Browsing by Subject "Polymer"
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Item Open Access Analysis of polymers using evolved-gas and direct-pyrolysis techniques(Royal Society of Chemistry, 1994) Fares, M. M.; Yalcin, T.; Hacaloglu, J.; Gungor, A.; Süzer, ŞefikThermal analysis of polystyrene, poly(p-methylstyrene) and poly(α-methylstyrene) has been carried out using evolved-gas analysis by infrared and mass spectrometry, and direct-pyrolysis analysis by mass spectrometric techniques. Evolved-gas analysis, both by infrared and mass spectrometry, reveals features due mainly to the corresponding monomers or stable, volatile, and low relative molecular mass degradation products. In direct-pyrolysis mass spectrometry, however, primary decomposition products and heavier fragments such as dimers and trimers can also be detected. The ion-temperature profiles of the corresponding monomer ions reveal information about the thermal stability of the polymers.Item Open Access Bacteria-immobilized electrospun fibrous polymeric webs for hexavalent chromium remediation in water(Springer Berlin Heidelberg, 2016) Sarioglu, O.F.; Celebioglu A.; Tekinay, T.; Uyar, TamerThe development of hexavalent chromium remediating fibrous biocomposite mats through the immobilization of a hexavalent chromium reducing bacterial strain, Morganella morganiiSTB5, on the surfaces of electrospun polystyrene and polysulfone webs is described. The bacteria-immobilized biocomposite webs have shown removal yields of 93.60 and 93.79 % for 10 mg/L, 99.47 and 90.78 % for 15 mg/L and 70.41 and 68.27 % for 25 mg/L of initial hexavalent chromium within 72 h, respectively, and could be reused for at least five cycles. Storage test results indicate that the biocomposite mats can be stored without losing their bioremoval capacities. Scanning electron microscopy images of the biocomposite webs demonstrate that biofilms of M. morganii STB5 adhere strongly to the fibrous polymeric surfaces and are retained after repeated cycles of use. Overall, the results suggest that reusable bacteria-immobilized fibrous biocomposite webs might be applicable for continuous hexavalent chromium remediation in water systems.Item Open Access Biomimicry of multifunctional nanostructures in the neck feathers of mallard (Anas platyrhynchos L.) drakes(Nature Publishing Group, 2014-04-22) Khudiyev, T.; Dogan, T.; Bayındır, MehmetBiological systems serve as fundamental sources of inspiration for the development of artificially colored devices, and their investigation provides a great number of photonic design opportunities. While several successful biomimetic designs have been detailed in the literature, conventional fabrication techniques nonetheless remain inferior to their natural counterparts in complexity, ease of production and material economy. Here, we investigate the iridescent neck feathers of Anas platyrhynchos drakes, show that they feature an unusual arrangement of two-dimensional (2D) photonic crystals and further exhibit a superhydrophobic surface, and mimic this multifunctional structure using a nanostructure composite fabricated by a recently developed top-down iterative size reduction method, which avoids the above-mentioned fabrication challenges, provides macroscale control and enhances hydrophobicity through the surface structure. Our 2D solid core photonic crystal fibres strongly resemble drake neck plumage in structure and fully polymeric material composition, and can be produced in wide array of colors by minor alterations during the size reduction process.Item Open Access Dispersion of multi-walled carbon nanotubes in an aqueous medium by water-dispersible conjugated polymer nanoparticles(2010) Baykal, B.; Ibrahimova, V.; Er, G.; Bengü, E.; Tuncel, D.Vertically aligned multi-walled carbon nanotubes (MWCNTs) synthesized by the alcohol catalytic CVD (ACCVD) technique are dispersed in water with the aid of water-dispersible conjugated polymer nanoparticles (CPNs). The interactions between CPNs and CNTs are studied with spectroscopy (UV-Vis, fluorescence and Raman) and electron microscopy techniques are used to confirm attachment of CPNs to the CNT sidewalls.Item Open Access Effect of triboelectric charges on friction and wear of polymers at macro scale(2017-12) Sayfidinov, KhaydaraliThe interest towards the study of underlying mechanism behind tribology has gained enormous attention recently since almost one-fourth of the total produced global energy is consumed by friction and wear. Dry sliding or rubbing two dielectric polymers on each other results in surface charging showing significant effects on friction coefficients and wear. Determination of the correlation between triboelectricity and tribologic events like friction and wear, the control of friction coefficient, and reducing wear by surface charging constitutes the main idea and research topic of this thesis. However, tribological events are very complicated considering the fact that diverse processes encompassing of physical and chemical changes occur at the counterface. Therefore, the fundamentals of friction is still controversial. Owing to tribological actions that occur due to contact between different phases of the matter, interfaces generate tribocharges due to electron, ion, and material transfer mechanisms. Even though the fundamental mechanism is still vague and under debate, it is believed that static electrification due to tribological actions are utterly because of electron transfer. Current studies unveiled that physical based phenomena are not the only source of surface electrification but also chemical changes such as bond rupturing and following surface oxidation that can take place as a result of mechanical actions on an insulating polymer. Consequently, these two groups of surface events; surface electrification and friction are expected to demonstrate a mutual relation, and detailed study concerning this relation needs to be investigated in order to solve e.g. energy loss and wear problems in tribology. To achieve this goal, it is essential to understand the main mechanisms and processes involved, and reveal the connections between tribological events and establish a relationship between all the intrinsic and extrinsic properties of materials from molecular, nano to meso scale. Thus, in this study, we investigated the contribution of triboelectrification to friction by taking into account some factors - surface area, load, atmosphere - between common polymers and pure cellulose under dry friction conditions.Item Open Access Electrostatics of Polymer Translocation Events in Electrolyte Solutions(American Institute of Physics Inc., 2016) Buyukdagli, S.; Ala-Nissila, T.We develop an analytical theory that accounts for the image and surface charge interactions between a charged dielectric membrane and a DNA molecule translocating through the membrane. Translocation events through neutral carbon-based membranes are driven by a competition between the repulsive DNA-image-charge interactions and the attractive coupling between the DNA segments on the trans and the cis sides of the membrane. The latter effect is induced by the reduction of the coupling by the dielectric membrane. In strong salt solutions where the repulsive image-charge effects dominate the attractive trans-cis coupling, the DNA molecule encounters a translocation barrier of ∼10 kBT. In dilute electrolytes, the trans-cis coupling takes over image-charge forces and the membrane becomes a metastable attraction point that can trap translocating polymers over long time intervals. This mechanism can be used in translocation experiments in order to control DNA motion by tuning the salt concentration of the solution.Item Open Access Evaluation of fiber diameter and morphology differences for electrospun fibers on bacterial immobilization and bioremediation performance(Elsevier, 2017-05) Sarioglu O.F.; Celebioglu A.; Tekinay, T.; Uyar, TamerIn this report, morphology and fiber diameter differences of electrospun polysulfone (PSU) fibers on bacterial immobilization and bioremediation performance were evaluated. PSU fibers were produced with aligned or randomly oriented morphologies, and PSU fibers with thinner and thicker diameters were also produced. PSU fibers were utilized as carrier matrices for bacterial integration and the sample showing highest bacterial immobilization was tested for bioremediation of ammonium and methylene blue dye in water. It was found that randomly oriented and thinner PSU fibers are the optimal system for bacterial immobilization, hence bioremediation studies were performed with this sample. The results demonstrated that bacteria immobilized PSU fibers are promising candidates for simultaneous removal of ammonium and methylene blue dye, and they have a potential to be used in remediation of water systems.Item Open Access Influence of channel layer thickness on the electrical performances of inkjet-printed In-Ga-Zn oxide thin-film transistors(IEEE, 2010-12-10) Wang, Y.; Sun, X. W.; Goh, G. K. L.; Demir, Hilmi Volkan; Yu, H. Y.Inkjet-printed In-Ga-Zn oxide (IGZO) thin-film transistors (TFTs) with bottom-gate bottom-contact device architecture are studied in this paper. The impact of the IGZO film thickness on the performance of TFTs is investigated. The threshold voltage, field-effect mobility, on and off drain current, and subthreshold swing are strongly affected by the thickness of the IGZO film. With the increase in film thickness, the threshold voltage shifted from positive to negative, which is related to the depletion layer formed by the oxygen absorbed on the surface. The field-effect mobility is affected by the film surface roughness, which is thickness dependent. Our results show that there is an optimum IGZO thickness, which ensures the best TFT electrical performance. The best result is from a 55-nm-thick IGZO TFT, which showed a field-effect mobility in the saturation region of 1.41 cm(2)/V . s, a threshold voltage of 1 V, a drain current on/off ratio of approximately 4.3 x 10(7), a subthreshold swing of 384 mV/dec, and an off-current level lower than 1 pA.Item Open Access Inorganic / polymeric assemblies as catalysts for water splitting(2018-09) Kap, ZeynepSplitting water with sunlight is an attractive and promising research topic over the last two decades since it produces a non-carbon-based resource, hydrogen, which is a suitable energy carrier due to its high energy output and for being environmentally friendly. A great deal of research in this eld has been centered on the development of e cient water oxidation and reduction catalysts. The rst part of the thesis focuses on a novel photosensitizer-water oxidation catalyst (PS-WOC) dyad. A Ru metal coordinated pyridine-based ligand and a cobalt-iron pentacyanoferrate have been used as the photosensitizer and water oxidation catalyst, respectively. In this assembly, poly(4-vinylpyridine) serves as the bridging group between two units mainly to enhance the performance and stability of the system compared to its analogous intermolecular system. A 5-fold improvement on the catalytic activity has been achieved with a turnover frequency (TOF) of 5:6 10-4 s-1 under 1 hour light illumination and a turnover number (TON) of 11 in a 6-hour catalytic study. Evolved oxygen was quanti ed with gas chromatography. Structural characterization was carried out by Fourier Transform Infrared Spectroscopy (FTIR), Ultraviolet-Visible Spectroscopy (UV-Vis), X-Ray Photoelectron Spectroscopy (XPS), X-Ray Powder Di raction (XRD), Scanning Electron Microscopy (SEM), and Energy-dispersive X-Ray Spectroscopy (EDX) techniques. Comparative XPS and FTIR studies were performed on pristine and post-catalytic samples to con rm the stability of the dyad. In the second part of the study, a facile synthetic pathway using poly(4- vinylpyridine) as a polypyridyl platform has been reported for the formation of a cobalt-based metallopolymer. Electrochemical studies indicate that the metallopolymer acts as an e cient H2 evolution catalyst similar to cobalt-polypyridyl complexes. Furthermore, metallopolymer can be transformed to cobalt particles when a cathodic potential is applied in the presence of an acid. It has been found that these cobalt particles also serve as e cient hydrogen evolution catalysts. Approximately 80 µmoles of H2 gas can be collected during 2 h of electrolysis at -1.5 V (vs. Fc+/0) in the presence of 60 mM of acetic acid. A comprehensive study of the electrochemical and electrocatalytic behavior of cobalt-poly(4-vinylpyridine) was discussed in detail.Item Open Access Lignin as an antistatic additive for common polymers(2018-01) Bedük, TutkuStatic electricity is a common phenomenon that can causes million-dollar loses in industries such as polymer, air and space, and drug manufacture due to the detrimental effects of electrostatic discharge of the accumulated charges on surfaces. Doping of the materials, i.e. polymers, with antistatic agents can reduce or prevent these problems. So far, the antistatic additives used were chosen to make the final material/composite conductive to dissipate the surface charges, by either directly doping with conductive materials (e.g. metals or carbon powder), or by doping with additives (e.g. ions) to increase surface humidity. The doped materials usually lose their inherent properties such as the mechanical properties because of the high concentrations of the additive. To provide a more universal solution to this problem and avoid the changes in the material properties after doping, the mechanism of static charge formation, which has been on debate for many years, should be clarified. Recent studies of our group and others have shown that the main mechanism behind the charge formation on electrified (polymer) materials is the bond-breakages on the surfaces of the materials, which lead to mechanoanion, mechanocation, mechanoradical active ends. The former two accounts for the charge on the surfaces and, as we have shown, the latter group (mechanoradicals) stabilizes the charged species. Previously, in our group, it was shown that by removing the mechanoradicals with radical scavenger antioxidants one can destabilize the charges – doping with antioxidants makes materials antistatic. However, the scavenger antioxidants we had used in this example to show the antistatic behavior were far from being practical in use for general polymers -that are produces in millions of tons per year- because of their individual prices. Lignin is the world’s second most abundant polymer. It has antioxidant properties, so it is a good candidate as an antistatic agent for common polymers. In this study we assess the lignin’s antistatic action by doping it into common polymers - elastomers (silicon rubber) and thermoplastics (PE, PP, PVC), and comparing the accumulated net charge on the doped and undoped polymers upon contact electrification. It was shown that the increase in lignin concentration and decrease in particle size of the lignin enhances the antistatic property in the polymers, due to an increase in radical scavenging OH groups, as verified by 31P-NMR analysis. We certify that the antistatic property is because of the radical scavenging action and not by increase in the surface conductivity. By doping polymers with cheap and abundant lignin, we provide a more universal, environment-friendly method for preventing electrostatic charge accumulation on common polymers, which are produced in millions of tons per year.Item Open Access Liquid-liquid diffusion ‐ assisted crystallization: a fast and versatile approach toward high quality mixed quantum dot ‐ salt crystals(Wiley-VCH Verlag, 2015) Adam, M.; Wang, Z.; Dubavik, A.; Stachowski, G. M.; Meerbach, C.; Soran-Erdem, Z.; Rengers, C.; Demir, Hilmi Volkan; Gaponik N.; Eychmuller, A.Here, a new, fast, and versatile method for the incorporation of colloidal quantum dots (QDs) into ionic matrices enabled by liquid-liquid diffusion is demonstrated. QDs bear a huge potential for numerous applications thanks to their unique chemical and physical properties. However, stability and processability are essential for their successful use in these applications. Incorporating QDs into a tight and chemically robust ionic matrix is one possible approach to increase both their stability and processability. With the proposed liquid-liquid diffusion-assisted crystallization (LLDC), substantially accelerated ionic crystallization of the QDs is shown, reducing the crystallization time needed by one order of magnitude. This fast process allows to incorporate even the less stable colloids including initially oil-based ligand-exchanged QDs into salt matrices. Furthermore, in a modified two-step approach, the seed-mediated LLDC provides the ability to incorporate oil-based QDs directly into ionic matrices without a prior phase transfer. Finally, making use of their processability, a proof-of-concept white light emitting diode with LLDC-based mixed QD-salt films as an excellent color-conversion layer is demonstrated. These findings suggest that the LLDC offers a robust, adaptable, and rapid technique for obtaining high quality QD-salts.Item Open Access Materials for articular cartilage regeneration(Bentham Science Publishers B.V., 2012) Tombuloglu, Ayşegül; Tekinay, Ayşe B.; Güler, Mustafa O.Many health problems remaining to be untreatable throughout the human history can be overcome by utilizing new biomedical materials. Healing cartilage defects is one of the problems causing significant health issue due to low regeneration capacity of the cartilage tissue. Scaffolds as three-dimensional functional networks provide promising tools for complete regeneration of the cartilage tissue. Diversity of materials and fabrication methods give rise to many forms of scaffolds including injectable and mechanically stable ones. Various approaches can be considered depending on the condition of cartilage defect. A scaffold should maintain tissue function within a short time, and should be easily applied in order to minimally harm the body. This review will cover several patents and other publications on materials for cartilage regeneration with an outlook on essential characteristics of materials and scaffolds.Item Open Access Mechanism of triboelectricity: a novel perspective for studying contact electrification based on metal-polymer and polymer-polymer interactions(2016-08) Musa, Umar GishiwaThe static electricity that is generated when two identical or different materials come in contact with each other and separated is a well known physical phenomenon that has been studied for over 25 centuries. Contact charging occurs in technological and natural aspects of our everyday life. Generation of lightning and the feeling of unexpected shocks on dry days are excellent examples of naturally occurring phenomenon, while in technology it is used for photocopying and laser printing. Owing to the increase in energy consumption around the globe and demand for carbon emissions free energy sources, the triboelectric effect has recently being utilized as an e ffective means of harvesting mechanical energy and converting it into electricity for novel applications like powering portable electronic devices and self powered active sensing. Despite the fact that it has been known and applied for many years, the fundamental mechanism of contact electrification is still not fully understood. This study proposes a mechanism for triggering such triboelectric charge based on polymer-polymer and metal-polymer interactions. Conventionally, the mechanism of electrostatic charge generation is being presumed as a process giving rise to a combination of positive (arising from contact) and negative (arising from separation) charges in every single contact and separation. However, in our mechanism we propose a concept that shows combination of both positive and negative charges as \contact" and either positive or negative charge, depending on the initial contact-charge polarity of the material (due to surface charge mosaic), as \separation" charge. Different kinds of polymers like polydimethylsiloxane (PDMS), polytetra uoroethylene (PTFE), Polyethersulfone (PES) and polypropene (PP) were used in this study and similar characteristic was observed for all of the polymers. Thus, our perception of the working principle of triboelectri cation between two dielectric materials or a metal and a dielectric material is consistent and potentially vital in comprehending some unresolved controversies on triboelectricity.Item Open Access Pd nanocube decoration onto flexible nanofibrous mats of core-shell polymer-ZnO nanofibers for visible light photocatalysis(Royal Society of Chemistry, 2017) Arslan, O.; Topuz, F.; Eren, H.; Bıyıklı, Necmi; Uyar, TamerPlasmonic enhancement for electron-hole separation efficiency and visible light photocatalysis was achieved by Pd nanocube decoration on a ZnO nanolayer coated onto electrospun polymeric (polyacrylonitrile (PAN)) nanofibers. Since exciton formation and sustainable electron-hole separation have a vital importance for realizing better solar energy in photovoltaic and photocatalytic devices, we achieved visible light photocatalysis by Pd nanocube decoration onto well designed core-shell nanofibers of ZnO@PAN-NF. By controlling the cubic Pd nanoparticle size and the thickness of the crystalline ZnO nanolayer deposited onto electrospun PAN nanofibers via atomic layer deposition (ALD), defect mediated visible light photocatalysis efficiency can be increased. By utilizing nanofabrication techniques such as thermal decomposition, electrospinning and ALD, this fabricated template became an efficient, defect mediated, Pd nanocube plasmon enhanced photocatalytic system. Due to the enhanced contact features of the Pd nanocubes, an increase was observed for the visible light photocatalytic activity of the flexible and nanofibrous mat of Pd@ZnO@PAN-NF.Item Open Access Polymer-free electrospun nanofibers from sulfobutyl ether7-beta-cyclodextrin (SBE7-β-CD) inclusion complex with sulfisoxazole: fast-dissolving and enhanced water-solubility of sulfisoxazole(Elsevier, 2017-10) Yildiz, Z. I.; Celebioglu A.; Uyar, TamerIn this study, our aim was to develop solid drug-cyclodextrin inclusion complex system having nanofibrous morphology in order to have fast-dissolving property and enhanced water-solubility of poorly water-soluble drug. Here, we prepared a highly concentrated aqueous solution of inclusion complex between sulfisoxazole and sulfobutyl ether7-beta-cyclodextrin (SBE7-β-CD, Captisol®), and then, without using any polymeric matrix, the electrospinning of sulfisoxazole/SBE7-β-CD-IC nanofibers was performed in order to obtain free-standing and handy nanofibrous web. As a control sample, nanofibers from pure SBE7-β-CD was also electrospun and free-standing nanofibrous web was obtained. The SEM imaging revealed that the bead-free and uniform nanofiber morphology with the average fiber diameter (AFD) of 650 ± 290 nm for sulfisoxazole/SBE7-β-CD-IC NF and 890 ± 415 nm for pure SBE7-β-CD NF was obtained. The inclusion complex formation between sulfisoxazole and SBE7-β-CD in sulfisoxazole/SBE7-β-CD-IC NF sample was confirmed by 1H NMR, TGA, DSC, XRD and FTIR analyses. Due to the combined advantage of cyclodextrin inclusion complexation and high surface area of electrospun nanofibers, fast-dissolving property with enhanced water-solubility was successfully achieved for sulfisoxazole/SBE7-β-CD-IC NF. Our findings suggest that electrospun nanofibers/nanowebs from CD-IC of poorly water-soluble drugs may offer applicable approaches for high water-solubility and fast-dissolving tablet formulations for drug delivery systems.Item Open Access Polymer-free nanofibers from vanillin/cyclodextrin inclusion complexes: high thermal stability, enhanced solubility and antioxidant property(Royal Society of Chemistry, 2016) Celebioglu A.; Kayaci-Senirmak, F.; Ipek, S.; Durgun, Engin; Uyar, TamerVanillin/cyclodextrin inclusion complex nanofibers (vanillin/CD-IC NFs) were successfully obtained from three modified CD types (HPβCD, HPγCD and MβCD) in three different solvent systems (water, DMF and DMAc) via an electrospinning technique without using a carrier polymeric matrix. Vanillin/CD-IC NFs with uniform and bead-free fiber morphology were successfully produced and their free-standing nanofibrous webs were obtained. The polymer-free CD/vanillin-IC-NFs allow us to accomplish a much higher vanillin loading (∼12%, w/w) when compared to electrospun polymeric nanofibers containing CD/vanillin-IC (∼5%, w/w). Vanillin has a volatile nature yet, after electrospinning, a significant amount of vanillin was preserved due to complex formation depending on the CD types. Maximum preservation of vanillin was observed for vanillin/MβCD-IC NFs which is up to ∼85% w/w, besides, a considerable amount of vanillin (∼75% w/w) was also preserved for vanillin/HPβCD-IC NFs and vanillin/HPγCD-IC NFs. Phase solubility studies suggested a 1:1 molar complexation tendency between guest vanillin and host CD molecules. Molecular modelling studies and experimental findings revealed that vanillin:CD complexation was strongest for MβCD when compared to HPβCD and HPγCD in vanillin/CD-IC NFs. For vanillin/CD-IC NFs, water solubility and the antioxidant property of vanillin was improved significantly owing to inclusion complexation. In brief, polymer-free vanillin/CD-IC NFs are capable of incorporating a much higher loading of vanillin and effectively preserve volatile vanillin. Hence, encapsulation of volatile active agents such as flavor, fragrance and essential oils in electrospun polymer-free CD-IC NFs may have potential for food related applications by integrating the particularly large surface area of NFs with the non-toxic nature of CD and inclusion complexation benefits, such as high temperature stability, improved water solubility and an enhanced antioxidant property, etc.Item Open Access Preparation of Au and Au-Pt nanoparticles within PMMA matrix using UV and X-ray irradiation(2009) Ozkaraoglu, E.; Tunc, I.; Süzer, ŞefikAu and Au-Pt alloy nanoparticles are prepared and patterned at room temperature within the PMMA polymer matrix by the action of 254 nm UV light or X-rays. The polymer matrix enables us to entangle the kinetics of the photochemical reduction from the nucleation and growth processes, when monitored by UV-vis spectroscopy. Accordingly, increase of the temperature to 50 °C of the reaction medium increases the nucleation and growth rates of the nanoparticle formation by more than one order of magnitude, due to enhanced diffusion and nucleation at the higher temperature, but has no effect on the photochemical reduction process. Presence of Pt ions also increases the same rate, but by a factor two only. Similar photochemical reduction and particle growth take also place within the PMMA matrix, when these metal ions are subjected to prolonged exposure to X-rays, as evidenced by XPS analysis. Both angle-resolved and charge-contrast measurements using XPS reveal that the resultant Au and Pt species are in close proximity to each other, indicating the Au-Pt alloy formation to be the most likely case.Item Open Access Synthesis of blue-shifted luminescent colloidal GaN nanocrystals through femtosecond pulsed laser ablation in organic solution(Springer Netherlands, 2016-05) Demirel, A.; Öztaş T.; Kurşungöz, C.; Yılmaz, İ.; Ortaç, B.We demonstrate the synthesis of GaN nanocrystals (NCs) with the sizes of less than the doubled exciton Bohr radius leading quantum confinement effects via a single-step technique. The generation of colloidal GaN nanoparticles (NPs) in organic solution through nanosecond (ns) and femtosecond (fs) pulsed laser ablation (PLA) of GaN powder was carried out. Ns PLA in ethanol and polymer matrix resulted in amorphous GaN-NPs with the size distribution of 12.4 ± 7.0 and 6.4 ± 2.3 nm, respectively, whereas fs PLA in ethanol produced colloidal GaN-NCs with spherical shape within 4.2 ± 1.9 nm particle size distribution. XRD and selected area electron diffraction analysis of the product via fs PLA revealed that GaN-NCs are in wurtzite structure. Moreover, X-ray photoelectron spectroscopy measurements also confirm the presence of GaN nanomaterials. The colloidal GaN-NCs solution exhibits strong blue shift in the absorption spectrum compared to that of the GaN-NPs via ns PLA in ethanol. Furthermore, the photoluminescence emission behavior of fs PLA-generated GaN-NCs in the 295–400 nm wavelength range is observed with a peak position located at 305 nm showing a strong blue shift with respect to the bulk GaN.Item Open Access Theoretical analysis of effects of π-conjugating substituents on building blocks for conducting polymers(American Chemical Society, 1999) Salzner, U.; Lagowski, J. B.; Pickup, P. G.; Poirier, R. A.Geometries of 4-dicyanomethylene-4H-cyclopenta[2,1-b:3,4-b'] dithiophene 1 and its C=O, C=S, C=CH2, C=CF2, and C=C(SR)2 analogues were optimized using density functional theory. Three of the above groups, C=C(CN)2, C=O, and C=S, were also examined on dipyrrole, difuran, dicyclopentadiene, and diborole. Electronic structures were analyzed with respect to their suitability as building blocks for conducting polymers with the natural bond orbital (NBO) method. All bridging groups investigated decrease HOMO-LUMO gaps compared to the unsubstituted parent dimers. Substitution affects HOMO and LUMO energies. Energy gap reduction is caused by a stronger decrease of LUMO energies compared to HOMO energies. The C=S group leads to even smaller energy gaps than the dicyanomethylene group since the HOMO is lowered less in energy with C=S. Compared to unsubstituted dimers, the strongest substituent effects are found with pyrroles and furans. Boroles and thiophenes are least affected. The smallest HOMO-LUMO gaps are obtained for electron-poor systems such as boroles followed by cyclopentadienes. This is analogous to the trend for the unsubstituted parent systems. All of the bridging groups are potential π-acceptors due to their low-lying π*-orbitals, and the corresponding polymers are predicted to be n-dopable. In aromatic structures, the LUMO is localized around the bridging substituent and the coefficients at the α-carbon atoms that reflect electron density are small. This might contribute to the poor conductivity of the n-doped form of poly-1. Electron- poor monomers and polymers tend to switch to quinoid structures. In quinoid repeat units, the HOMO is localized but not as strongly as the LUMO in the aromatic repeat units. The LUMO in quinoid repeat units is delocalized with large coefficients at the α-carbon atoms. Quinoid polymers could therefore be good conductors in the n-doped state.