Hammett Correlation in the Accelerated Formation of 2,3-Diphenylquinoxalines in Nebulizer Microdroplets

The accelerated formation of 2,3-diphenylquinoxalines in microdroplets generated in a nebulizer has been investigated by competition experiments in which equimolar quantities of 1,2-phenylenediamine, C₆H₄(NH₂)₂, and a 4-substituted homologue, XC₆H₃(NH₂)₂ [X = F, Cl, Br, CH₃, CH₃O, CO₂CH₃, CF₃, CN or NO₂], or a 4,5-disubstituted homologue, X₂C₆H₂(NH₂)₂ [X = F, Cl, Br, or CH₃], compete to condense with benzil, (C₆H₅CO)₂. Electron-donating substituents (X = CH₃ and CH₃O) accelerate the reaction; in contrast, electron-attracting substituents (X = F, Cl, Br and particularly CO₂CH₃, CN, CF₃ and NO₂) retard it. A structure–reactivity relationship in the form of a Hammett correlation has been found by analyzing the ratio of 2,3-diphenylquinoxaline and the corresponding substituted-2,3-diphenylquinoxaline, giving a ρ value of −0.96, thus confirming that the electron density in the aromatic ring of the phenylenediamine component is reduced in the rate-limiting step in this accelerated condensation. This correlation shows that the phenylenediamine acts as a nucleophile in the reaction.     

Understanding neuromotor strategy during functional upper extremity tasks using symbolic dynamics

The ability to model and quantify brain activation patterns that pertain to natural neuromotor strategy of the upper extremities during functional task performance is critical to the development of therapeutic interventions such as neuroprosthetic devices. The mechanisms of information flow, activation sequence and patterns, and the interaction between anatomical regions of the brain that are specific to movement planning, intention and execution of voluntary upper extremity motor tasks were investigated here. This paper presents a novel method using symbolic dynamics (orbital decomposition) and nonlinear dynamic tools of entropy, self-organization and chaos to describe the underlying structure of activation shifts in regions of the brain that are involved with the cognitive aspects of functional upper extremity task performance. Several questions were addressed: (a) How is it possible to distinguish deterministic or causal patterns of activity in brain fMRI from those that are really random or non-contributory to the neuromotor control process? (b) Can the complexity of activation patterns over time be quantified? (c) What are the optimal ways of organizing fMRI data to preserve patterns of activation, activation levels, and extract meaningful temporal patterns as they evolve over time? Analysis was performed using data from a custom developed time resolved fMRI paradigm involving human subjects (N=18) who performed functional upper extremity motor tasks with varying time delays between the onset of intention and onset of actual movements. The results indicate that there is structure in the data that can be quantified through entropy and dimensional complexity metrics and statistical inference, and furthermore, orbital decomposition is sensitive in capturing the transition of states that correlate with the cognitive aspects of functional task performance.     

On Turbulent Jets Issuing from Notched-Rectangular and Circular Orifice Plates

This paper reports an experimental investigation of the near-field flow characteristics of two air/air turbulent jets issuing respectively from notched-rectangular and circular orifice plates with identical opening areas or equivalent diameters (D _e ). Planar particle image velocimetry (PIV) was used to measure the velocity field at the same Reynolds number, based on D _e , of Re = 72,000. Consistent with previous work on other noncircular jets, the present study finds that the notched jet has a higher rate of mixing than does the circular counterpart. In particular, this jet in the very near field transfers its momentum to the surroundings at a greater rate, evidenced by a notably shorter unmixed core and faster turbulence intensity growth. The higher rates of overall decay and spread of the notched jet are maintained over the entire measurement region and likely beyond. In addition, the phenomenon of axis switching is also found to occur in this jet.     

Demonstration of chalcogenide glass racetrack microresonators

We have demonstrated what we believe to be the first chalcogenide glass racetrack microresonator using a complementary metal-oxide semiconductor-compatible lift-off technique with thermally evaporated As(2)S(3) films. The device simultaneously features a small footprint of 0.012 mm x 0.012 mm, a cavity Q (quality factor) of 10,000, and an extinction ratio of 32 dB. These resonators exhibit a very high sensitivity to refractive index changes with a demonstrated detection capability of Dn(As(2)S(3)=(4.5 x 10(-6)+/-10%) refractive index unit. The resonators were applied to derive a photorefractive response of As(2)S(3) to lambda=550 nm light. The resonator devices are a versatile platform for both sensing and glass material property investigation.     

Three-dimensional molecular mapping in a microfluidic mixing device using fluorescence lifetime imaging

Fluorescence lifetime imaging (FLIM) is used to quantitatively map the concentration of a small molecule in three dimensions in a microfluidic mixing device. The resulting experimental data are compared with computational fluid-dynamics (CFD) simulations. A line-scanning semiconfocal FLIM microscope allows the full mixing profile to be imaged in a single scan with submicrometer resolution over an arbitrary channel length from the point of confluence. Following experimental and CFD optimization, mixing times down to 1.3+/-0.4 ms were achieved with the single-layer microfluidic device.     

Improved sectioning in a slit scanning confocal microscope

We describe a simple implementation of a slit scanning confocal microscope to obtain an axial resolution better than that of a point-scanning confocal microscope. Under slit illumination, images of a fluorescent object are captured using an array detector instead of a line detector so that out-of-focus light is recorded and then subtracted from the adjacent images. Axial resolution after background subtraction is 2.2 times better than the slit confocal resolution, and out-of-focus image suppression is calculated to attenuate with defocus faster by 1 order of magnitude than in the point confocal case.     

Planar waveguide-coupled, high-index-contrast, high-Q resonators in chalcogenide glass for sensing

High-index-contrast compact microdisk resonators in thermally evaporated As2S3 and Ge17Sb12S71 chalcogenide glass films are designed and fabricated using standard UV lithography and characterized. Our pulley coupler configuration demonstrates coupling of the resonators to monolithically integrated photonic wire waveguides without resorting to demanding fine-line lithography. Microdisk resonators in As2S3 support whispering-gallery-mode with cavity quality factors (Q) exceeding 2 x 10(5), the highest Q value reported in resonator structures in chalcogenide glasses to the best of our knowledge. We have successfully demonstrated a lab-on-a-chip prototype sensor device with the integration of our resonator with planar microfluidic systems. The sensor shows a refractive index sensitivity of 182 nm/RIU (refractive index unit) and a wavelength resolution of 0.1 pm through a resonant peak fit. This corresponds to a refractive index detection limit of 8 x 10(-7) RIU at 1550 nm in wavelength, which could be further improved by shifting the operating wavelength to a region where water absorption is reduced.     

Onset of diffusive behavior in confined transport systems

We investigate the onset of diffusive behavior in polygonal channels for disks of finite size, modeling simple microporous membranes. It is well established that the point-particle case displays anomalous transport, because of slow correlation decay in the absence of defocusing collisions. We investigate which features of point-particle transport survive in the case of finite-sized particles (which undergo defocusing collisions). A similar question was investigated by Lansel, Porter, and Bunimovich [Chaos 16, 013129 (2006)], who found that certain integrals of motion and multiple ergodic components, characteristic of the point-particle case, remain in "mushroom"-like systems with few finite-sized particles. We quantify the time scales over which the transport of disks shows features typical of the point particles, or is driven toward diffusive behavior. In particular, we find that interparticle collisions drive the system toward diffusive behavior more strongly than defocusing boundary collisions. We illustrate how, and at what stage, typical thermodynamic behavior (consistent with kinetic theory) is observed, as particle numbers grow and mean free paths diminish. These results have both applied (e.g., nanotechnological) and theoretical interest.     

An empirical characterization of the quality of DTI data and the efficacy of dyadic sorting

Metrics calculated from images acquired using the diffusion tensor imaging (DTI) technique possess a systematic bias that depends on signal-to-noise ratio (SNR). Dyadic sorting provides a simple method for remediating some of this bias within a region(s) of interest (ROI). Although this bias and its removal using dyadic sorting have been studied previously within a theoretical framework, one can employ precise geometric knowledge of microstructures to perform an empirical comparison between expected DTI results and those measured with a scanner. In this project, the biasing effect of low SNR (approximately 1-10) on DTI eigenvalues was measured directly using water-filled capillary structures of two different sizes, and the magnitude of the corrective effect of dyadically sorting eigenvector-eigenvalue pairs was characterized. Multiple DTI series were acquired for determining DTI metrics at eight unique SNR values, using T(R) to vary signal intensity via T(1) contrast. Differences between the second and third eigenvalues, which should be equal for prolate geometry, ranged from approximately 23% to 45% and from 19% to 41% for large and small inner diameter capillaries after sorting eigenvalues by magnitude, and ranged from approximately 1% to 18% and from 1% to 4% after dyadic sorting. A high-resolution DTI series was used to observe the effect of ROI size on dyadic sorting. For restriction of diffusion on the scale of the small capillary at SNR approximately 18, an ROI with > or =50 pixels is adequate to determine fractional anisotropy to 99% accuracy, while larger ROI are required to resolve the two smaller eigenvalues to the same accuracy ( approximately 330-390 pixels). At low values of SNR, the iteration of dyadic sorting is suggested to achieve good accuracy. A method for the incorporation of empirical measurements into a bias-correction map, which would be useful for characterizing uncertainty and for reducing systematic bias in DTI data, is introduced.