Two-dimensional supramolecular polymers: controlled formation and visualization on the surface

Self – assembly is a powerful tool for the construction of highly organized nanostructures. Therefore, the possibility to control and predict pathways of molecular ordering on the nanoscale level is a critical issue for the production of materials with tunable and adaptive macroscopic properties. 2D polymers are attractive objects for the field of material sciences due to their exceptional properties. [1] As shown before, amphiphilic oligopyrenotides (produced via automated solid-phase synthesis) form rod–like supramolecular polymers in water. [2] These assemblies form 1D objects. [3] By applying certain changes to the design of the oligopyrenotide units the dimensionality of the formed assemblies can be influenced. Herein, we demonstrate that Py3 (see Figure 1) forms defined supramolecular assemblies under thermodynamic conditions in water. To study Py3 self-assembly, we carried out whole set of spectroscopic (UV/vis, fluorescence, DLS) and microscopic experiments (AFM). The obtained results suggest that oligopyrenotides with the present type of geometry and linker length leads to formation of 2D supramolecular assemblies.

Two-dimensional supramolecular polymers

One of the biggest issues of modern materials science is developing of strategies to create large and ordered assemblies in the form of discrete nanoscale objects. Oligopyrenotides (OPs) represent novel class of amphiphilic molecules which tend to self-assemble forming highly ordered structures. As has been already shown OPs are able to form 1D («rod-like») supramolecular polymer [1]. Since programmed arraying of polyaromatic hydrocarbons in structurally defined objects could offer enhanced performance over the individual components, prediction and controlling of their spatial arrangement remains challenging. Herein we demonstrate that certain changes to design of pyrene’s molecular core allow Py3 form 2D supramolecular assemblies («nanosheets») instead of 1D. Two dimensional supramolecular polymers are attractive objects due to their exceptional properties which originate from in-plan alignment of molecular units in the sheets with constant thickness ~ 2 nm [2]. These assemblies have high degree of internal order: the interior consists of hydrophobic pyrenes and alkyl chains, whereas the exterior exists as a net of hydrophilic, negatively charged phosphates. The Py3 units are hold up by non-covalent interactions what makes these assemblies totally reversible. Moreover the polymerization occurs via nucleation-elongation mechanism. To study Py3 self-assembly, we carried out whole set of spectroscopic (UV/vis, fluorescence, DLS) and microscopic experiments (AFM)

Two-dimensional supramolecular polymers

One of the biggest issues of modern materials science is developing of strategies to create large and ordered assemblies in the form of discrete nanoscale objects. Oligopyrenotides (OPs) represent novel class of amphiphilic molecules which tend to self-assemble forming highly ordered structures. As has been already shown OPs are able to form 1D («rod-like») supramolecular polymer [1]. Since programmed arraying of polyaromatic hydrocarbons in structurally defined objects could offer enhanced performance over the individual components, prediction and controlling of their spatial arrangement remains challenging. Herein we demonstrate that certain changes to design of pyrene’s molecular core allow Py3 form 2D supramolecular assemblies («nanosheets») instead of 1D. Two dimensional supramolecular polymers are attractive objects due to their exceptional properties which originate from in-plan alignment of molecular units in the sheets with constant thickness ~ 2 nm [2]. These assemblies have high degree of internal order: the interior consists of hydrophobic pyrenes and alkyl chains, whereas the exterior exists as a net of hydrophilic, negatively charged phosphates. The Py3 units are hold up by non-covalent interactions what makes these assemblies totally reversible. Moreover the polymerization occurs via nucleation-elongation mechanism. To study Py3 self-assembly, we carried out whole set of spectroscopic (UV/vis, fluorescence, DLS) and microscopic experiments (AFM)

Two-dimensional and three-dimensional oxygen mapping by 3He-MRI validation in a lung phantom

The aim of this study was to validate oxygen-sensitive 3He-MRI in noninvasive determination of the regional, two- and three-dimensional distribution of oxygen partial pressure. In a gas-filled elastic silicon ventilation bag used as a lung phantom, oxygen sensitive two- and three-dimensional 3He-MRI measurements were performed at different oxygen concentrations which had been equilibrated in a range of normal and pathologic values. The oxygen partial pressure distribution was determined from 3He-MRI using newly developed software allowing for mapping of oxygen partial pressure. The reference bulk oxygen partial pressure inside the phantom was measured by conventional respiratory gas analysis. In two-dimensional measurements, image-based and gas-analysis results correlated with r=0.98; in three-dimensional measurements the between-methods correlation coefficient was r=0.89. The signal-to-noise ratio of three-dimensional measurements was about half of that of two-dimensional measurements and became critical (below 3) in some data sets. Oxygen-sensitive 3He-MRI allows for noninvasive determination of the two- and three-dimensional distribution of oxygen partial pressure in gas-filled airspaces.

Quantification of Mitral Regurgitation with Multiple Jets: In Vitro Comparison of Two-dimensional PISA techniques

Purpose: Traditionally, the proximal isovelocity surface area (PISA) is based on the assumption of a single hemisphere (hemispheric PISA), but this technique has not been validated for the quantification of mitral regurgitation (MR) with multiple jets. Methods: The left heart simulator was actuated by a pulsatile pump at various stroke amplitudes. The regurgitant volume (Rvol) passing through the mitral valve phantoms with single and double regurgitant orifices of varying size and interspace was quantified by a flowmeter as reference technique. Color Doppler 3-D full-volumes were obtained, and Rvol were derived from 2-D PISA surfaces on the basis of hemispheric and hemicylindric assumption with one base (partial hemicylindric PISA) or 2 bases (total hemicylindric PISA). Results: 72 regurgitant volumes (Rvol range: 8 to 76 ml/beat) were obtained. Hemispheric PISA Rvol correlated well with reference Rvol by one orifice (R²=0.97; bias -2.7±3.2ml), but less by ≥ one orifice (R²=0.89). When a fusion of two PISAs occured, addition of two hemispheric PISA overestimated Rvol (bias 9.1±12.2ml, fig.1), and single hemispheric PISA underestimated Rvol (bias -12.4±4.9ml). If an integrated approach was used (hemispheric in single orifice, total hemicylindric in two non-fused PISAs and partial hemicylindric in two fused PISAs), the correlation was R²=0.95, bias -1.6±5.6ml (fig.2). In the ROC analysis, the cutoff to detect ≥ moderate-to-severe Rvol (≥45ml) was 42ml (AUC 0.99, sens. 100%, spec. 93%). Conclusions: In MR with two regurgitant jets, the 2-D hemicylindric assumption of the PISA offers a better quantification of Rvol than the hemispheric assumption. Quantification of MR using 2-D PISA requires an integrated approach that considers number of regurgitant orifices and fusion of the PISAs.

Comparison of dynamic effects of high-speed traffic load on ballasted track using a simplified two-dimensional and full three-dimensional model.

The vertical dynamic actions transmitted by railway vehicles to the ballasted track infrastructure is evaluated taking into account models with different degree of detail. In particular, we have studied this matter from a two-dimensional (2D) finite element model to a fully coupled three-dimensional (3D) multi-body finite element model. The vehicle and track are coupled via a non-linear Hertz contact mechanism. The method of Lagrange multipliers is used for the contact constraint enforcement between wheel and rail. Distributed elevation irregularities are generated based on power spectral density (PSD) distributions which are taken into account for the interaction. The numerical simulations are performed in the time domain, using a direct integration method for solving the transient problem due to the contact nonlinearities. The results obtained include contact forces, forces transmitted to the infrastructure (sleeper) by railpads and envelopes of relevant results for several track irregularities and speed ranges. The main contribution of this work is to identify and discuss coincidences and differences between discrete 2D models and continuum 3D models, as wheel as assessing the validity of evaluating the dynamic loading on the track with simplified 2D models

Two-dimensional direct rainfall hydraulic models applied to direct calculation of hydrologic events in dams to prevent overtopping

One of the main concerns when conducting a dam test is the acute determination of the hydrograph for a specific flood event. The use of 2D direct rainfall hydraulic mathematical models on a finite elements mesh, combined with the efficiency of vector calculus that provides CUDA (Compute Unified Device Architecture) technology, enables nowadays the simulation of complex hydrological models without the need for terrain subbasin and transit splitting (as in HEC-HMS). Both the Spanish PNOA (National Plan of Aereal Orthophotography) Digital Terrain Model GRID with a 5 x 5 m accuracy and the CORINE GIS Land Cover (Coordination of INformation of the Environment) that allows assessment of the ground roughness, provide enough data to easily build these kind of models

Dynamics of fluorescence fluctuations in green fluorescent protein observed by fluorescence correlation spectroscopy

We have investigated the pH dependence of the dynamics of conformational fluctuations of green fluorescent protein mutants EGFP (F64L/S65T) and GFP-S65T in small ensembles of molecules in solution by using fluorescence correlation spectroscopy (FCS). FCS utilizes time-resolved measurements of fluctuations in the molecular fluorescence emission for determination of the intrinsic dynamics and thermodynamics of all processes that affect the fluorescence. Fluorescence excitation of a bulk solution of EGFP decreases to zero at low pH (pKa = 5.8) paralleled by a decrease of the absorption at 488 nm and an increase at 400 nm. Protonation of the hydroxyl group of Tyr-66, which is part of the chromophore, induces these changes. When FCS is used the fluctuations in the protonation state of the chromophore are time resolved. The autocorrelation function of fluorescence emission shows contributions from two chemical relaxation processes as well as diffusional concentration fluctuations. The time constant of the fast, pH-dependent chemical process decreases with pH from 300 μs at pH 7 to 45 μs at pH 5, while the time-average fraction of molecules in a nonfluorescent state increases to 80% in the same range. A second, pH-independent, process with a time constant of 340 μs and an associated fraction of 13% nonfluorescent molecules is observed between pH 8 and 11, possibly representing an internal proton transfer process and associated conformational rearrangements. The FCS data provide direct measures of the dynamics and the equilibrium properties of the protonation processes. Thus FCS is a convenient, intrinsically calibrated method for pH measurements in subfemtoliter volumes with nanomolar concentrations of EGFP.

Fluorescence correlation spectroscopy reveals fast optical excitation-driven intramolecular dynamics of yellow fluorescent proteins

Fast excitation-driven fluctuations in the fluorescence emission of yellow-shifted green fluorescent protein mutants T203Y and T203F, with S65G/S72A, are discovered in the 10−6–10−3-s time range, by using fluorescence correlation spectroscopy at 10−8 M. This intensity-dependent flickering is conspicuous at high pH, with rate constants independent of pH and viscosity with a minor temperature effect. The mean flicker rate increases linearly with excitation intensity for at least three decades, but the mean dark fraction of the molecules undergoing these dynamics is independent of illumination intensity over ≈6 × 102 to 5 × 106 W/cm2. These results suggest that optical excitation establishes an equilibration between two molecular states of different spectroscopic properties that are coupled only via the excited state as a gateway. This reversible excitation-driven transition has a quantum efficiency of ≈10−3. Dynamics of external protonation, reversibly quenching the fluorescence, are also observed at low pH in the 10- to 100-μs time range. The independence of these two bright–dark flicker processes implies the existence of at least two separate dark states of these green fluorescent protein mutants. Time-resolved fluorescence measurements reveal a single exponential decay of the excited state population with 3.8-ns lifetime, after 500-nm excitation, that is pH independent. Our fluorescence correlation spectroscopy results are discussed in terms of recent theoretical studies that invoke isomerization of the chromophore as a nonradiative channel of the excited state relaxation.

Coherent electron dynamics in a two-dimensional random system with mobility edges

We study numerically the dynamics of a one-electron wavepacket in a two-dimensional random lattice with long-range correlated diagonal disorder in the presence of a uniform electric field. The time-dependent Schrodinger equation is used for this purpose. We find that the wavepacket displays Bloch-like oscillations associated with the appearance of a phase of delocalized states in the strong correlation regime. The amplitude of oscillations directly reflects the bandwidth of the phase and allows us to measure it. The oscillations reveal two main frequencies whose values are determined by the structure of the underlying potential in the vicinity of the wavepacket maximum.

Spin splitting in a polarized quasi-two-dimensional exciton gas

We have observed a large spin splitting between "spin" +1 and -1 heavy-hole excitons, having unbalanced populations, in undoped GaAs/AlAs quantum wells in the absence of any external magnetic field. Time-resolved photoluminescence spectroscopy, under excitation with circularly polarized light, reveals that, for high excitonic density and short times after the pulsed excitation, the emission from majority excitons lies above that of minority ones. The amount of the splitting, which can be as large as 50% of the binding energy, increases with excitonic density and presents a time evolution closely connected with the degree of polarization of the luminescence. Our results are interpreted on the light of a recently developed model, which shows that, while intraexcitonic exchange interaction is responsible for the spin relaxation processes, exciton-exciton interaction produces a breaking of the spin degeneracy in two-dimensional semiconductors.

Optics and Optoelectronics of Two-dimensional Semiconducting Monolayers and Heterostructures

Thesis (Ph.D.)--University of Washington, 2016-06

Evaluation of individual protein errors in silver-stained two-dimensional gels

The relationship between spot volume and variation for all protein spots observed on large format 2D gels when utilising silver stain technology and a model system based on mammalian NSO cell extracts is reported. By running multiple gels we have shown that the reproducibility of data generated in this way is dependent on individual protein spot volumes, which in turn are directly correlated with the coefficient of variation. The coefficients of variation across all observed protein spots were highest for low abundant proteins which are the primary contributors to process error, and lowest for more abundant proteins. Using the relationship between spot volume and coefficient of variation we show it is necessary to calculate variation for individual protein spot volumes. The inherent limitations of silver staining therefore mean that errors in individual protein spot volumes must be considered when assessing significant changes in protein spot volume and not global error. (C) 2003 Elsevier Science (USA). All rights reserved.

Capillary phenomena in the framework of the two-dimensional density functional theory

We present results of application of the density functional theory (DFT) to adsorption and desorption in finite and infinite cylindrical pores accounting for the density distribution in radial and axial directions. Capillary condensation via formation of bridges is considered using canonical and grand canonical versions of the 2D DFT. The potential barrier of nucleation is determined as a function of the bulk pressure and the pore diameter. In the framework of the conventional assumptions on intermolecular interactions both 1D and 2D DFT versions lead to the same results and confirm the classical scenario of condensation and evaporation: the condensation occurs at the vapor-like spinodal point, and the evaporation corresponds to the equilibrium transition pressure. The analysis of experimental data on argon and nitrogen adsorption on MCM-41 samples seems to not completely corroborate this scenario, with adsorption branch being better described by the equilibrium pressure - diameter dependence. This points to the necessity of the further development of basic representations on the hysteresis phenomena.

Comparison of two-dimensional speckle and tissue velocity based strain and validation with harmonic phase magnetic resonance imaging

Two-dimensional (2-D) strain (epsilon(2-D)) on the basis of speckle tracking is a new technique for strain measurement. This study sought to validate epsilon(2-D) and tissue velocity imaging (TVI)based strain (epsilon(TVI)) with tagged harmonic-phase (HARP) magnetic resonance imaging (MRI). Thirty patients (mean age. 62 +/- 11 years) with known or suspected ischemic heart disease were evaluated. Wall motion (wall motion score index 1.55 +/- 0.46) was assessed by an expert observer. Three apical images were obtained for longitudinal strain (16 segments) and 3 short-axis images for radial and circumferential strain (18 segments). Radial epsilon(TVI) was obtained in the posterior wall. HARP MRI was used to measure principal strain, expressed as maximal length change in each direction. Values for epsilon(2-D), epsilon(TVI), and HARP MRI were comparable for all 3 strain directions and were reduced in dysfunctional segments. The mean difference and correlation between longitudinal epsilon(2-D) and HARP MRI (2.1 +/- 5.5%, r = 0.51, p < 0.001) were similar to those between longitudinal epsilon(TVI), and HARP MRI (1.1 +/- 6.7%, r = 0.40, p < 0.001). The mean difference and correlation were more favorable between radial epsilon(2-D) and HARP MRI (0.4 +/- 10.2%, r = 0.60, p < 0.001) than between radial epsilon(TVI), and HARP MRI (3.4 +/- 10.5%, r = 0.47, p < 0.001). For circumferential strain, the mean difference and correlation between epsilon(2-D) and HARP MRI were 0.7 +/- 5.4% and r = 0.51 (p < 0.001), respectively. In conclusion, the modest correlations of echocardiographic and HARP MRI strain reflect the technical challenges of the 2 techniques. Nonetheless, epsilon(2-D) provides a reliable tool to quantify regional function, with radial measurements being more accurate and feasible than with TVI. Unlike epsilon(TVI), epsilon(2-D) provides circumferential measurements. (c) 2006 Elsevier Inc. All rights reserved.