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Theoretical Calculations of The Second Hyperpolarizability inSubstituted meta-xylylene DiradicalsHarczuk, Ignat January 2012 (has links)
The electronic state ordering is calculated in substituted meta-xylylene diradicals for reproduction and comparison of results previously published by other authors. The second hyperpolarizability, γ, is calculated in the same systems using different methods. The diradical character is calculated for comparison and discussion of the γ values. The obtained electronic state ordering agrees qualitatively with previous findings. The γ values obtained from the finite-field method, which are related to the diradical character, agree with theory. The γ values obtained from the sum-over-states method, which relate to the vertical state ordering, are unsatisfactory.
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SYNTHESIS OF FUNCTIONALIZED [2.2] PARACYCLOPHANE PRECURSORS FOR FUNCTIONAL POLY(PARA-XYLYLENE) THIN FILM DEPOSITIONRahimi Razin, Saeid 12 March 2015 (has links)
Functionalized poly(para-xylylene) (PPX) coatings can be useful for biomaterials applications due to their biocompatibility and useful chemistry for the immobilization of biomolecules. However, their application is not widespread due to the difficulty in synthesizing the corresponding precursors. Here, a two-step method for amine functionalization of [2.2]paracyclophane (PCP) via direct nitration and reduction is developed. Nitration at super acidic conditions and temperatures as low as -78 °C, improved the stability of PCP toward strong acids and successfully minimized side reactions such as oxidation and polymerization. This procedure resulted in quantitative yields of 4-nitro-PCP, which was successively reduced by Raney nickel catalysis with sodium borohydride. Compared to the many other reduction systems, this method is simple, inexpensive and applicable in large scales. Additionally, carboxylation of PCP using the Freidel-Crafts acylation was attempted and so far, we have been able to show the synthesis of intermediate acylated products. Then, through the chemical vapour deposition polymerization of amino-PCP amine-functionalized poly(para-xylylene) (PPX-A) thin films were coated on Si wafer substrates. The substrates coated with PPX-A showed a higher surface energy compared with those of coated with un-substituted or chlorine substituted PPX films. Furthermore, results of the surface characterization demonstrated that the CVD process was able to transfer the functionalities of the precursors to deposited polymer films without alteration. However, the stability of primary amine groups in air and aqueous solutions is a matter of concern. Aging of amino-PCP and corresponding PPX-A films showed a decrease in the amount of primary amines which was accompanied by the appearance and increase of oxygen, indicating that the decrease of available amine groups is associated with oxidation. Nevertheless, both aminated precursor and polymer films remained intact under argon. The method presented here has great potential for widespread application of PPX-A as a convenient biomaterial for microarrays and cell culture. / Thesis / Master of Science (MSc)
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SYNTHESIS OF FUNCTIONALIZED [2.2]PARACYCLOPHANE PRECURSORS FOR FUNCTIONAL POLY(PARA-XYLYLENE) THIN FILM DEPOSITIONRahimi Razin, Saeid January 2015 (has links)
Functionalized reactive polymer coatings can be used in various biomaterials applications such as immunoassays and biomolecule immobilization. Poly(para-xylelene) is a relatively new biomaterial that has attracted attention over the past few decades in these areas due to its unique properties and biocompatibility. The introduction of functionalized, particularly aminated, poly(para-xylylene) will extend the application of these polymer coatings to a wide variety of biological studies. However, their application is not widespread due to the difficulty in synthesizing the corresponding precursors. Here, a two-step method for amine functionalization of [2.2]paracyclophane via direct nitration and reduction is developed. Nitration at super acidic conditions and temperatures as low as -78 °C, improved the stability of [2.2]paracyclophane toward strong acids and successfully minimized side reactions such as oxidation and polymerization. This procedure resulted in quantitative yields of 4-nitro[2.2]para-cyclophane, which was successively reduced by Raney nickel catalysis with sodium borohydride. Compared to the many other reduction systems, this method is simple, inexpensive and applicable in large scales. It does not require harsh reaction conditions and within short reaction times, delivers quantitative amounts of the reduced product. At the end, 4-amino[2.2]paracyclophane was collected in 77% overall yield. Additionally, carboxylation of [2.2]paracyclophane using the Freidel-Crafts acylation was attempted and so far, we have been able to show the synthesis of intermediate acylated products. The successful syntheses of products were verified by FT-IR, NMR and MS, and comparison of their solubility and physical properties showed significant changes upon substitution of the pristine [2.2]paracyclophane. Then, through the chemical vapour deposition polymerization of 4-amino[2.2]paracyclophane amine-functionalized thin films were coated on Si wafer substrates and their properties were compared with Parylene N and C, two well-known poly(para-xylylene) films. The substrates coated with amino-poly(para-xylylene) showed a higher surface energy compared with those of coated with un-substituted or chlorine substituted poly(para-xylylene) films. Furthermore, results of the surface characterization conducted by grazing angle reflectance IR spectroscopy and XPS, demonstrated that the CVD process was able to transfer the functionalities of the precursors to deposited polymer films without alteration. However, with the applied process parameters we obtained a higher functional density of amine groups on the surface.
These polymer films can be deposited on a variety of substrates and be used as functional surfaces for a variety of applications. However, the stability of primary amine groups in air and aqueous solutions is a matter of concern. Aging of 4-amino-[2.2]paracyclophane and corresponding poly(para-xylylene) films in air and mili-Q water was studied via XPS and NMR spectroscopies. The results showed a decrease in the amount of primary amines with storage time in air or water for both aminated precursor and polymer. The kinetics for these changes, however, were not equal for the precursors and polymer films. The decay of amine groups was accompanied by the appearance and increase of oxygen, indicating that the decrease of available amine groups is associated with oxidation which can transform them to more stable amide and nitro compounds. In total, practical challenges involved in manufacture, durability and applications of amine-functionalized Parylene coatings are discussed and a reliable scheme for fabricating such films with high tunabiliy of the surface functional density is demonstrated. The highly practical method presented here provides great potential for widespread application of amine-functionalized poly(para-xylylene) as an outstanding biomaterial for microarrays, tissue engineering and cell culture studies. / Thesis / Master of Science (MSc)
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Multifunctional Metallo-Supramolecular Matrials and SensorsBurnworth, Mark Gross 14 March 2011 (has links)
No description available.
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Příprava poly-para-xylylenových vrstev a charakteriazace jejich vlastností / Poly-para-xylylene films preparation and characterization of their propertiesMenčík, Přemysl January 2012 (has links)
Poly-p-xylylene is a basic polymer of parylene family. It was discovered in 50s of the 20th century. In practical applications, there are used several derivates. Most of them are discussed in this thesis. Poly-p-xylylene has many utility properties, like barrier, thermal and mechanical properties. It can be used for conservation and protection of electronic equipments, medical tools and devices or museum exhibits. The most important property of parylene is its low dielectric constant which enables parylene to have good insulating properties in form of very thin layer. The most common precursor used for parylene coatings by Chemical Vapor Deposition (CVD) is [2,2]paracyclophane. Special device invented for this process was described in this thesis, including every part and assembly. The main aim of this thesis was to test properties of thin parylene layers on metal samples. High degree of polymer crystallinity was confirmed by confocal laser microscopy and optical microscopy in the polarized light measurements. Problems in the conventional method of production of parylene layers were found during the measurement of thickness of layers. Purity of deposited films was determined using Infrared spectroscopy (IR). Parylene barrier properties were quantified by the measurement of Oxygen Transmission Rate through a layer deposited on the surface of PP foil. Because the research has been mainly focused on protection of museum exhibits, the corrosion resistance test is the most important. Metal samples with thin parylene film were compared to samples with conventional restoration coating. The samples with parylene protection were slowly corroded by point corrosion. In contrast to them, the samples conserved by conventional restoration method were almost destroyed by corrosion.
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