Single-molecule spectroscopy of uniaxially oriented terrylene in polyethylene.

Single terrylene molecules doped into linear low-density polyethylene can be oriented by tensile deformation of the matrix. In measurements on ensembles at ambient and on single terrylene molecules at cryogenic temperature, strong orientation along the stretching direction was observed by polarization-resolved confocal microscopy. At cryogenic temperatures narrow and spectrally stable zero-phonon lines were found. The low saturation intensity of 0.07 W cm(-2) is consistent with an uniaxial orientation of terrylene in the sample plane.     

Dynamics of vacancy defects in 2-D crystalline monolayers under chiral smectic thin films studied by scanning tunnelling microscopy

Scanning tunnelling microscopy (STM) can be used to image adsorbed organic molecules in real space and real time. The technique seems especially well suited for imaging 2-D crystalline monolayers formed under liquid crystal films. In addition to observing perfect 2-D crystals, STM provides the ability to observe crystal defects, and to observe how these defects evolve over time. In this study two different vacancy defects in 2-D lamellar monolayers of chiral liquid crystal molecules under bulk smectic films were observed in situ. Both vacancies showed dynamic behaviour and an unexpected transport anisotropy.     

Photoblinking and photobleaching of rylene diimide dyes

We investigate photoblinking and photobleaching of perylene diimide (PDI) and its higher homologue terrylene diimide (TDI). Single molecule fluorescence trajectories of the dye molecules embedded in PMMA under ambient conditions exhibit "on"-"off" blinking in the time range from ms to s. Due to the limited statistics of individual trajectories we construct ensemble distributions of "on" and "off" times which follow power laws with similar power law coefficients (m(on) ≈ 1.18, m(off) ≈ 1.31). The blinking is attributed to reversible formation of radical cations which are presumably created by electron transfer from higher excited triplet states T(n) of the molecules to acceptor levels in the PMMA host. This view is corroborated by the properties of TDI, which blinks at an excitation wavelength of 520 nm but does not at lower energy excitation (647 nm). In line with this observation, T(1)-T(n) absorption data of TDI (and PDI) indicate that above a certain illumination wavelength population of higher excited triplet states T(n) does not occur, preventing blinking. It is furthermore argued that the long-lived dark ("off") states, i.e. the radical cations, are precursors for the photobleaching process of the dye molecules. Consequently, the photobleaching quantum yield Y(bl) for TDI is very small at an excitation wavelength of 647 nm (Y(bl) = 2 × 10(-10)) but increases by two orders of magnitude at 520 nm (Y(bl) = 2 × 10(-8)), which lies in the range observed for PDI investigated with an excitation wavelength of 488 nm. Additional studies of a PDI-TDI donor-acceptor dyad give further insights into the blinking and bleaching processes. Important findings include the observation of power law blinking of TDI and PDI (after bleaching of TDI) with similar coefficients as found for the isolated chromophores. Furthermore, in the dyad the photostability of TDI decreases due to efficient population of the states T(n) by singlet-triplet annihilation, while that of PDI (after bleaching of TDI) is the same as for the isolated dye. These findings support the conclusions drawn for the isolated chromophores, in particular the involvement of the triplet manifold in the blinking (and bleaching) behavior.     

Two-dimensional protein crystals on a solid substrate: effect of surface ligand concentration

Proteins imbedded in solid-supported lipid bilayers can serve as model systems for investigations of cellular membranes and protein behavior on surfaces. We have investigated the self-assembly of streptavidin on mica-supported bilayer membranes. Using fluorescence microscopy and atomic force microscopy, our studies reveal that the concentration of surface ligand influences the molecular packing of the resulting protein arrays, which in turn affects overall crystal morphology. Two-dimensional streptavidin crystals are obtained when the biotinylated lipid density on the substrate reaches 1.5% mole fraction, yielding high-aspect morphologies that comprise primarily of crystals with P1 symmetry. At 3% and above, crystals with C222 symmetry are formed and result in H-shaped and confluent structures. In intermediate densities between 2 and 3%, a coexistence of P1 and C222 crystal forms is observed. The relationship between macroscopic morphology and molecular configuration is similar to previously reported data obtained at the air/water interface. This suggests that, under our experimental conditions, protein interactions with the supporting substrate are less significant for defining self-assembly behavior than interactions between protein molecules. Ligand-inhibition and fluorescence recovery after photobleaching were used to elucidate the concentration-dependent mechanism for the divergent crystal forms. We have measured the diffusion coefficient of molecules in P1-forming conditions to be approximately twice that of molecules in C222-forming concentrations, which is consistent with proteins bound to the surface through one and two ligands, respectively. The differential flexibility associated with the binding state is therefore likely to alter the subtle protein interactions involved in crystallization.     

Charge injection and photooxidation of single conjugated polymer molecules

The complex, coupled mechanisms of charge transfer and oxidative damage in organic electronic devices (such as organic light-emitting diodes (OLED), solar cells, etc.) have been elucidated by a new technique that combines single-molecule spectroscopy with charge injection from a metal electrode. The experiments employed a sandwich device architecture (Au/TPD/MEH-PPV:PMMA/SiO2/ITO), essentially a modified OLED with a charge-blocking layer (SiO2) to suppress charge injection at the ITO electrode. The fluorescence (photoluminescence) of isolated MEH-PPV conjugated polymer molecules imbedded in the device was observed to exhibit diverse time- and electrical bias-dependent effects. These include: (i) fluorescence quenching due to interactions between MEH-PPV and holes in the TPD hole-transport layer; (ii) fluorescence quenching, or "photobleaching", due to chemical defects at MEH-PPV generated by photooxidation; and (iii) a novel process, reductive "repair" of the oxidative chemical defects by externally injected carriers. These results demonstrate a very different mechanism for photobleaching of organic conjugated materials than is generally assumed to operate and, furthermore, suggest an intimate relationship among photobleaching, charge transport, and persistent photoconductivity in organic materials.     

3D Electron Diffraction Structure Determination of Terrylene,a Promising Candidate for Intermolecular Singlet Fission

Herein we demonstrate the prowess of the 3D electron diffraction approach by unveiling the structure of terrylene, the third member in the series of peri-condensed naphthalene analogues, which has eluded structure determination for 65 years. The structure was determined by direct methods using electron diffraction data and corroborated by dispersion-inclusive density functional theory optimizations. Terrylene crystalizes in the monoclinic space group P2₁/a, arranging in a sandwich-herringbone packing motif, similar to analogous compounds. Having solved the crystal structure, we use many-body perturbation theory to evaluate the excited-state properties of terrylene in the solid-state. We find that terrylene is a promising candidate for intermolecular singlet fission, comparable to tetracene and rubrene.     

血浆溶液中竹红菌乙素和2-牛磺酸修饰的竹红菌乙素的光漂白

光动力学疗法是应用光敏剂受激光激发后对靶体产生光化学作用来治疗病变。光漂白是光动力学治疗过程中普遍现象，在光动力疗法治疗血管类疾病中，光敏剂与血浆中的生物分子相互作用及其在血管中的光漂白行为直接关系到治疗效果。本文考察了HB和THB与血浆的作用和在血浆溶液中的光漂白过程，研究表明在富氧条件下，以单重态氧漂白为主；在有血浆生物分子溶液中光产物与水溶液中的光产物不同。研究表明光敏剂的结构和氧化电位导致了它们不同的光漂白机制，HB和THB与生物分子的相互作用加速了它们光漂白并影响了光产物。     

Microscopic description of elementary growth processes and classification of structural defects in pentacene thin films

Elementary growth processes such as kink initiation, adding a molecule to a kink, and adding a molecule between two neighboring kinks and between two grains are theoretically studied in pentacene films by adding one molecule at a time to a predefined aggregate. For each molecule, the potential energy surface is calculated using the MM3 molecular mechanics force field, which allowed one to identify useful parameters like the energy barrier for diffusion and the energy to create kinks, as well as defect configurations. Depending on the properties of the potential energy surface and the resulting growth-condition-dependent probabilities of initiating defect configurations in the film, three types of pentacene defects are identified: a thermally activated defect, an intrinsic defect, and a kinetic defect. Upon film growth, most defects relax into the ideal crystal configuration. Bulk defects that resist relaxation have densities lower than 10(16) defects/cm3 at typical growth conditions. Grain boundary defects, on the other hand, are very stable. Moreover, interstitial molecules at grain boundaries are identified as a source of compressive stress.     

Many-photon dynamics of photobleaching

A detailed dynamical theory of photobleaching by periodical sequences of laser pulses is presented. The theory is used for interpretation of recent experiments with pyrylium salts. Our simulations are based on first-principles simulations of photoabsorption cross-sections and on empirical rate constants. Two competitive channels of photobleaching, namely, photobleaching from the lowest excited singlet and triplet states and from higher excited states, are found to explain different intensity dependences of the photobleaching rates in different samples. The process includes two-photon excitation from the ground state to the first or second excited singlet states and one-photon excitation from the first singlet or triplet states to higher excited states. The fluorescence follows double-exponential dynamics with two characteristic times. The first and the shorter one is the equilibrium settling time between the ground and the lowest triplet states. The second characteristic time, the time of photobleaching, is responsible for the long-term dynamics. The effective rate of photobleaching from the first excited singlet and lowest triplet states depends differently on the irradiance in comparison with the photobleaching in higher states. The first channel is characterized by a quadratic intensity dependence in contrast to the second channel that shows a cubic dependence. The competition between these photobleaching channels is very sensitive to the rate constants as well as to the repetition rate, the pulse duration, and the peak intensity. The double-exponential decay of the fluorescence is explained by the spatial inhomogeneity of the light beam. The findings in this work are discussed in terms of the possibility of using many-photon-induced photobleaching for new three-dimensional read-write devices.     

Single molecule study of perylene orange photobleaching in thin sol-gel films

The paper reports on photobleaching mechanisms of perylene orange embedded in thin sol-gel films, derived from single molecule studies. The experimental configuration uses wide-field illumination and one photon excitation of the molecules. Measurements have been performed both at ambient conditions and under vacuum in order to get information on the influence of oxygen on photobleaching in such porous samples. We have also recorded the evolution of photobleaching with respect to the excitation intensity. The results demonstrate that photobleaching from excited states higher than the first singlet and triplet states has a nonnegligible contribution as soon as the excitation energy exceeds a few hundred W/cm2 and that this process is favored in the presence of air. The study also demonstrates that perylene orange in sol-gel films is not a very efficient emitter but that photobleaching can be slow, which explains the interest for perylene orange as a good candidate to produce long lifetime solid-state lasers when embedded in monoliths of sol-gel.     

Terrylene in hexadecane revisited: a hole burning study

Holes burnt into the absorption spectrum of terrylene in hexadecane have quite unusual features: spectral diffusion behavior under thermal cycles shows a narrowing regime at very low temperatures (2-5 K) followed by a plateau region (up to about 13 K) and a broadening regime (T>13 K). Thermal line broadening (quasihomogeneous linewidth) shows a nonmonotonous behavior as a function of temperature: at around 4 K there is a maximum followed by a flat minimum and the onset of strong broadening at higher temperatures. Finally, the central hole shows one-sided narrowly spaced side features. This behavior is interpreted within the frame of a two-site model. One of the two sites can be well described by a standard two level system; the other, however, shows characteristic features of a multilevel system. The two sites are characterized by strongly different optical linewidths, phototransformation yields, and thermal stabilities.     

The mobility of water molecules through gas hydrates

Crystal growth simulations of gas hydrates have suggested that hydrate cages may occasionally be occupied by H(2)O rather than guest molecules, leaving interstitial defects within the hydrate crystal. Further inspection of the behavior of these interstitial H(2)O molecules has revealed that they are relatively highly mobile entities within a gas hydrate. In this paper, we report these observations and examine the molecular mechanisms responsible for the transport of these interstitial molecules through hydrate crystals. Four distinct pathways for the H(2)O molecule transport between cages are found, each facilitated by the presence of empty cages. The relative richness of the observed behavior of interstitial defects suggests that interstitial diffusion could be an important mechanism for the mass transport of H(2)O molecules through gas hydrates.     

Oriented Two‐Dimensional Porous Organic Cage Crystals

The formation of two‐dimensional (2D) oriented porous organic cage crystals (consisting of imine‐based tetrahedral molecules) on various substrates (such as silicon wafers and glass) by solution‐processing is reported. Insight into the crystallinity, preferred orientation, and cage crystal growth was obtained by experimental and computational techniques. For the first time, structural defects in porous molecular materials were observed directly and the defect concentration could be correlated with crystal growth rate. These oriented crystals suggest potential for future applications, such as solution‐processable molecular crystalline 2D membranes for molecular separations.     

Photobleaching in Two‐Photon Scanning Fluorescence Correlation Spectroscopy

Two‐photon excitation in fluorescence correlation spectroscopy (FCS) is often preferred to one‐photon excitation because of reduced bulk photobleaching and photodamage, and deeper penetration into scattering media, such as thick biological specimens. Two‐photon FCS, however, suffers from lower signal‐to‐noise ratios which are directly related to the lower molecular brightness achieved. We compare standard FCS with a fixed measurement volume with scanning FCS, where the measurement volume is scanned along a circular path. The experimental results show that photobleaching is the dominant cause of the effects observed at the high excitation powers necessary for good signal‐to‐noise ratios. Theoretical calculations assuming a nonuniform excitation intensity profile, and using the concept of generalized volume contrast, provide an explanation for the photobleaching effects commonly observed in two‐photon FCS at high excitation intensities, without having to assume optical saturation. Scanning alleviates these effects by spreading the photobleaching dose over a larger area, thereby reducing the depletion of fluorescent molecules in the measurement volume. These results, which facilitate understanding of the photobleaching in FCS and of the positive effects of scanning, are particularly important in studies involving the autocorrelation amplitude g(0), such as concentration measurements or binding studies using fluorescence cross‐correlation between two labeled species.     

Photobleaching of reduced nicotinamide adenine dinucleotide and the development of highly fluorescent lesions in rat basophilic leukemia cells during multiphoton microscopy

Endogenous reduced nicotinamide adenine dinucleotide (NADH) fluorescence provides an intrinsic indicator of the cellular metabolic state, but prolonged monitoring is limited by photobleaching and/or phototoxicity. Multiphoton excitation of NADH by ultrashort, 740-nm laser pulses provides a significant improvement over UV excitation by eliminating peripheral photobleaching; however, molecules within the subfemtoliter excitation volume remain susceptible. We have investigated the photophysical mechanisms responsible for multiphoton photobleaching of NADH in living cells to permit the imaging technique to be optimized. The loss of fluorescence because of multiphoton photobleaching was measured by repetitively imaging individual planes within rat basophilic leukemia cells. The photobleaching rate was proportional to the fourth power of the laser intensity. Based on these measurements, we propose a double-biphotonic, four-photon photobleaching mechanism and estimate the quantum yield of photobleaching of intracellular NADH to be 0.0073 +/- 0.0002 by this mechanism. In addition to photobleaching, the development of bright, punctate fluorescent lesions can also be observed. The frequency of lesion formation also increased approximately as the fourth power of the laser intensity after an intensity-dependent threshold number of images had been exceeded. The consequences for two-photon metabolic imaging are discussed.     

High-resolution spectroscopy and the analysis of ro-vibrational transitions of molecules in solid parahydrogen

Solid parahydrogen provides a novel matrix for isolation spectroscopy of atoms and molecules. Ro-vibrational motion of molecules embedded in solid parahydrogen is well quantized on account of the weak interactions in the crystal and of the softness of the crystal being characteristic of quantum crystals. Most of the observed spectral linewidths are one or two orders of magnitude sharper than those observed in conventional rare gas matrices. The sharp linewidths make the parahydrogen crystal an excellent matrix for the study of ro-vibrational states and dynamics of dopant molecules in the condensed phase by high-resolution spectroscopy. In this article, we have summarized the most fundamental part of our study, that is, the theory of ro-vibrational states of dopant molecules in the crystal, which is necessary for the quantitative analysis of high-resolution infrared spectra. We also discuss what we have learned from the analysis of high-resolution infrared spectra in solid parahydrogen. These include perturbations to rotational motion of dopant molecules, reduction of rotational constants, vibrational dephasing and relaxation. Outstanding questions to be solved are also discussed herein.     

The impact of vertical π-extension on redox mechanisms of aromatic diimide dyes

The impact of vertical π-extension on redox mechanisms of aromatic diimides in the organic lithium-ion batteries have been carefully studied by a combined experiment and theoretical analyses.     

In situ observation of the four-step dehydration process of the 1 beta-methylcarbapenem antibiotic CS-834 crystal by X-rays

The 1 beta-methylcarbapenem antibiotic CS-834 takes six crystalline forms depending on ambient conditions. The X-ray powder diffraction revealed that the dihydrate crystal (B2-form) was changed to the monohydrate (B1-form) through the intermediate form (B2'-form). The monohydrate form was then changed to the dehydrate (B0-form) through the intermediate B1'-form. The progress of the dehydration along the needle axis (c-axis) was observed under a microscope. When a single crystal of the B2-form was mounted on a diffractometer and the humidity was reduced, the crystal was gradually changed to the various dehydration forms with retention of the single crystal. The crystals of B2- to B0-forms form isostructures to each other except the solvent water molecules. In the crystal structure of the B1-form, the pivaloyloxymethyl moiety is disordered. One is nearly similar to that of the B2-form, while another is similar to that of the B0-form. Each crystal structure consists of a columnar arrangement of CS-834 along the c-axis, and the water molecules are located between the columns and form a characteristic hydrogen bond network. When the water molecules leave the crystal, the columns slide slightly following the slight conformational change in the pivaloyloxymethyl groups and are connected by another type of hydrogen bond network. Such a rearrangement of the hydrogen bond network should be a motive force of the phase change to the next step due to the dehydration. Since the hydrogen bond network extends along the c-axis, the dehydration proceeds along the c-axis as observed microscopically.     

Probing the crossover in CO desorption from single crystal to nanoparticulate Ru model catalysts

Using model catalysts, we demonstrate that CO desorption from Ru surfaces can be switched from that typical of single crystal surfaces to one more characteristic of supported nanoparticles. First, the CO desorption behaviour from Ru nanoparticles supported on highly oriented pyrolytic graphite was studied. Both mass-selected and thermally evaporated nanoparticles were deposited. TPD spectra from the mass-selected nanoparticles exhibit a desorption peak located around 410 K with a broad shoulder extending from around 480 K to 600 K, while spectra obtained from thermally evaporated nanoparticles exhibit a single broad feature from ～350 K to ～450 K. A room temperature deposited 50 ? thick Ru film displays a characteristic nanoparticle-like spectrum with a broad desorption feature at ～420 K and a shoulder extending from ～450 K to ～600 K. Subsequent annealing of this film at 900 K produced a polycrystalline morphology of flat Ru(001) terraces separated by monatomic steps. The CO desorption spectrum from this surface resembles that obtained on single crystal Ru(001) with two large desorption features located at 390 K and 450 K due to molecular desorption from terrace sites, and a much smaller peak at ～530 K due to desorption of dissociatively adsorbed CO at step sites. In a second experiment, ion sputtering was used to create surface defects on a Ru(0 1 54) single crystal surface. A gradual shift away from the desorption spectrum typical of a Ru(001) surface towards one resembling desorption from supported Ru nanoparticles was observed with increasing sputter time.