No description available.

Polysiloxanes represent a unique class of synthetic polymers, employing a completely inorganic backbone structure comprised of repeating –(Si–O)n– 'siloxane' main chain linkages. This results in an assortment of diverse properties exclusive to the siloxane bond that clearly distinguish them from the –(C–C)n– backbone of purely organic polymers. Previous work has elucidated a methodology for fabricating flexible and elastic crosslinked poly(dimethyl siloxane) (PDMS) constructs with high Mc through a simultaneous crosslinking and chain-extension methodology. However, these constructs suffer the poor mechanical properties typical of lower molecular weight crosslinked siloxanes (e.g. modulus, tear strength, and strain at break). Filled PDMS networks represent another important class of elastomers in which fillers, namely silica and siloxane-based fillers, impart improved mechanical properties to otherwise weak PDMS networks. This work demonstrates that proper silicon-based reinforcing agent selection (e.g. siloxane-based MQ copolymer nanoparticles) and incorporation provides a synergistic enhancement to mechanical properties, whilst maintaining a low viscosity liquid composition, at high loading content, without the use of co-solvents or heating. Rheological analysis evaluates the viscosity while photorheology and photocalorimetry measurements evaluate rate and extent of curing of the various MQ-loaded formulations, demonstrating theoretical printability up to 40 wt% MQ copolymer nanoparticle incorporation. Dynamic mechanical analysis (DMA) and tensile testing evaluated thermomechanical and mechanical properties of the cured nanocomposites as a function of MQ loading content, demonstrating a 3-fold increase in ultimate stress at 50 wt% MQ copolymer nanoparticle incorporation. VP AM of the 40 wt% MQ-loaded, photo-active PDMS formulation demonstrates facile amenability of photo-active PDMS formulations with high MQ-loading content to 3D printing processes with promising results. PDMS polyureas represent an important class of elastomers with unique properties derived from the synergy between the nonpolar nature, unusual flexibility, and low glass transition temperature (Tg) afforded by the backbone siloxane linkages (-Si-O)n- of PDMS and the exceptional hydrogen bond ordering and strength evoked by the bidentate hydrogen bonding of urea. The work herein presents an improved melt polycondensation synthetic methodology, which strategically harnesses the spontaneous pyrolytic degradation of urea to afford a series of PDMS polyureas via reactions at high temperatures in the presence of telechelic amine-terminated oligomeric poly(dimethyl siloxane) (PDMS1.6k-NH2) and optional 1,3-bis(3-aminopropyl)tetramethyldisiloxane (BATS) chain extender. This melt polycondensation approach uniquely circumvents the accustomed prerequisite of isocyanate monomer, solvent, and metal catalysts to afford isocyanate-free PDMS polyureas using bio-derived urea with the only reaction byproduct being ammonia, a fundamental raw ingredient for agricultural and industrial products. As professed above, reinforcement of polysiloxane materials is ascertained via the incorporation of reinforcing fillers or nanoparticles (typically fumed silica) or blocky or segmented development of polymer chains eliciting microphase separation, in order to cajole the elongation potential of polysiloxanes. Herein, a facile approach is detailed towards the synergistic fortification of PDMS-based materials through a collaborative effort between both primary methods of polysiloxane reinforcement. A novel one-pot methodology towards the facile, in situ incorporation of siloxane-based MQ copolymer nanoparticles into segmented PDMS polyureas to afford MQ-loaded thermoplastic and thermoplastic elastomer PDMS polyureas is detailed. The isocyanate-free melt polycondensation achieves visible melt dispersibility of MQ copolymer nanoparticles (good optical clarity) and affords segmented PDMS polyureas while in the presence of MQ nanoparticles, up to 40 wt% MQ, avoiding post-polymerization solvent based mixing, the only other reported alternative. Incorporation of MQ copolymer nanoparticles into segmented PDMS polyureas provides significant enhancements to modulus and ultimate stress properties: results resemble traditional filler effects and are contrary to previous studies and works discussed in Chapter 2 implementing MQ copolymer nanoparticles into chemically-crosslinked PDMS networks. In situ MQ-loaded, isocyanate-free, segmented PDMS polyureas remain compression moldable, affording transparent, free-standing films. / Master of Science / Polysiloxanes, also referred to as 'silicones' encompass a unique and important class of polymers harboring an inorganic backbone. Polysiloxanes, especially poly(dimethyl siloxane) (PDMS) the flagship polymer of the family, observe widespread utilization throughout industry and academia thanks to a plethora of desirable properties such as their incredible elongation potential, stability to irradiation, and facile chemical tunability. A major complication with the utilization of polysiloxanes for mechanical purposes is their poor resistance to defect propagation and material failure. As a result polysiloxane materials ubiquitously observe reinforcement in some fashion: reinforcement is achieved either through the physical or chemical incorporation of a reinforcing agent, such as fumed silica, or through the implementation of a chemical functionality that facilitates reinforcement via phase separation and strong associative properties, such as hydrogen bonding. This research tackles polysiloxane reinforcement via both of these strategies. Facile chemical modification permits the construction PDMS polymer chains that incorporate hydrogen bonding motifs, which phase separate to afford hydrogen bond-reinforced phases that instill vast improvements to elastic behavior, mechanical and elongation properties, and upper-use temperature. Novel nanocomposite formulation through the incorporation of MQ nanoparticles (which observe widespread usage in cosmetics) facilitate further routes toward improved mechanical and elongation properties. Furthermore, with growing interest in additive manufacturing strategies, which permit the construction of complex geometries via an additive approach (as opposed to conventional manufacturing processes, which require subtractive approaches and are limited in geometric complexity), great interest lies in the capability to additively manufacture polysiloxane-based materials. This work also illustrates the development of an MQ-reinforced polysiloxane system that is amenable to conventional vat photopolymerization additive manufacturing: chemical modification of PDMS polymer chains permits the installation of UV-activatable crosslinking motifs, allowing solid geometries to be constructed from a liquid precursor formulation.

First part of this thesis is a theoretical essay which deals with the basics of the variable pressure scanning electron microscope, includes detection of secondary electrons with a view to a scintillation detector. The first applied part of the thesis is focused on prediction, measuring and setting-up optional working parley in vacuum electrodes scintillation detector system, with a stress small diameter hole in screenings C1 and C2. Second applied part was verify a change of working distance between sample and detector in consequence to optional solution for another work.

Diese Dissertation untersucht das variable Verhalten von sogenannten „bare nouns“ (Nominale ohne Artikel) im Persischen. Dieses Verhalten kann jedoch nicht verstanden werden ohne eine Reihe von entscheidenden Eigenschaften der persischen Satzstruktur zu betrachten. Dazu gehören Informationsstruktur, Prosodie und Wortstellung, sowie die semantischen und syntaktischen Funktionen verschiedener morphologischer Markierungen im Persischen. Die vorliegende Dissertation kann daher zum besseren Verständnis von satzinterner Syntax, Semantik und Prosodie des Persischen beitragen. Ich beginne meine Untersuchung mit dem Vergleich der BNs in verschiedenen Positionen mit Nominalen, die mit verschiedenen Morphemen gekennzeichnet sind. Die quasi-inkorporierten Nominale im Persischen scheinen zur Klasse der diskursintransparenten inkorporierenden Sprachen zu gehören. Doch dies scheint nicht immer zu stimmen, unter bestimmten Umständen zeigen persische BNs Diskurstransparenz. In Kapitel 3 untersuche ich daher, unter welchen Umständen BNs Diskurstransparenz zeigen und warum. In Kapitel 3 präsentiere ich einen Alternativvorschlag zu Farkas & de Swart, in dem ich darlege, dass ein BN tatsächlich einen neuen Diskursreferenten einführt. Aber der Numerus von BNs ist neutral (numerusneutralen Diskursreferenten).In der zweiten Hälfte der Dissertation wird die Interpretation von BNs in verschiedenen Positionen und mit unterschiedlichen grammatischen Funktionen diskutiert. Kapitel 4 konzentriert sich auf BNs in Objektposition. Wir stellen einen direkten Vergleich an zwischen BNs als tatsächliche BNs, d.h. Nominale, die nicht mit einem Morphem markiert sind, und Kontexten, in denen sie mit dem Morphem -ra auftreten. Ich werde argumentieren, dass -ra lediglich markiert, dass ein BN oder auch ein anderes Nominal nicht in seiner VP-internen Position interpretiert, sondern in eine VP-externe Domäne bewegt wird. Das bedeutet, das Morphem -ra ist ein syntaktisches Morphem auf Phrasenebene. / This thesis explores the variable behavior of bare nouns in Persian. Bare singular nouns realize different grammatical functions, including subject, object and indirect object. They receive different interpretations, including generic, definite and existential readings. However, the task of understanding the reasons for, and limits on, this variation cannot be achieved without understanding a number of pivotal features of Persian sentential architecture, including Information Structure, prosody, word order, and the functions of various morphological markers in Persian. With respect to the discourse transparency of Incorporated Nominals, under certain circumstances, Persian bare nouns show discourse transparency. These circumstances are examined in chapter 3, and it is proposed that bare nouns do introduce a number neutral discourse referent. This proposal is phrased within Discourse Representation Theory. In the second half of the dissertation, the interpretation of bare nouns in different positions and with different grammatical functions are discussed. Under the independently supported hypothesis of position>interpretation mapping developed by Diesing (1992), we will see the role of the suffix -ra in indicating that an object has been moved out of VP. For subjects, there is no morphological marking corresponding to –ra on objects, and we have to rely on prosody and word order to determine how a VP is interpreted using theories of the interaction of accent and syntactic structure. It is proposed that both subject and object originate within the VP, and can move out to the VP-external domain. The motivation for these movements are informational-structural in nature, relating in particular to the distinctions between given and new information, and default and non-default information structure.

This dissertation reports very novel solutions for the trimming and compensation of various parameters of silicon micromechanical resonators and resonator-arrays. Post-fabrication trimming of resonance frequency to a target value is facilitated by diffusing in a deposited thin metal layer into a Joule-heated silicon resonator. Up to ~400 kHz of trimming-up and trimming-down in a 100 MHz Silicon Bulk Acoustic Resonators (SiBARs) are demonstrated via gold and aluminum diffusion respectively. The dependence of the trimming range on the duration of Joule heating and value of current passed are presented and the possibility of extending the trimming range up to ~4 MHz is demonstrated. Passive temperature compensation techniques are developed to drastically reduce the temperature coefficient of frequency (TCF) of silicon resonators. The dependence of TCF on the charge carriers in silicon are extensively studied and exploited for the very first time to achieve temperature compensation. A charge surplus via degenerate doping using boron and aluminum is shown to reduce a starting TCF of -30 ppm/°C to -1.5 ppm/°C while a charge depletion effected by creating multiple pn-junctions reduces the TCF to -3 ppm/°C. Further, shear acoustic waves in silicon microresonators have also been identified to effect a TCF reduction and have been excited in a concave SiBAR (or CBAR) to exhibit a TCF that is 15 ppm/°C lesser than that of a conventional rectangular SiBAR. The study on quality factor (Q) sensitivity to the various crystallographic axis of transduction in silicon resonators show that the non-repeatability of Q across various fabrication batches are due to the minor angular misalignment of ≤ 0.5° during the photolithography processes. Preferred axes of transduction for minimal misalignment sensitivity are identified and novel low-loss resonator-array type performances are also reported from a single resonator while transduced along certain specific crystallographic axes. Details are presented on an unprecedented new technique to create and fill charge traps on the silicon resonator which allows the operation of the capacitive SiBARs without the application of any polarization voltages (Vp) for the first time, making them very attractive candidates for ultra-low-power oscillator and sensor applications. Finally, a fabrication process that integrates both the capacitive and piezoelectric actuation/sensing schemes in microresonators is developed and is shown to compensate for the parasitics in capacitive silicon resonators while maintaining their high-Q.

No description available.

This master’s thesis deals with a design and optimization of an experimental scintillation secondary electron detector for the environmental scanning electron microscope and with a description of a detector operation principle. The experiment is founded on simulations of a gas flow in detector inner sections and on simulations of secondary electron trajectories in electrostatic fields of the detector. On the basis of the simulations, new solutions of the detector designs are proposed. For these designs, same simulations as previous are performed and designs that seem to be feasible for the secondary electron detection in environmental scanning electron microscope are selected.

This thesis deals with scanning electron microscope working at higher pressure in the specimen chamber. The main goal was to study the voltage contrast on the PN junction of the transistor under suitable working conditions for using environmental scanning microscope. The observation of sample was enabled by a scintillation detector designed for observation of high pressure.

This item contains the agenda, minutes, and attachments for the Faculty Senate meeting on this date. There may be additional materials from the meeting available at the Faculty Center.

Cancer is a leading cause of death that affects millions of people across the globe each year. Photodynamic therapy (PDT) is a relatively new treatment approach for cancer in which anticancer drugs are activated by light at an appropriate wavelength to generate highly cytotoxic reactive oxygen species (ROS) and achieve tumor destruction. Compared with conventional chemo- and radiotherapy, PDT can be performed with minimal invasiveness, local targeting and reduced side effects. However, most of the currently available PDT drugs mainly absorb in the visible part of the spectrum, where light penetration depth into human tissues is very limited. Therefore, increasing the treatment depth of PDT has been considered to be an important approach to improve the effectiveness of PDT for treating larger and thicker tumor masses. In this thesis, we present our investigation into the potential of two-photon activated PDT (2-γ PDT), combination therapy of PDT and chemotherapy, and bioluminescence-activated PDT as a means to increase the treatment depth of this modality. In 2-γ PDT, the photosensitizing agents are activated through simultaneous absorption of two photons. This approach allows the use of near-infrared (NIR) light that can penetrate deeper into tissues and thus, has the potential of treating deep-seated tumors and reducing side effects, while the non-linear nature of two-photon excitation (TPE) may improve tumor targeting. We have evaluated the PDT efficacy of a second-generation photosensitizer derived from chlorophyll a, pyropheophorbide a methyl ester (MPPa), through both one- and two-photon activation. We observed that MPPa had high one-photon (1-γ PDT efficacy against both cisplatin-sensitive human cervical (HeLa) and cisplatin-resistant human lung (A549) and ovarian (NIH:OVCAR-3) cancer cells when activated by femtosecond (fs) laser pulses at 674 nm. At a low light dose of 0.06 J cm-2, the MPPa concentration required to produce a 50% cell killing effect (IC50) was determined to be 5.3 ± 0.3, 3.4 ± 0.3 and 3.6 ± 0.4 μM in HeLa, A549 and NIH:OVCAR-3 cells, respectively. More significantly, we also found that MPPa could be effectively activated at the optimal tissue-penetrating wavelength of 800 nm through TPE. At a light dose of 886 J cm-2, where no measurable photodamage was observed in the absence of MPPa, the IC50 values were measured to be 4.1 ± 0.3, 9.6 ± 1.0 and 1.6 ± 0.3 μM in HeLa, A549 and NIH:OVCAR-3 cells, respectively. We obtained corresponding LD50 (the light dose required to produce a 50% killing effect) values of 576 ± 13, 478 ± 18 and 360 ± 16 J cm-2 for 10 μM MPPa, which were approximately 3-5 times lower than the published 2-γ LD50 of Visudyne® and 20-30 times lower than that of Photofrin®. These results indicate that MPPa may serve as a photosensitizer for both 1- and 2-γ activated PDT treatment of difficult-to-treat tumors by conventional therapies. Indocyanine green (ICG), a dye having an absorption maximum near 800 nm, has been considered to be a potential NIR PDT agent. However, the PDT efficacy of ICG has been found to be very limited probably due to the low yield of cytotoxic ROS. In the present work, we have evaluated the combination effects of ICG-mediated PDT with conventional chemotherapy mediated by two types of chemotherapeutic drugs, namely the type II topoisomerase (TOPII) poisons etoposide (VP-16)/teniposide (VM-26) and the platinum-based drugs cisplatin (CDDP)/oxaliplatin (OXP). Synergistic enhancement of cytotoxicity and increased yields of DNA double strand breaks (DSBs) were observed in HeLa, A549 and NIH:OVCAR-3 cancer cells treated with the combination of ICG-PDT and VP-16. The presence of VP-16 during the laser irradiation process was found to be critical for producing a synergistic effect. An electron-transfer-based mechanism, in which ICG could increase the yield of highly cytotoxic VP-16 metabolites, was proposed for the observed synergistic effects, although direct spectroscopic detection of the reaction products was found to be very challenging. Moreover, we observed a much lower degree of synergy in the human normal fibroblast GM05757 cells than that in the three cancer cell lines investigated. Synergistic effects were also observed in A549 cells treated with the combination of ICG-PDT and VM-26 (i.e. an analog of VP-16). Furthermore, the combination of low-dose CDDP/OXP and ICG-PDT was demonstrated to produce an additive or synergistic effect in selected cancer cell lines. These preliminary results suggest that the combination of ICG-PDT with VP-16/VM-26 or CDDP/OXP chemotherapy may offer the advantages of enhancing the therapeutic effectiveness of ICG-PDT and lowering the side effects associated with the chemotherapeutic drugs. Bioluminescence, the generation of light in living organisms through chemical reactions, has been explored as an internal light source for PDT in recent years. This approach, in principle, does not suffer from the limited tissue penetration depth of light. In the present project, we have evaluated the effectiveness of luminol bioluminescence in activating the porphyrin photosensitizers meso-tetra(4-sulfonatophenyl)porphine dihydrochloride (TPPS4) and Fe(III) meso-tetra(4-sulfonatophenyl)porphine chloride (FeTPPS). The combination treatment induced significant killing of HeLa cells, while additive effects were observed in two normal human fibroblast cell lines (GM05757 and MRC-5). Our observations indicate that bioluminescence of luminol may generate sufficient light for intracellular activation of PDT sensitizers. Furthermore, the combination treatment may have intrinsic selectivity towards cancerous tissues. In summary, we have demonstrated effective killing of cancer cells by MPPa-mediated 1- and 2-γ PDT, combination of ICG-PDT and VP-16/VM-26 or CDDP/OXP chemotherapy, and bioluminescence of luminol activated PDT mediated by TPPS4/FeTPPS. These positive preliminary results indicate that all these three approaches have the potential of increasing the treatment depth of PDT and facilitating the development of more effective PDT treatment strategies.