resonances such as surface plasmon polaritons. The use of the signal obtained through the lock-in amplifier using a feedback on the vertical vibration of the probe is shown to enable the reconstruction of the near field without the use of the slower technique of approach curves. Therefore, a tomography of the near field is directly available.     

Exploring the mechanism of flexible biomolecular recognition with single molecule dynamics

Combining a single-molecule study of protein binding with a coarse grained molecular dynamics model including solvent (water molecules) effects, we find that biomolecular recognition is determined by flexibilities in addition to structures. Our single-molecule study shows that binding of CBD (a fragment of Wiskott-Aldrich syndrome protein) to Cdc42 involves bound and loosely bound states, which can be quantitatively explained in our model as a result of binding with large conformational changes. Our model identified certain key residues for binding consistent with mutational experiments. Our study reveals the role of flexibility and a new scenario of dimeric binding between the monomers: first bind and then fold.     

Scanning near-field optical images of ordered polystyrene particle layers in transmission and luminescence excitation modes

Scanning near-field optical images of hexagonally close-packed layers of polystyrene spherical particles with a diameter of 1.0 microm have been investigated. The layers were composed of particles that were doped either totally or partially with an organic fluorescent dye. Observations were made in the transmission and luminescence excitation modes with a scanning near-field optical microscope (SNOM) with a spatial resolution shorter than the wavelength of light. The patterns observed in the SNOM images are significantly dependent on the microstructures of layers, that is, the layers are either single or double layered, and the particles are either totally or partially doped. These results are discussed in terms of specific modes of electromagnetic waves transmitting across and along the layers after the local excitation at the tip end of the scanning microprobe.     

Coherent nonlinear optical response of single quantum dots studied by ultrafast near-field spectroscopy

The nonlinear response of single GaAs quantum dots is studied in femtosecond near-field pump-probe experiments. At negative time delays, transient reflectivity spectra show pronounced oscillatory structure around the quantum dot exciton line, providing the first evidence for a perturbed free induction decay of the excitonic polarization. Phase-disturbing Coulomb interactions between the excitonic polarization and continuum excitations dominate the optical nonlinearity on ultrafast time scales. A theoretical analysis based on the semiconductor Bloch equations accounts for this behavior.     

A single molecule as a probe of optical intensity distribution

Single terrylene molecules embedded in microscopic p-terphenyl crystals are identified with the technique of fluorescence excitation spectroscopy. By use of the architecture of a scanning-probe microscope at T = 1.4 K , a single molecule is scanned through an excitation laser beam while the fluorescence signal is recorded. In this manner we have mapped the intensity distribution in a one-dimensional optical standing wave, demonstrating the potential of a single molecule as a nanometric probe. We discuss future experiments aimed at combining the high spatial and spectral sensitivity of a single molecule.     

Mastering the molecular dynamics of a bistable molecule by single atom manipulation

At low temperature (5 K), a single biphenyl molecule adsorbed on a Si(100) surface behaves as a bistable device which can be reversibly switched by electronic excitation with the scanning tunneling microscope tip. Density functional theory suggests that the biphenyl molecule is adsorbed with one dissociated hydrogen atom bonded to a neighbor surface silicon atom. By desorbing this hydrogen atom with the STM tip, the interaction of the molecule with the surface is modified such that it becomes transformed into a multistable device with four stable states having switching yields increased by almost 2 orders of magnitude.     

Mechanical properties of H2Pc self-assembled monolayers at the single molecule level by noncontact atomic force microscopy

The mechanical properties of molecular self-assembled monolayers (SAMs) play an important role in understanding the interactions between molecules in the self-assembly, the interactions between molecules and substrate, and thus the formation mechanism of SAMs. Using a high-resolution noncontact atomic force microscope (NC-AFM) combined with a scanning tunneling microscope (STM), we have successfully obtained the sub-molecular resolution of a H(2)Pc self-assembled monolayer grown on a Pb(111) surface. A 2 × 2 superstructure was observed in both AFM and STM topographic images. The lateral critical force of removing a H(2)Pcmolecule from its SAM and moving a single H(2)Pc molecule on Pb(111) were measured. An oscillation of the critical force along the edge of the H(2)Pc SAM with a period of two molecular sites was observed, which can be attributed to the 2 × 2 superstructure. The lateral critical force caused by intermolecular interaction was found to be 25 pN on average and is typically two times larger than the molecule-substrate interaction.     

A study of the local dynamics of polymers using single impurity center spectroscopy (Review)

A review of one-and two-photon counting methods in single impurity center spectroscopy is reported, and advantages and drawbacks of these methods are discussed. The jumps of spectral lines, which are manifested as the so-called spectral trajectories, are discussed. Examples of the use of the theory of two-photon correlators and autocorrelation functions for experimental data processing are presented. Data are reported that demonstrate that the local dynamics of approximately 30% of single impurity centers cannot be described within the framework of the standard tunneling system model suggested by P. Anderson et al. to explain the low-temperature anomalies observed in glasses.     

Nonrenormalizability of Einstein-Yang-Mills interactions at the one-loop level

The interactions between the quantized Einstein and quantized Yang-Mills fields are one-loop nonrenormalizable.     

Direct observation of variations of optical properties in single quantum dots by using time-resolved near-field scanning optical microscope

We study the variations of optical properties of self-assembled In_0.5Ga_0.5As single quantum dots (QDs) in the spatial and time domains by combining a near-field scanning optical microscope with an ultrafast pulsed laser. Through the examinations of several tens of QDs, we find that the variations of photoluminescence (PL) intensity strongly depend on the condition of the initial carrier creation. The differences in quantum efficiency and those in the carrier flow rate into QDs cause the large distribution of PL intensity when the carriers are excited in the barrier layers. From the results of time-resolved PL decay measurements, we find that there are two types of QDs exhibiting quite different PL decay profiles.