Structure-reactivity correlations in the selective aerobic oxidation of cinnamyl alcohol:in situ XAFS

The structural evolution of a Pd/C catalyst during the liquid phase selective aerobic oxidation of cinnamyl alcohol has been followed by in situ XAFS and XPS. The fresh catalyst comprised highly dispersed, heavily oxidised Pd particles. Cinnamyl alcohol oxidation resulted in the rapid reduction of surface palladium oxide and a small degree of concomitant particle growth. These structural changes coincided with a large drop in catalytic activity. Prereduced Pd/C exhibited a significantly lower initial oxidation rate demonstrating the importance of surface metal oxide in effecting catalytic oxidation. Use of a Pd black model system confirmed that the oxide→metal transformation was the cause, and not result, of catalyst deactivation.

Recent advances in the field of vertical-external-cavity surface-emitting lasers

Vertical-external-cavity surface-emitting lasers (VECSELs) have proved to be versatile lasers which allow for various emission schemes which on the one hand include remarkably high-power multi-mode or single-frequency continuouswave operation, and on the other hand two-color as well as mode-locked emission. Particularly, the combination of semiconductor gain medium and external cavity provides a unique access to high-brightness output, a high beam quality and wavelength flexibility. Moreover, the exploitation of intra-cavity frequency conversion further extends the achievable radiation wavelength, spanning a spectral range from the UV to the THz. In this work, recent advances in the field of VECSELs are summarized and the demonstration of self-mode-locking (SML) VECSELs with sub-ps pulses is highlighted. Thereby, we present studies which were not only performed for a quantum-well-based VECSEL, but also for a quantum-dot VECSEL.

A simulation of the surface EMG for analysis of muscle activity during whole body vibratory stimulation

Many studies have accounted for whole body vibration effects in the fields of exercise physiology, sport and rehabilitation medicine. Generally, surface EMG is utilized to assess muscular activity during the treatment; however, large motion artifacts appear superimposed to the raw signal, making sEMG recording not suitable before any artifact filtering. Sharp notch filters, centered at vibration frequency and at its superior harmonics, have been used in previous studies, to remove the artifacts. [6, 10] However, to get rid of those artifacts some true EMG signal is lost. The purpose of this study was to reproduce the effect of motor-unit synchronization on a simulated surface EMG during vibratory stimulation. In addition, authors mean to evaluate the EMG power percentage in those bands in which are also typically located motion artifact components. Model characteristics were defined to take into account two main aspect: the muscle MUs discharge behavior and the triggering effects that appear during local vibratory stimulation. [7] Inter-pulse-interval, was characterized by a polimodal distribution related to the MU discharge frequency (IPI 55-80ms, σ=12ms) and to the correlation with the vibration period within the range of ±2 ms due to vibration stimulus. [1, 7] The signals were simulated using different stimulation frequencies from 30 to 70 Hz. The percentage of the total simulated EMG power within narrow bands centered at the stimulation frequency and its superior harmonics (± 1 Hz) resulted on average about 8% (± 2.85) of the total EMG power. However, the artifact in those bands may contain more than 40% of the total power of the total signal. [6] Our preliminary results suggest that the analysis of the muscular activity of muscle based on raw sEMG recordings and RMS evaluation, if not processed during vibratory stimulation may lead to a serious overestimation of muscular response.

Simulation of surface EMG for the analysis of muscle activity during whole body vibratory stimulation

This study aims to reproduce the effect of motor-unit synchronization on surface EMG recordings during vibratory stimulation to highlight vibration evoked muscle activity. The authors intended to evaluate, through numerical simulations, the changes in surface EMG spectrum in muscles undergoing whole body vibration stimulation. In some specific bands, in fact, vibration induced motion artifacts are also typically present. In addition, authors meant to compare the simulated EMGs with respect to real recordings in order to discriminate the effect of synchronization of motor units discharges with vibration frequencies from motion artifacts. Computations were performed using a model derived from previous studies and modified to consider the effect of vibratory stimulus, the motor unit synchronization and the endplates-electrodes relative position on the EMG signal. Results revealed that, in particular conditions, synchronization of MUs' discharge generates visible peaks at stimulation frequency and its harmonics. However, only a part of the total power of surface EMGs might be enclosed within artifacts related bands (±1. Hz centered at the stimulation frequency and its superior harmonics) even in case of strong synchronization of motor units discharges with the vibratory stimulus. © 2013 Elsevier Ireland Ltd.

Development of potent and selective tissue transglutaminase inhibitors:their effect on TG2 function and application in pathological conditions

Potent-selective peptidomimetic inhibitors of tissue transglutaminase (TG2) were developed through a combination of protein-ligand docking and molecular dynamic techniques. Derivatives of these inhibitors were made with the aim of specific TG2 targeting to the intra- and extracellular space. A cell-permeable fluorescently labeled derivative enabled detection of in situ cellular TG2 activity in human umbilical cord endothelial cells and TG2-transduced NIH3T3 cells, which could be enhanced by treatment of cells with ionomycin. Reaction of TG2 with this fluorescent inhibitor in NIH3T3 cells resulted in loss of binding of TG2 to cell surface syndecan-4 and inhibition of translocation of the enzyme into the extracellular matrix, with a parallel reduction in fibronectin deposition. In human umbilical cord endothelial cells, this same fluorescent inhibitor also demonstrated a reduction in fibronectin deposition, cell motility, and cord formation in Matrigel. Use of the same inhibitor in a mouse model of hypertensive nephrosclerosis showed over a 40% reduction in collagen deposition.

Selective oxidation of cyclohexene through gold functionalized silica monolith microreactors

Two simple, reproducible methods of preparing evenly distributed Au nanoparticle containing mesoporous silica monoliths are investigated. These Au nanoparticle containing monoliths are subsequently investigated as flow reactors for the selective oxidation of cyclohexene. In the first strategy, the silica monolith was directly impregnated with Au nanoparticles during the formation of the monolith. The second approach was to pre-functionalize the monolith with thiol groups tethered within the silica mesostructure. These can act as evenly distributed anchors for the Au nanoparticles to be incorporated by flowing a Au nanoparticle solution through the thiol functionalized monolith. Both methods led to successfully achieving even distribution of Au nanoparticles along the length of the monolith as demonstrated by ICP-OES. However, the impregnation method led to strong agglomeration of the Au nanoparticles during subsequent heating steps while the thiol anchoring procedure maintained the nanoparticles in the range of 6.8 ± 1.4 nm. Both Au nanoparticle containing monoliths as well as samples with no Au incorporated were tested for the selective oxidation of cyclohexene under constant flow at 30 °C. The Au free materials were found to be catalytically inactive with Au being the minimum necessary requirement for the reaction to proceed. The impregnated Au-containing monolith was found to be less active than the thiol functionalized Au-containing material, attributable to the low metal surface area of the Au nanoparticles. The reaction on the thiol functionalized Au-containing monolith was found to depend strongly on the type of oxidant used: tert-butyl hydroperoxide (TBHP) was more active than H2O2, likely due to the thiol induced hydrophobicity in the monolith.

Biosensor based on excessively tilted fiber grating in thin-cladding optical fiber for sensitive and selective detection of low glucose concentration

We report a highly sensitive, high Q-factor, label free and selective glucose sensor by using excessively tilted fiber grating (Ex-TFG) inscribed in the thin-cladding optical fiber (TCOF). Glucose oxidase (GOD) was covalently immobilized on optical fiber surface and the effectiveness of GOD immobilization was investigated by the fluorescence microscopy and highly accurate spectral interrogation method. In contrast to the long period grating (LPG) and optical fiber (OF) surface Plasmon resonance (SPR) based glucose sensors, the Ex-TFG configuration has merits of nearly independent cross sensitivity of the environmental temperature, simple fabrication method (no noble metal deposition or cladding etching) and high detection accuracy (or Q-factor). Our experimental results have shown that Ex-TFG in TCOF based sensor has a reliable and fast detection for the glucose concentration as low as 0.1~2.5mg/ml and a high sensitivity of ~1.514nm·(mg/ml)−1, which the detection accuracy is ~0.2857nm−1 at pH 5.2, and the limit of detection (LOD) is 0.013~0.02mg/ml at the pH range of 5.2~7.4 by using an optical spectrum analyzer with a resolution of 0.02nm.

An investigation of support effects on the Pt-catalysed selective transformation of α,β-unsaturated substrates

Pt catalyst series were prepared on mesoporous SBA-15, SBA-16, KIT-6, true liquidcrystal-templated meso-macroporous SBA-15 and a commercial, low surface area silicasupport. Support structure can be easily fabricated using surfactant templating as a mode ofstringent control on porosity, surface area and internal structure. The impact of varying Pt-support physicochemical properties was systematically studied for the selective transformation of allylic substrates under chemoselective oxidation and hydrogenation regimes, a class of reactions highly applicable to industry. Pt-based heterogeneous catalysts are well-known for their utilisation in the hydrogenation of α,β-unsaturated aldehydes,although the mode of action and lack of systematic studies in the literature fuels continuing debate into the role of Pt nanoparticles and support choice for this area. This project attempts to shed some light on several frequently asked questions in this field. Successful support synthesis and stability after Pt impregnation is confirmed through HRTEM, XRD and N2 porosimetry. Decreasing metal loading promoted dispersion values,regardless of support choice, with surface PtO2 content also showing visible enhancement.Increasing support surface area and mesoporosity exhibited the following trend on Pt dispersion augmentation; low surface area commercial silica < true liquid crystal-templated SBA-15 < SBA-15 < SBA-16 ~ KIT-6. For the selective oxidation of cinnamyl alcohol,increasing PtO2 surface population confers substantial rate enhancements, with turnover frequencies evidencing PtO2 to be the active species .In the Pt-catalysed hydrogenation of cinnamaldehyde, strong support insensitivity was observed towards catalytic activity; as turnover frequencies normalised to Pt metal reveal constant values. However, structure sensitivity to the desired unsaturated alcohol arose,evidencing the requirement of flat, extended Pt (111) facets for C=O hydrogenation. Pt/SBA-15 proved the most selective, reflecting suppressed cinnamyl alcohol hydrogenation, with DRIFTS and in-situ ATR-IR evidencing the key role of support polarity in re-orientation of cinnamaldehyde to favour di-σCO adsorption and C=O versus C=C hydrogenation. High pressures increased activity, whilst a dramatic shift in selectivity from dominant C=C (1 bar)to C=O hydrogenation (10 bar) was also observed, attributed to surface crowding and suppression of di-σCC and η4 di-σCO+πC=C cinnamaldehyde binding modes.

Development of surface flaw thresholds for pre-cured fiber reinforced polymer and groove size tolerance for near surface mounted fiber reinforced polymer retrofit systems

Since the introduction of fiber reinforced polymers (FRP) for the repair and retrofit of concrete structures in the 1980’s, considerable research has been devoted to the feasibility of their application and predictive modeling of their performance. However, the effects of flaws present in the constitutive components and the practices in substrate preparation and treatment have not yet been thoroughly studied. This research aims at investigating the effect of surface preparation and treatment for the pre-cured FRP systems and the groove size tolerance for near surface mounted (NSM) FRP systems; and to set thresholds for guaranteed system performance. This study was conducted as part of the National Cooperative Highway Research Program (NCHRP) Project 10-59B to develop construction specifications and process control manual for repair and retrofit of concrete structures using bonded FRP systems. The research included both analytical and experimental components. The experimental program for the pre-cured FRP systems consisted of a total of twenty-four (24) reinforced concrete (RC) T-beams with various surface preparation parameters and surface flaws, including roughness, flatness, voids and cracks (cuts). For the NSM FRP systems, a total of twelve (12) additional RC T-beams were tested with different grooves sizes for FRP bars and strips. The analytical program included developing an elaborate nonlinear finite element model using the general purpose software ANSYS. The bond interface between FRP and concrete was modeled by a series of nonlinear springs. The model was validated against test data from the present study as well as those available from the literature. The model was subsequently used to extend the experimental range of parameters for surface flatness in pre-cured FRP systems and for groove size study in the NSM FRP systems. Test results, confirmed by further analyses, indicated that contrary to the general belief in the industry, the impact of surface roughness on the global performance of pre-cured FRP systems was negligible. The study also verified that threshold limits set for wet lay-up FRP systems can be extended to pre-cured systems. The study showed that larger surface voids and cracks (cuts) can adversely impact both the strength and ductility of pre-cured FRP systems. On the other hand, frequency (or spacing) of surface cracks (cuts) may only affect system ductility rather than its strength. Finally, within the range studied, groove size tolerance of ±1/8 in. does not appear to have an adverse effect on the performance of NSM FRP systems.

Fluorescence-enhanced optical imaging on three-dimensional phantoms using a hand-held probe based frequency-domain intensified charge coupled device (ICCD) optical imager

Fluorescence-enhanced optical imaging is an emerging non-invasive and non-ionizing modality towards breast cancer diagnosis. Various optical imaging systems are currently available, although most of them are limited by bulky instrumentation, or their inability to flexibly image different tissue volumes and shapes. Hand-held based optical imaging systems are a recent development for its improved portability, but are currently limited only to surface mapping. Herein, a novel optical imager, consisting primarily of a hand-held probe and a gain-modulated intensified charge coupled device (ICCD) detector, is developed towards both surface and tomographic breast imaging. The unique features of this hand-held probe based optical imager are its ability to; (i) image large tissue areas (5×10 sq. cm) in a single scan, (ii) reduce overall imaging time using a unique measurement geometry, and (iii) perform tomographic imaging for tumor three-dimensional (3-D) localization. Frequency-domain based experimental phantom studies have been performed on slab geometries (650 ml) under different target depths (1-2.5 cm), target volumes (0.45, 0.23 and 0.10 cc), fluorescence absorption contrast ratios (1:0, 1000:1 to 5:1), and number of targets (up to 3), using Indocyanine Green (ICG) as fluorescence contrast agents. An approximate extended Kalman filter based inverse algorithm has been adapted towards 3-D tomographic reconstructions. Single fluorescence target(s) was reconstructed when located: (i) up to 2.5 cm deep (at 1:0 contrast ratio) and 1.5 cm deep (up to 10:1 contrast ratio) for 0.45 cc-target; and (ii) 1.5 cm deep for target as small as 0.10 cc at 1:0 contrast ratio. In the case of multiple targets, two targets as close as 0.7 cm were tomographically resolved when located 1.5 cm deep. It was observed that performing multi-projection (here dual) based tomographic imaging using a priori target information from surface images, improved the target depth recovery over using single projection based imaging. From a total of 98 experimental phantom studies, the sensitivity and specificity of the imager was estimated as 81-86% and 43-50%, respectively. With 3-D tomographic imaging successfully demonstrated for the first time using a hand-held based optical imager, the clinical translation of this technology is promising upon further experimental validation from in-vitro and in-vivo studies.

Selective and specific activation of Rab5 during endocytosis of receptor tyrosine kinases

The Rab family of proteins are low molecular weight GTPases that have the ability to switch between GTP- (active) and GDP- (inactive) bound form, and in that sense act as molecular switches. Through distinct localization on various vesicles and organelles and by cycling through GTP/GDP bound forms, Rabs are able to recruit and activate numerous effector proteins, both spatially and temporally, and hence behave as key regulators of trafficking in both endocytic and biosynhtetic pathways. The Rab5 protein has been shown to regulate transport from plasma membrane to the early endosome as well as activate signaling pathways from the early endosome. This dissertation focused on understanding Rab5 activation via endocytosis of receptor tyrosine kinases (RTKs). First, tyrosine kinase activity of RTKs was linked to endosome fusion by demonstrating that tyrosine kinase inhibitors block endosome fusion and activation of Rab5, and a constitutively active form of Rab5 is able to rescue endosome fusion. However, depending on how much ligand is available at the cell surface, the receptor-ligand complexes can be internalized via a number of distinct pathways. Similarly, Rab5 was activated in a ligand-dependent concentration dependent manner via clathrin- and caveolin-mediated pathways, as well as a pathway independent of both. However, overexpression Rabex-5, a nucleotide exchange factor for Rab5, is able to rescue activation even when all of the pathways of EGF-receptor internalization were blocked. Next, the three naturally occurring splice variants of Rabex-5 selectively activated Rab5. Lastly, Rabex-5 inhibits differentiation of 3T3-L1 and PC12 cells through 1) degradation of signaling endosome via Rab5-dependent fusion with the early endosome, 2) and inhibition of signaling cascade via ubiquitination of Ras through the ZnF domain at the N-terminus of Rabex-5. In conclusion, these data shed light on complexity of the endosomal trafficking system where tyrosine kinase activity of the receptor is able to affect endosome fusion; how different endocytic pathways affect activation of one of the key regulators of early endocytic events; and how selective activation of Rab5 via Rabex-5 can control adipogenesis and neurogenesis.

Intra -organizational turnover in a self -selective team environment

Four-hundred twenty-seven firefighter/paramedics and firefighter/emergency medical technicians completed questionnaires regarding past and current turnover decisions. The employees, who work in teams of either three or four, have a collective bargaining benefit that allows them to "bid for" (request) new positions/teams every six months; positions are awarded on the basis of seniority. Because employees are leaving neither the organization nor their job, the "bid" process creates intra-organizational turnover on a regular basis. It was hypothesized that those individuals higher in teamwork/social cohesion expectations, higher in interpersonal orientation, and lower in conflict tolerance would report placing greater importance on interpersonal reasons (teamwork/social cohesion) in past bid/assignment decisions. Creation of a conflict tolerance scale was the goal of a preliminary study. It was further hypothesized that current bid/assignment satisfaction would predict the current turnover decision (during the cycle in which the study was conducted), and that past individual turnover frequency would also predict current turnover. All hypotheses were supported. ^

Through wafer 3D Vertical Micro-Coaxial Probe for high frequency material characterization and millimeter wave packaging systems

This work presents the development of an in-plane vertical micro-coaxial probe using bulk micromachining technique for high frequency material characterization. The coaxial probe was fabricated in a silicon substrate by standard photolithography and a deep reactive ion etching (DRIE) technique. The through-hole structure in the form of a coaxial probe was etched and metalized with a diluted silver paste. A co-planar waveguide configuration was integrated with the design to characterize the probe. The electrical and RF characteristics of the coaxial probe were determined by simulating the probe design in Ansoft's High Frequency Structure Simulator (HFSS). The reflection coefficient and transducer gain performance of the probe was measured up to 65 GHz using a vector network analyzer (VNA). The probe demonstrated excellent results over a wide frequency band, indicating its ability to integrate with millimeter wave packaging systems as well as characterize unknown materials at high frequencies. The probe was then placed in contact with 3 materials where their unknown permittivities were determined. To accomplish this, the coaxial probe was placed in contact with the material under test and electromagnetic waves were directed to the surface using the VNA, where its reflection coefficient was then determined over a wide frequency band from dc-to -65GHz. Next, the permittivity of each material was deduced from its measured reflection coefficients using a cross ratio invariance coding technique. The permittivity results obtained when measuring the reflection coefficient data were compared to simulated permittivity results and agreed well. These results validate the use of the micro-coaxial probe to characterize the permittivity of unknown materials at high frequencies up to 65GHz.

Development of Surface Flaw Thresholds for Pre-Cured Fiber Reinforced Polymer and Groove Size Tolerance for Near Surface Mounted Fiber Reinforced Polymer Retrofit Systems

Since the introduction of fiber reinforced polymers (FRP) for the repair and retrofit of concrete structures in the 1980’s, considerable research has been devoted to the feasibility of their application and predictive modeling of their performance. However, the effects of flaws present in the constitutive components and the practices in substrate preparation and treatment have not yet been thoroughly studied. This research aims at investigating the effect of surface preparation and treatment for the pre-cured FRP systems and the groove size tolerance for near surface mounted (NSM) FRP systems; and to set thresholds for guaranteed system performance. The research included both analytical and experimental components. The experimental program for the pre-cured FRP systems consisted of a total of twenty-four (24) reinforced concrete (RC) T-beams with various surface preparation parameters and surface flaws, including roughness, flatness, voids and cracks (cuts). For the NSM FRP systems, a total of twelve (12) additional RC T-beams were tested with different grooves sizes for FRP bars and strips. The analytical program included developing an elaborate nonlinear finite element model using the general purpose software ANSYS. The model was subsequently used to extend the experimental range of parameters for surface flatness in pre-cured FRP systems, and for groove size study in the NSM FRP systems. Test results, confirmed by further analyses, indicated that contrary to the general belief in the industry, the impact of surface roughness on the global performance of pre-cured FRP systems was negligible. The study also verified that threshold limits set for wet lay-up FRP systems can be extended to pre-cured systems. The study showed that larger surface voids and cracks (cuts) can adversely impact both the strength and ductility of pre-cured FRP systems. On the other hand, frequency (or spacing) of surface cracks (cuts) may only affect system ductility rather than its strength. Finally, within the range studied, groove size tolerance of +1/8 in. does not appear to have an adverse effect on the performance of NSM FRP systems.

Development of a surface-enhanced raman spectroscopy method for the detection of benzodiazepines in urine

Benzodiazepines are among the most prescribed compounds for anti-anxiety and are present in many toxicological screens. These drugs are also prominent in the commission of drug facilitated sexual assaults due their effects on the central nervous system. Due to their potency, a low dose of these compounds is often administered to victims; therefore, the target detection limit for these compounds in biological samples is 10 ng/mL. Currently these compounds are predominantly analyzed using immunoassay techniques; however more specific screening methods are needed. ^ The goal of this dissertation was to develop a rapid, specific screening technique for benzodiazepines in urine samples utilizing surface-enhanced Raman spectroscopy (SERS), which has previously been shown be capable of to detect trace quantities of pharmaceutical compounds in aqueous solutions. Surface enhanced Raman spectroscopy has the advantage of overcoming the low sensitivity and fluorescence effects seen with conventional Raman spectroscopy. The spectra are obtained by applying an analyte onto a SERS-active metal substrate such as colloidal metal particles. SERS signals can be further increased with the addition of aggregate solutions. These agents cause the nanoparticles to amass and form hot-spots which increase the signal intensity. ^ In this work, the colloidal particles are spherical gold nanoparticles in aqueous solution with an average size of approximately 30 nm. The optimum aggregating agent for the detection of benzodiazepines was determined to be 16.7 mM MgCl2, providing the highest signal intensities at the lowest drug concentrations with limits of detection between 0.5 and 127 ng/mL. A supported liquid extraction technique was utilized as a rapid clean extraction for benzodiazepines from urine at a pH of 5.0, allowing for clean extraction with limits of detection between 6 and 640 ng/mL. It was shown that at this pH other drugs that are prevalent in urine samples can be removed providing the selective detection of the benzodiazepine of interest. ^ This technique has been shown to provide rapid (less than twenty minutes), sensitive, and specific detection of benzodiazepines at low concentrations in urine. It provides the forensic community with a sensitive and specific screening technique for the detection of benzodiazepines in drug facilitated assault cases.^