Solvent and pH Effects on the Fluorescence of 7-(Dimethylamino)-2-Fluorenesulfonate

A novel water-soluble solvatochromic molecule, 7-(dimethylamino)-2-fluorenesulfonate (2,7-DAFS), was prepared by a three-step reaction from 2-nitrofluorene in good overall yield. The pH and solvent effects on the UV-VIS absorption and fluorescence spectra of 2,7-DAFS have been studied. Protonation of the dimethylamino group switches the absorption from intramolecular charge-transfer (ICT) to π → π* transition. The ground state pKa value of 2,7-DAFS was determined as 4.51. The fluorescence spectrum of the excited basic form, *(DAFS), shows a structureless single band with a large Stokes shift, whereas that of the acidic form, *(⁺HDAFS), exhibits a structured band with a small Stokes shift. The emission intensities of the basic and acidic forms versus pH/Ho plots show stretched sigmoidal curves and indicate that (1) the rate of deprotonation of *(⁺HDAFS) is comparable to the fluorescence decay of the species, and (2) the efficient proton-induced quenching of *(DAFS) fluorescence occurs. The pKa* was estimated as −1.7 from the fluorescence titration curve. The fluorescence maximum of *(DAFS) is blue-shifted as the polarity of solvent decreases. However, no clear dependency of the emission intensity and spectral half width, and thus fluorescence quantum yield, on the solvent polarity was revealed. It appears that the fluorescence sensitivity of 2,7-DAFS is 15 ∼ 25 times greater than the sensitivity of a widely utilized fluorescent probe, 5-(dimethylamino)-1-naphthalenesulfonate. This higher sensitivity, together with the ease of derivatization, would provide the fluorene-based fluorescent molecules significant advantages for a variety of applications.     

Control of polarity and defects in the growth of AlN films on Si (111) surfaces by inserting an Al interlayer

We discuss the role of the Al interlayer in the suppression of pinhole formations and also look at the polarity transition of the AlN layers from N-polarity to Al-polarity when this Al interlayer is present. The AlN layers were grown by molecular beam epitaxy on an AlN nucleation layer. A thin Al interlayer was deposited on the initial nucleated AlN layer after the nitridation of the Al-soaked Si (111) substrates. The AlN layer with an Al interlayer showed a relatively smooth surface with a reduced density of pinholes compared with the AlN layer grown without an Al interlayer. In addition, the AlN layer with an Al interlayer showed some stacking faults in the interface between the Si substrate and the A1N layer. We also identify the polarity change of the AlN layer after the insertion of a thin Al interlayer from N-polarity to Al-polarity by chemical etching. A simple model is constructed to explain the polarity change and the pinhole suppression due to the Al interlayer.     

Leader-following consensus criteria for multi-agent systems with time-varying delays and switching interconnection topologies

We consider multi-agent systems with time-varying delays and switching interconnection topologies.By constructing a suitable Lyapunov-Krasovskii functional and using the reciprocally convex approach,new delay-dependent consensus criteria for the systems are established in terms of linear matrix inequalities(LMIs),which can be easily solved by using various effective optimization algorithms.Two numerical examples are given to illustrate the effectiveness of the proposed methods.     

Complete condensation in a zero range process on scale-free networks

We study a zero range process on scale-free networks in order to investigate how network structure influences particle dynamics. The zero range process is defined with the rate p(n) = n(delta) at which particles hop out of nodes with n particles. We show analytically that a complete condensation occurs when delta < or = delta(c) triple bond 1/(gamma-1) where gamma is the degree distribution exponent of the underlying networks. In the complete condensation, those nodes whose degree is higher than a threshold are occupied by macroscopic numbers of particles, while the other nodes are occupied by negligible numbers of particles. We also show numerically that the relaxation time follows a power-law scaling tau approximately L(z) with the network size L and a dynamic exponent z in the condensed phase.     

Asymmetrically coupled directed percolation systems

We introduce a dynamical model of coupled directed percolation systems with two particle species. The two species A and B are coupled asymmetrically in that A particles branch B particles, whereas B particles prey on A particles. This model may describe epidemic spreading controlled by reactive immunization agents. We study nonequilibrium phase transitions with attention focused on the multicritical point where both species undergo the absorbing phase transition simultaneously. In one dimension, we find that the inhibitory coupling from B to A is irrelevant and the model belongs to the unidirectionally coupled directed percolation class. On the contrary, a mean-field analysis predicts that the inhibitory coupling is relevant and a new universality appears with a variable dynamic exponent. Numerical simulations on small-world networks confirm our predictions.     

Memory characteristics of platinum nanoparticle-embedded MOS capacitors

The capacitance characteristics of platinum nanoparticle (NP)-embedded metal–oxide–semiconductor (MOS) capacitors with gate Al₂O₃ layers are studied in this work. The capacitance versus voltage (C–V) curves obtained for a representative MOS capacitor exhibit flat-band voltage shifts, demonstrating the presence of charge storages in the platinum NPs. The counterclockwise hysteresis and flat-band voltage shift, observed from the C–V curves imply that electrons are stored in a floating gate layer consisting of the platinum NPs present between the tunneling and control oxide layers in the MOS capacitor and that these stored electrons originate from the Si substrate. Moreover, the charge remains versus time curve for the platinum NP-embedded MOS capacitor is investigated in this work.     

Polymer assisted assembling of the semiconductor particles: Structural and electrical studies

CdS and Si semiconductor nanopraticles were embedded in a polymer matrix and characterized using various techniques. The surface properties and size distribution of the nanoparticles were monitored by POM and SEM and found to be uniform but around the crystalline frameworks of the polymer. XRD and FTIR analysis have been used to ensure the composite nature and particle size of the semiconductor loaded films. The electrical conductivity of these films were evaluated and found to increase with semiconductor dispersion and attains a percolation threshold at optimum composition. This composition and the distribution of the clusters is shown to vary with the type of the semiconductor, i.e., CdS or Si.     

Coevolutionary extremal dynamics on gasket fractal

We considered a Bak-Sneppen model on a Sierpinski gasket fractal. We calculated the avalanche size distribution and the distribution of distances between subsequent minimal sites. To observe the temporal correlations of the avalanche, we estimated the return time distribution, the first-return time, and the all-return time distribution. The avalanche size distribution follows the power law, P(s)∼s−τ, with the exponent τ=1.004(7). The distribution of jumping sites also follows the power law, P(r)∼r−π, with the critical exponent π=4.12(4). We observe the periodic oscillation of the distribution of the jumping distances which originated from the jumps of the level when the minimal site crosses the stage of the fractal. The first-return time distribution shows the power law, Pf(t)∼t−τf, with the critical exponent τf=1.418(7). The all-return time distribution is also characterized by the power law, Pa(t)∼t−τa, with the exponent τa=0.522(4). The exponents of the return time satisfy the scaling relation τf+τa=2 for τf?2.     

Ex vivo study of carotid endarterectomy specimens: quantitative relaxation times within atherosclerotic plaque tissues

Purpose

Previous studies reporting relaxation times within atherosclerotic plaque have typically used dedicated small-bore high-field systems and small sample sizes. This study reports quantitative T₁, T₂ and T₂^? relaxation times within plaque tissue at 1.5 T using spatially co-matched histology to determine tissue constituents.

Methods

Ten carotid endarterectomy specimens were removed from patients with advanced atherosclerosis. Imaging was performed on a 1.5-T whole-body scanner using a custom built 10-mm diameter receive-only solenoid coil. A protocol was defined to allow subsequent computation of T₁, T₂ and T₂^? relaxation times using multi-flip angle spoiled gradient echo, multi-echo fast spin echo and multi-echo gradient echo sequences, respectively. The specimens were subsequently processed for histology and individually sectioned into 2-mm blocks to allow subsequent co-registration. Each imaging sequence was imported into in-house software and displayed alongside the digitized histology sections. Regions of interest were defined to demarcate fibrous cap, connective tissue and lipid/necrotic core at matched slice-locations. Relaxation times were calculated using Levenberg-Marquardt's least squares curve fitting algorithm. A linear-mixed effect model was applied to account for multiple measurements from the same patient and establish if there was a statistically significant difference between the plaque tissue constituents.

Results

T₂ and T₂^? relaxation times were statistically different between all plaque tissues (P=.026 and P=.002 respectively) [T₂: lipid/necrotic core was lower 47±13.7 ms than connective tissue (67±22.5 ms) and fibrous cap (60±13.2 ms); T₂^?: fibrous cap was higher (48±15.5ms) than connective tissue (19±10.6 ms) and lipid/necrotic core (24±8.2 ms)]. T₁ relaxation times were not significantly different (P=.287) [T₁: Fibrous cap: 933±271.9 ms; connective tissue (1002±272.9 ms) and lipid/necrotic core (1044±304.0 ms)]. We were unable to demarcate hemorrhage and calcium following histology processing.

Conclusions

This study demonstrates that there is a significant difference between qT₂ and qT₂^? in plaque tissues types. Derivation of quantitative relaxation times shows promise for determining plaque tissue constituents.     

Domain growth and aging scaling in coarsening disordered systems

We explore the electronic and transport properties out of a biased multilayer hexagonal boron nitride (h-BN) by first-principles calculations. The band gaps of multilayer h-BN decrease almost linearly with increasing perpendicular electric field, irrespective of the layer number N and stacking manner. The critical electric filed (E ₀) required to close the band gap decreases with the increasing N and can be approximated by E ₀ = 3.2 / (N ? 1) (eV). We provide a quantum transport simulation of a dual-gated 4-layer h-BN with graphene electrodes. The transmission gap in this device can be effectively reduced by double gates, and a high on-off ratio of 3000 is obtained with relatively low voltage. This renders biased MLh-BN a promising channel in field effect transistor fabrication.