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Research Project Design and Synthesis of Novel Compounds Based on Dithienylpyrrole Systems Containing Azobenzene Units and Their Electrochemical and Optical Properties as well as Their Processable Conducting PolymersChemical EngineeringTwo dithienylpyrroles based on azo dyes, namely 2,5’-dimethyl-[4-(2,5-di-thiophen-2-yl-pyrrol-1- yl)-phenyl]azobenzene (1) and 2,5’-dimethyloxy-[4-(2,5-di-thiophen-2-yl-pyrrol-1-yl)-phenyl] azobenzene (2), were synthesized and their corresponding polymers (P1 and P2) were successfully obtained via electropolymerization. The monomers have lower oxidation potentials (0.75 V and 0.80 V vs. Ag/AgCl for 1 and 2, respectively) when compared to their analogous. Both monomers exhibited photoisomerism properties under irradiation at 360 nm. During the irradiation process, for example, the color of monomer 2 changes from yellow to greenish yellow. The electroactive polymer films have well-defined and reversible redox couples with a good cycle stability in both aqueous and organic solutions. The polymer films also exhibited electrochromic behaviors; color changes from yellowish green to dark green for the P1 (λma= 435 nm and Eg= 2.31 eV) and from mustard color to green for P2 (λmax= 430 nm and Eg= 2.34 eV). Furthermore, the soluble polymers demonstrated different hues of yellow and green colors. The electrochemical and optical properties of a novel conducting copolymer called poly(3,4- ethylenedioxythiophene-co-1)-(P(EDOT-co-1)) are reported. Electrochemically synthesized P(EDOTco- 1) based on the azo dye has a well-defined and reversible redox couple (0.37 V vs. Ag/AgCl) with good cycle stability. The copolymer film exhibits high conductivity (13 S/cm) as well as electrochromic behavior (magenta when neutralized and transmissive sky blue when oxidized). Furthermore, electrooptically active copolymer film has a low band gap of 1.79 eV with a π−π* transition at 555 nm.Research Project Design and Synthesis of Novel Compounds Based on Donor-Acceptor Systems and the Applications of Their Conducting PolymersChemical EngineeringConducting polymers continues to facinate many scientists and to become the subject of many researchs in technological and academic areas. The reason for the popularity of the conducting polymers is that they trigger the development of advanced technological materials. Bearing in mind that, desired properties (processability, stability, conductivity, optical properties and so on) of these materials depend on the design and the synthesis of starting monomers. The conducting polymers obtained from the marvellous monomers can be amenable to practical use: (bio)sensors, artificial muscles, displays, electrochromic, memory and photovoltaic devices, supercapacitors, solar cells, light emitting diodes, etc. In this study, the design, synthesis and chemical and/or electrochemical polymerization of monomers (1-6) which are necessary for the generation of processable, low band gap, environmetally stable, reversible electronic and optical properties during n- and p-type dopings, fast switching of the electronic states and different hues of various colors and novel conducting polymers based on donor-acceptor-donor system. Selenium and/or oxygen atoms will be used instead of sulfur atom in benzothiodiazole unit known as acceptor unit in literature. When compared to sulfur, selenium is less electronegative and has larger size, which will obviously affect the electronic and optical properties of obtained conducting polymers. The polymers can be used as RGB (red, green, blue) displays due to green color in its neutral state and transparency in its oxidized state, as supercapacitors due to large and fast doping/dedoping capability, as solar cells due to absorption bands in the region of UV-vis, as photovoltaic devices and radar system due to the high absorption/transmittance values and the emission bands beyond NIR region, as antistatic coatings due to high transparency in the oxidized state, and as n-/p-type transistors due to their reversible and stable n- and p-type dopings. Also, some pre-works on the monomers studied in this project showed that one of the conducting polymers has green color and the modification on the monomer structure of this polymer can open a new door for the discovery of cyan color in the CMY (cyan, magenta, yellow) color system. In this project, initially the monomers (1-6) mentioned above, which is the basic unit for the polymers to be useful in the desired applications, wil be designed, synthesized and characterized. After the characterization of the monomers (by NMR, elemental analysis, FTIR, mass, UV-vis, X-Ray and voltammetric techniques), they will be polymerized into suitable medium via chemical and/or electrochemical polymerization methods. Then, the electronic and optical properties of the obtained conducting polymers will be characterized to be amenable for use in RGB displays, solar cells, supercapacitors, photovoltaic devices, transistors and so on).Research Project Design, Synthesis and Investigation of New Nano-Dimensional CompoundsChemical EngineeringCombination of conjugated polymers and Polyhedral oligomeric silsesquioxane (POSS) units under the same roof was taken place recently. In very few numbers of studies in the literature, it was reported that POSS units gave thermal, mechanical, optical and electrochemical stability to the condujugated polymers. In this study, in order to overcome the problems faced by the industrial field of conjugated polymers (insolubility, thermal, mechanical, optical and electrochemical instability, etc.) the inorganic (POSS) and organic (thiophene) units will be melted in the same pot for producing new POSS based polymeric materials. While the most important reason for using POSS as inorganic segment in the hybrid compound that will be synthesized is not only being nanosized but also the ability to give thermal and electrochemical stability and make the polymer soluble, 3,4-ethylenedioxythiophene and 3,4-propylenedioxythiophene, which are easily and linearly polymerized and provide to obtain electroactive polymers, will be used as organic segments. In the first stage of the project, our aim is primarily to sythesize and analyze the compounds whose structures were designed and specified and the sythetic pathways were determined. In the next step, necessary conditions to obtain electroactive polymers (homopolymer and copolymer) will be determined by investigating the electochemical and optical properties of compunds. With the realization of the project, it will be a milestone progress towards polymerization and applications (hydrophobic surfaces, electrochromic devices and polymeric light emitting diodes) of these compounds. The results of the study have the ability to be “know-how” and “patent”. Also, these results will be a data source for the future projects that can be pursued with “public” and “private” sectors. Besides, the subject of the project will be a part of a doctoral thesis, with the originality of the scope of the project and the outcomes have potential to contribute the researcher identity of Atilim University. Besides there is possibility for outcomes to become a patent, they have strong possibility to be published in prestigious journals and presented in conferences.Research Project Design, Synthesis and Technological Applications of New Inorganic-Organic Hybrid Polymeric MaterialsChemical EngineeringIn this study, a new carborane based electron donor-acceptor-donor type electroactive monomer (1) was synthesized successfully. Monomer 1 has an irreversible oxidation peak at 0.90 V (vs Ag/AgCl) and by the help of repeting cyclic voltammetry between -0.90 V and 1.00 V it was polymerized via electrochemical method. Electrochemical polymerization was performed in 0.1 M tetrabutylammonium hexafluorophosphate (TBAH) /acetonitrile and 0.1 M TBAH/DKM. Electrochemical and optical properties of the corresponding polymer (P1) were investigated. The presence of carborane unit in the polymer backbone preserve the polymer against the ambient conditions, high overoxidation potentials;therefore, the polymer become robust and preserve its properties (optical and electronic). For example, after 1000 cycles, P1 has 96% of its electroactivity. P1 having a narrow band gap like 1.64 eV also have different colors at various oxidation states: therefore, it proved that it is a promising material as an electrochromic material: light violet at neutral state and transmissive sky blue at oxidized state. This stuation was supported by the construction of an electrochromic device. Also, by the sake of comparison, the analog of monomer 1, monomer (59) and polymer (P59) were synthesized. As a result, it was proved that 1 and P1 materials are very precious materialsResearch Project Donör-akseptör düzeninde yeni bir bileşik grubununtasarımı, sentezi ve iletken polimerlerinin uygulama alanlarıChemical EngineeringDonor-acceptor-based electrochromic polymers, unknown in the literature, were synthesized and the optical and electrochemical properties of these materials were examined. In this study, in which both the donor effect and the acceptor effect were examined, soluble and processable materials with colors such as green, blue, cyan and black, although very few in number in the literature, were synthesized which are indispensable for their application areas. Necessary characterization studies have been carried out for the anticipated technological applications.Research Project Kimyasal ışıl-ışıma özelliğine sahip heterosiklik monomerlerin ve iletken polimerlerinin sentezlenmesi ve uygulama alanlarıChemical EngineeringA new group of compounds with chemiluminescence properties were designed and synthesized, and after their identification, their behavior towards metal ions was examined. Some of these compounds, which are likely to be used in both analytical chemistry and forensic science, have been successfully polymerized by electrochemical methods and their optical and electrochemical properties have been identified.Research Project Kükürtten Bağlanan Liganlar İçeren Yeni Platin Mavisi Komplekslerinin sentezi, Elektrokimyasal Karakterizasyonu ve Antitümör EtkileriChemical EngineeringPlatinum blues have generated substantial interest not only due to their activity but also for their brillant colors. The compounds involving various amide and pyrimidine ligands are intense blue, blue-green or purple. A variety of the structures that contain nitrogen, N, and oxygen, O, have been assigned to the platinum blues, however, no platinum blues compound containing sulphur, S and nitrogen has been reported. Apart from the above mentioned complexes, some platinum pyrimidine blues complexes having antitumor activity was also be studied, recently. The main objective of the proposed project is to senthesize the platinum blues compounds by using sulphur donor ligands, 2-aminothiophenol and 3-aminothiophenol at the first time. Analysis of the products will be performed by UV-Vis, IR, ESR, ESCA, 1H-NMR, 13C-NMR ve 195Pt-NMR methods and the crystal structures will be identified by using X-ray diffraction spectrophotometer. The change in the DNA (Deoxyribonucleic acid: gene) conformation that is generated by the interaction of the complexes will be determined by electrophoresis and the electrochemical methods. Electrochemical behaviour of the complexes will be studied by cyclic voltammetry (CV) and the constant potental electrolyses of the complexes will be carried out at the peak potentials. The changes in the electronic absorption spectra of the complexes will be followed in situ by UV-vis spectrophotometer during the electrolysis in order to identify the electrolysis products and possible reaction intermediates. The number of the electrons that are transferred during the electrolysis will be counted by coulommetric methods and the presence of the unpaired electrons or the radicals will be proved by electron spin resonance spectroscopy. Moreover, the charges pf the platinum ions present in the complex structure will be determined by ESCA and the structural identification of the complexes will also be performed by NMR (nuclear magnetic resonans) spectra besides X-ray diffraction spectrophotometer.Research Project Kurşun İçermeyen Yeni Nesil Primer Patlayıcı Tasarımı, Sentezi ve KarakterizasyonuChemical EngineeringMercury fulminate, lead azide and lead styphnate have been used as primary explosives for a long time. They are very good initiatory explosives, however, they have some serious drawbacks such as thermal, hydrolytic, chemical instability, highly sensitive to light, high toxicity of the compounds themselves, high sensitivity to mechanical stimuli. Today, improvement on the existing primary explosives is essential to find materials without heavy metals with safer production line and more efficient use compared to the present ones. The main aim of this study is to synthesize and explore the initiating performance of novel energetic organic and metallic compounds, which lead to providing the similar or even better performance with lower toxicity. For this purpose, 5-(kloronitrometil)-4-nitro-1H-imidazol ligand and its cobalt, copper, iron and zinc complexes in different geometries were synthesized. The characterization of the complexes was elucidated by elemental analysis, ESI-MS, IR and 1H-NMR spectroscopy techniques. The geometric and electronic properties of the complexes were determined using gas phase density functional theory calculations. Then, the explosive properties of the energetic materials obtained were studied with theoretical methods. The thermal stability of the materials was investigated by TG-TA methods. Explosion safety tests of the two most suitable complexes having exothermic energy profile were completed in the form of service procurement. The results obtained showed that the prepared complexes have very high thermal stability, they do not show the ability to be a primary explosive. However, the complexes having exothermic properties can be used as propelling power, and the complexes having endothermic properties can be used as additives to increase thermal stability against impact and friction in high energy rocket fuels.Research Project Oksim Türevi Ligandlar İçeren Yeni Platin(II) Komplekslerinin Sentezi, Elektrokimyasal Karakterizasyonu ve DNA’ya Bağlanma AktivitesiChemical EngineeringThe interest in platinum based antitumor drugs has been started in 1960’s with the serendipitous discovery by Rosenberg of the inhibition of cell division by platinum complexes. Cisplatin, cisdiamminedichloroplatinum(II), was approved by United Sates FDA in 1978 as an antitumor drug. It most effective against testicular and ovarian cancer. Despite the success of cisplatin chemotherapy, it has several serious side effects such as nausea, vomiting, nephrotoxicity, ototoxicity, neuropathy and myelosuppression. The other main reason for a failure of cisplatin chemotherapy is resistance of tumors to the drug. The resistance can be intrinsic or acquired and limits the applicability of cisplatin. Due to all of these reasons, the design and synthesis of more active, less toxic and orally active platinum drugs have been prompted in order to reduce severe side effects, to overcome drug resistance and to improve the patient’s quality of life. The main aim of this study is to synthesize novel platinum complexes with variety of ligands of oximes as potential anticancer drug leads providing better efficacy with low tissue resistance compared to cisplatin. Analysis of the products will be performed by UV-Vis, IR, ESR, ESCA, 1H-NMR, 13C-NMR ve 195Pt-NMR methods and the crystal structures will be identified by using X-ray diffraction spectrophotometer. The change in the DNA (Deoxyribonucleic acid: gene) conformation that is generated by the interaction (e.g groove binding, intercalation and H-bonding) of the complexes will be determined by electrophoresis with some spectroscopic and electrochemical methods.. Electrochemical behaviour of the complexes will be studied by cyclic voltammetry (CV) and the constant potental electrolyses of the complexes will be carried out at the peak potentials. The changes in the electronic absorption spectra of the complexes will be followed in situ by UV-vis spectrophotometer during the electrolysis in order to identify the electrolysis products and possible reaction intermediates. The number of the electrons that are transferred during the electrolysis will be counted by coulommetric methods and the presence of the unpaired electrons or the radicals will be proved by electron spin resonance spectroscopy. Moreover, the charges of the platinum ions present in the complex structure will be determined by ESCA and the structural identification of the complexes will also be performed by NMR (nuclear magnetic resonans) spectra besides X-ray diffraction spectrophotometer.Research Project Preparation of magnetic nanoparticles which enable the use of 18F-FDG as multi-modal imaging agents in PET-MRI applications/18F-FDG nin PET-MR görüntüleme uygulamalarında multi-modal görüntüleme ajanı olarak kullanılmasına yönelik manyetik nanoparçacıkların hazırlanmasıChemical EngineeringIt is becoming increasingly evident that PET-MRI multi-modal imaging systems have great potential in practical medicine and for basic scientific research. Consequently there is a wide interest in developing proper imaging agents for these applications. Superparamagnetic iron oxide (SPIO) nanoparticles are already, extensively, being used as MRI contrast agents. The labeling of these nanoparticles with radioactive isotopes provides a new generation for MRI agents. Combination of the required properties, in the body of the same sample for both measurement techniques, ensures that both images are coming from the same spot and simultaneously. This approach provides more accurate and reliable data for diagnosis and treatment of the illness. One of the candidates of the applicable radioactive isotopes is 18F, an easily available one and is being produced in our country. However its chemical binding to delivery agents requires several steps of exhaustive chemical treatments. A laboratory/firm which tends to fabricate iron oxide nanoparticles labeled with 18F should reconstruct a new manufacturing plant, which needs a laborious and a quite expensive operation. Instead, a new process, which can convert already available PET contrast agents into PET-MRI agents without requiring any special expertise, would be more practical and economical.Research Project Preparation of Multifunctional Photocatalytic Nanocomposit Materials and, Usage in Hydrogen Output and Environmental Remediation/Çok Fonksiyonlu Fotokatalitik Nanokompozit Malzemelerin Hazırlanması, Hidrojen Eldesinde ve Çevre Islahında KullanımıChemical EngineeringDue to the increasingly polluted environment and the limited energy reserves, the development of high efficiency renewable technologies, green energy sources and eco-friendly methods for environmental remediation and energy production is highly important. Hydrogen (H2), as a clean and carbonless energy source, is of great potential in solving the environmental pollution and energy shortage. Turkey is a country that clued-in textile production. But widespread discharge of wastewaters from the textile industries, which contain large amounts of dyes, has become a great concern to the environment and ecosystem due to their non-biodegradability, toxicity, and potential carcinogenicity. Therefore finding effective treatment methods and extending the treatment units which use them is necessary. The need to meet stringent international regulations and standards for wastewater discharge has motivated the development of efficient, non-toxic and low-cost photocatalytic materials for the photodegradation of organic pollutants with solar energy in wastewater. Besides mild operating conditions photocatalytic process can be powered by sunlight which significantly reducing the energy required and therefore the operating costs. Thus, semiconductor photocatalysis has attracted widespread attention in scientific community due to its potential application in environmental remediation and hydrogen production. Owing to the strong oxidizability, nontoxicity, and long-term photostability, nanostructured titanium dioxide (nano-TiO2) has many advantages when compared with other photocatalysts. However, there are still some shortcomings, such as the lack of a visible light response, a low quantum yield, and lower photocatalytic activity. To overcome these problems, studies have been focused on some strategies, including noble metal deposition, doping of metal or nonmetal ions, blending with another metal oxide, surface photosensitizing with dye, and compositing with polymer. In particular, organic/inorganic nanocomposite materials, where the organic major component is based on polymers, are a fast-growing area of research. Catalyst recovery and reuse are the two most important features for many catalytic processes. Most heterogeneous systems require a filtration or centrifugation step to recover the catalyst. However, magnetically supported catalysts can be recovered with an external magnet due to the paramagnetic character of the support thus remarkable catalyst recovery can be provided without the need for a filtration step and the catalysts can be subsequently reused in another cycle. In this study, it is planned to develop multifunctional organic-inorganic nanocomposite photocatalysts for H2 production from harmful volatile organic compounds (VOC) founded in industry based waste waters and provide environmental remediation with the removal of organic dyes founded in waste waters from industry simultaneously with photocatalytic degradation by using sunlight. For this purpose, novel magnetically recyclable, Poly (3, 4-ethylenedioxythiophene (PEDOT) and noble metal modified TiO2 based (CoFe2O4-PEDOT-TiO2/M, (M=Ag, Au, Pd)) nanocomposites with high photocatalytic activity and well-separation property will be produced. The photocatalytic properties (enhanced light absorption and charge-transfer kinetics) of the nanocomposites aimed to be enhanced by the synergetic effects of TiO2 nanoparticles, noble metal nanoparticles and PEDOT loading. Besides, with the addition of magnetic silica coated cobalt ferrite (CoFe2O4@SiO2) nanoparticles into the nanocomposite structure, their separation from the liquid phase and reuse process can be done via application of an external magnetic field is the another aim of this study. The composition, structure, morphology, and optical properties of the prepared nanocomposites will be investigated by TEM, HR-TEM, STEM, FE-SEM, XPS, XRD, ICP-OES, N2-Ads.-Des., FTIR, Raman and UV-Vis. The comparative photocatalytic activity of the prepared catalysts will be investigated under different light sources (UV, Vis, sunlight). The ethanol which is an easily evaporable organic compound with a relatively low toxicity to study the photocatalytic degradation of VOC’s is chosen as model pollutant. To evaluate the photocatalytic activity of the produced catalysts in the degradation of organic dye, methyl orange (MO) and methylene blue (MB), typical pollutants in the textile industry which have the relatively high toxicity and complex structures make them difficult to be treated by physical and biological methods, will be investigated under UV and Vis light irradiation. Finally the efficiency of the prepared multifunctional advanced materials on the mixture of model compounds and real samples will be investigatedResearch Project Preparation of Novel Nanostructures with High Light to Heat Conversion and Investigation of their Fhotothermal Efficiencies and Toxicities/Yakın Kızılötesi Bölgede Yüksek Işık-Isı Çevrimine Sahip Özgün Nanoyapıların Hazırlanması, Fototermal Etkinliklerinin ve Toksisitelerinin AraştırılmasıChemical EngineeringCancer is known as one of the main causes of death and according to Centers for Disease Control and Prevention Organization accounted for 8.2 million deaths worldwide in 2012 with an increasing incidence rate. For this reason, progressing efficient therapeutic strategies with low toxicities to eradicate tumours specificly, is considered as the main object in the cancer treatments. Poor specificity toward malignant tissues, systemic side effects, low efficacy and drug resistance are the well-known disadvantages of widely applied radiation and chemotherapies. Thus, to improve the cancer therapy, it is expected that the therapeutic methods should eliminate only diseased cells/tissues without causing collateral damage selectively. The development of new protocols for biomedical application are encouraged by advanced nanotechnologies and production of novel nanomaterials. When it is compared the conventional tratment like surgery, radiation therapy, and chemotherapy with nanoparticle approach, nanoparticle treatments are minimally invasive and should result in minimal side effects. Accordingly, novel and effective therapeutics with unique light-to-heat conversion property of nanoscale materials can be utilized for cancer treatment. Among them, near-infrared (NIR) region photothermal therapy (PTT) has become more popular and developed quickly due to minimally invasive treatments for patients. Generally, photothermal therapy depends on the photosensitizers taken up by cancer cells to transfer light to heat, leading to photoablation of the cells and subsequent cell death. Therefore, photosensitizing agents are a key factor in photothermal therapy. In PTT, due to its easy operation, ability to be locally focused on a specific region and minimal absorbance by skin and tissues to allow for noninvasive penetration of reasonably deep tissues, near-infrared (NIR) light (700–1000 nm) is preferred. Recently, due to their high photothermal conversion efficiency and the ease of synthesis and modification, inorganic based fotothermal therapy agents (PTA) have received great interest. Among them, gold nanoparticles (AuNPs) are considered as a special photosensitizer due to their strong localized surface plasmon resonance (LSPR). Different types of Au nanoparticle based photosensitizers in photothermal therapy, like nanorods, nanocages, and nano-core–shells, nanostars have been reported. Unfortunately, the problem related to the potential toxicity induced by photothermal agents (especially for carbon nanotubes or graphene, CTAB coated Au rods, copper sulfide crystals and iron oxide nanoparticles (Fe3O4 NPs), is still an unresolved debate, which will inevitably limit future clinic applications of PTT. Therefore, it is significant to explore an effective fototermal therapy agent in order to decrease the extra-high-dose nanoparticles used in photothermal ablation of cancer with NIR irradiation which can generate potential toxicity to the body. In addition, with the presence of effective agents in the near infrared region, deeper cases may be treated with photothermal therapy. In this project proposal, it is aimed to develop novel photothermal therapy agents, which can reduce toxic effect, using in very small quantities, by increasing the light to heat conversion efficiency and be able to provide treatment even in deeper case due to the effective light to heat conversion in the near infrared region (NIR) because of the different and improved plasmon resonance properties than the photothermal agents in the literature.For this it is planned to prepare 6 different phototermal agent and detection of the efficiencies of them in photothermal therapy. The first two of these structures will be formed by adding gold (AuNPs) and gold-silver bimetallic nanoparticles (AuAgNPs) of 1-3 nm in size onto the hollow gold nanoparticles (Hollow AuNPs) with a 60-100 nm size and 5-10 nm shell thickness (AuNPs/HollowAuNPs(1. agent), AuAgNPs/HollowAuNPs (2. agent)). The third and fourth agents will be prepared by adding gold nanoparticles and gold-silver bimetallic nanoparticles of 1-3 nm in size on magnetic iron oxide nanoparticles coated with a thin silica shell (AuNPs/Fe3O4-SiO2 (3. agent) ve AuAgNPs/Fe3O4-SiO2 (4. agent)). The proposed last two agents will be formed with the addition of gold nanoparticles and gold-silver bimetallic nanoparticles onto the resulting structure formed by the addition of gold shells over the thin silica layer coated iron oxide nanoparticles (AuNPs/AuShell/Fe3O4-SiO2 (5. agent), ve AuAgNPs/AuShell/Fe3O4-SiO2 (6. agent)). Characterization of the photothermal therapy agents will be done by using HR-TEM, XPS, VSM, ICP-OES, XRD, UV-Vis, Raman. The photothermal effects of the prepared structures will then be measured by using an 808 nm wavelength laser irradiation in solution and then their activity in the cancer cell line (in vitro) will be investigated. Finally, toxicity studies of photothermal agents will be carried out.Research Project Quorum Sensing Inhibitör Özelliği Gösteren Yeni Moleküllerin Sentezi ve Çevreci Hidrojel Boya Sisteminde KullanımıChemical EngineeringBacteria present in the seawater quickly form a biofouling on the surfaces immersed in it. This process starts with the adhesion of organic nutrients such as protein and carbohydrates to the surface in the first seconds. Bacteria adhere to the nutrient film on the surface and form a protective biofilm of proteins and polysaccharides around them. The biological fouling process continues with the adhesion and development of diatoms (microalgae), macroalgae spores and macroorganism larvae such as of mussels. However, this sequential model is not valid in all cases. Biological fouling limits the maneuverability of water vehicles, increases fuel consumption and greenhouse gas emissions. Therefore, antifouling methods are important in terms of economy and environment issues. One of the methods to prevent microfouling on surfaces is to prevent communication between bacteria. Bacteria communicate with each other through "Quorum Sensing" (QS) molecules to permanently attach to surfaces. Gram-negative bacteria use acylated homoserine lactone (AHL) molecules for QS communication. Molecules resembling AHL have the potential to inhibit QS. Hydrogels with a three-dimensional polymer network are also considered promising coatings with high antifouling performances against marine organisms. The super hydrophilic property of hydrogel materials enables them to absorb large amounts of water into three-dimensional polymeric networks and form a hydrated layer on their surface, which can prevent the adhesion of micro or macroorganisms. For these reasons, in order to solve the problem of biological fouling within the scope of the proposed project, it is aimed to synthesize and characterize new QS analogs that will prevent bacteria from forming biofilms and settling on surfaces. As a result of the bacterial tests, the two compounds with the best antibiofilm properties will be used as biocides, and a water-based hydrogel paint formula with anti-QS properties will be developed. With the hydrogel technology, it is aimed to significantly reduce the friction force, fuel consumption and emissions together with the biofouling on the ship surface. The hydrogel paint designed within the scope of the project is water based, self-curing, can be easily applied to a ship surface by brushing or spraying and can be produced in powder form. Environmentalist methods were chosen in both synthesis stages. The use of organic solvents that cause volatile organic compounds (VOCs) to be released into the atmosphere is avoided.Research Project Self-Cleaning Surfaces: A New Approach for Water-Repellent SurfacesChemical EngineeringIt was observed that natural structures (such as lotus and rice leaves) which exhibit superhydrophobic (water-hating) and self-cleaning properties have micro- and nanoscale roughness on their surfaces. Typical superhydrophobic surface protects the surface from getting wet by repelling water drops. Owing to water repellency property, self-cleaning superhydrophobic surfaces have several applications in industry and daily life. In this study, the aim is to prepare superhydrophobic materials containing nano- and microscale surface roughness by using sol-gel and hydrothermal methods and to coat onto different surfaces (glass, paper,textile, metal etc.) In the study, in order to obtain nano- and microscale surface roughness, coating material will be prepared by using polymer, silica nanoparticles and metal complexes. Implementation of the prepared material onto the surface will be done via spray coating, spin-coating, and/or sol-dip-coating techniques. Hydrophobic and self-cleaning properties of the prepared material will be examined via contact angle and surface free energy measurements and the required optimizations will be done. Surface morphology, physical and chemical properties of the obtained surfaces will be characterized via SEM, TEM, UV-Vis and FTIR analysis. For the purpose of determining strength of material, some physical tests (film thickness, spreading and appearance, adhesion, strength, scratch resistance, brightness, adequacy of contamination, ultraviolet and temperature strength resistance) and chemical tests (detergent resistance and detergent /alkali) will be done. In the project, it is suggested that depending on coating type, surface can achieve properties such as antibacterial, anti-mold, antifungal, protection against acid, water and stain repellency, low contact adhesion, and preliminary studies for future are considered to be carried on in the biochemistry laboratory of our department. In the near future, when we consider the coating of surfaces exposing external factor that has mentioned above with this technology, the preparation of such a material at Atılım University and therewithal the production through industry partnership and introducing for usage while considering commercially carry great importance.Research Project Synthesis and Applications of High Sulfur Content Polymeric MaterialsChemical EngineeringSulfur has been used in various applications. With approximately 70 million tonnes produced each year from petroleum refining, elemental sulfur is widely available and inexpensive (∼$120 USD per tonne). A significant portion of sulfur is used in the production of sulfuric acid. Although elemental sulfur is not toxic, it is a flammable solid so finding productive uses for this stockpiled material under the open air is important. Finding large-scale uses for this sulfur, such as conversion to useful polymers, would be an important advance. Polymerization of elemental sulfur has long been studied. Sulfur polymerizes above 159 oC. Unfortunately, the polymeric sulfur undergoes depolymerization since elemental sulfur is more stable thermodynamically at room temperature. As a solution for this problem, in Pyun’s pioneering study, an alkene was used as an organic cross-linker via inverse vulcanization method. In this study, sulfur was heated to 185 °C to initiate ring-opening polymerization and then, addition of alkene resulted in cross-linking. Because of the high sulfur content (50-90 wt%) and the corresponding polysulfur copolymers represented several interesting chemical, material, and optical properties: redox acitivity (cathode materials for Li-S batteries), a high refractive index and a mid IR region of transparency (night vision, thermal imaging), self healing, heavy metal ions remediation, etc. These usage areas have inspired further exploration of inverse vulcanization with a variety of unsaturated cross-linkers to obtain polysulfides with various properties. On the other hand, today vegetable oils are the most important renewable raw material for the chemical industry. About 80% of the global oil and fat production is vegetable oil. These oils make highly pure fatty acids available such as oleic acid (OA) from sunflower, linoleic acid (LA) from soybean, linolenic acid (LnA) from linseed, and ricinoleic acid from castor oil (Figure 1.1(a)). Vegetable oils are expected to play a key role during the 21st century to synthesize polymers from renewable sources. Within this contribution, the project is aimed at the synthesis and application of new high sulfur content polymeric materials using fatty acids (Figure 1.1(a)). Figure 1. (a) Chemical structures of some fatty acids, (b) the synthesis and chemical modification (poly(S-r-OA)-PE) of a polsulfur copolymer (poly(S-r-OA)) via inverse vulcanization. Due to the presence of double bonds, these pure fatty acids will be used firstly for cross-linking by using inverse vulcanization method (Figure 1.1(b)). Correponding copolymers are expected to be soluble in common organic solvents, processable and electroactive. In particular, the effect of double bonds and the free alkyl chains on the polysulfur copolymers will be investigated systematically by using OA, LA and LnA. Another feature of the copolymers obtained from these fatty acids will be the presence of reactive functional units (-COOH), which makes it possible to make chemical modifications (amide, ester, etc. linkages) of the polysulfur copolymers and to convert them into new polymers with different properties. With this project, the first examples of high sulfur content derivatives of polyesters and polyamides (like poly(S-r-OA)-PE) may have been synthesized by the chemical modification (esterification and amidation) of polysulfur copolymers. After inverse vulcanization process, the characterization of the obtained polysulfur copolymers will be done by using NMR, Raman, FTIR, UV, GPC, SEM, DSC, TGA etc., techniques. Electrochemical, optical, and material properties of the polymers will be investigated and tested as potential promising materials for use in Li-S batteries, heavy metal ions remediation and photocatalytic dye removal. The properties of obtained polymers will be compared with each other as well as with the literature data. Lastly, studies will be carried out to produce polymers in kg scale, and the applicability of the method to be applied to the industry will be tested. With reaching the project targets, it will be possible to polymerize elemental sulfur with the renewable vegetable fatty acids; therefore, huge amounts of sulfur can be used more effectively and an important step for sustainable synthesis/production in the polymer industry will be realized.Research Project Synthesis and Applications of High Sulfur Content Polymeric Materials/Yüksek Kükürt İçerikli Polimerik Malzemelerin Sentezi ve UygulamalarıChemical EngineeringSulfur has been used in various applications. With approximately 70 million tonnes produced each year from petroleum refining, elemental sulfur is widely available and inexpensive (∼$120 USD per tonne). A significant portion of sulfur is used in the production of sulfuric acid. Although elemental sulfur is not toxic, it is a flammable solid so finding productive uses for this stockpiled material under the open air is important. Finding large-scale uses for this sulfur, such as conversion to useful polymers, would be an important advance. Polymerization of elemental sulfur has long been studied. Sulfur polymerizes above 159 oC. Unfortunately, the polymeric sulfur undergoes depolymerization since elemental sulfur is more stable thermodynamically at room temperature. As a solution for this problem, in Pyun’s pioneering study, an alkene was used as an organic cross-linker via inverse vulcanization method. In this study, sulfur was heated to 185 °C to initiate ring-opening polymerization and then, addition of alkene resulted in cross-linking. Because of the high sulfur content (50-90 wt%) and the corresponding polysulfur copolymers represented several interesting chemical, material, and optical properties: redox acitivity (cathode materials for Li-S batteries), a high refractive index and a mid IR region of transparency (night vision, thermal imaging), self healing, heavy metal ions remediation, etc. These usage areas have inspired further exploration of inverse vulcanization with a variety of unsaturated cross-linkers to obtain polysulfides with various properties. On the other hand, today vegetable oils are the most important renewable raw material for the chemical industry. About 80% of the global oil and fat production is vegetable oil. These oils make highly pure fatty acids available such as oleic acid (OA) from sunflower, linoleic acid (LA) from soybean, linolenic acid (LnA) from linseed, and ricinoleic acid from castor oil (Figure 1.1(a)). Vegetable oils are expected to play a key role during the 21st century to synthesize polymers from renewable sources. Within this contribution, the project is aimed at the synthesis and application of new high sulfur content polymeric materials using fatty acids (Figure 1.1(a)). Figure 1. (a) Chemical structures of some fatty acids, (b) the synthesis and chemical modification (poly(S-r-OA)-PE) of a polsulfur copolymer (poly(S-r-OA)) via inverse vulcanization. Due to the presence of double bonds, these pure fatty acids will be used firstly for cross-linking by using inverse vulcanization method (Figure 1.1(b)). Correponding copolymers are expected to be soluble in common organic solvents, processable and electroactive. In particular, the effect of double bonds and the free alkyl chains on the polysulfur copolymers will be investigated systematically by using OA, LA and LnA. Another feature of the copolymers obtained from these fatty acids will be the presence of reactive functional units (-COOH), which makes it possible to make chemical modifications (amide, ester, etc. linkages) of the polysulfur copolymers and to convert them into new polymers with different properties. With this project, the first examples of high sulfur content derivatives of polyesters and polyamides (like poly(S-r-OA)-PE) may have been synthesized by the chemical modification (esterification and amidation) of polysulfur copolymers. After inverse vulcanization process, the characterization of the obtained polysulfur copolymers will be done by using NMR, Raman, FTIR, UV, GPC, SEM, DSC, TGA etc., techniques. Electrochemical, optical, and material properties of the polymers will be investigated and tested as potential promising materials for use in Li-S batteries, heavy metal ions remediation and photocatalytic dye removal. The properties of obtained polymers will be compared with each other as well as with the literature data. Lastly, studies will be carried out to produce polymers in kg scale, and the applicability of the method to be applied to the industry will be tested. With reaching the project targets, it will be possible to polymerize elemental sulfur with the renewable vegetable fatty acids; therefore, huge amounts of sulfur can be used more effectively and an important step for sustainable synthesis/production in the polymer industry will be realized.Research Project Synthesis And Applications of New Conjugated Polymeric Materials Based on CarboraneChemical EngineeringCombination of conjugated polymers and carborane units under the same roof was taken place recently, for the first time in 2003. In very few number of studies in the literature, it was reported that carborane units gave thermal, mechanical, optical and electrochemical stability to the condujugated polymers. In this study, in order to overcome the problems faced by the industrial field of conjugated polymers (insolubility, thermal, mechanical, optical and electrochemical instability, etc.) the inorganic and organic units will be melted in the same pot for producing new carborane based polymeric materials. In the first two years of the project, initially carborane based electron donor-acceptor-donor (D-A-D) type new inorganic-organic hybrid monomers will be designed and synthesized and then soluble conjugated polymers (low band gap, reversible electronic and optical properties, n- and/or p-type doping behavior, fast switching of various redox states and different colors and environmetally and thermally stable novel florescent conjugated polymers) will be tried to obtain by use of electrochemical and chemical methods. While alkyl substituted 3,4-propylenedioxythiophene and carbazole units will be used as D unit, carborane units will be used as A unit. Tetrabutylammonium salts (perchlorate, tetrafluoroborate and hexafluorophosphate) as the supporting electrolyte and acetonitrile, dichloromethane and/or propylene carbonate will be used as the solvent in the electrochemical polymerization. For the chemical polymerization, Stille Coupling, anhydrous FeCl3 and / or CuI oxidant and/or Yamamoto type Ni (0) dehalogenation polymerization techniques will be used. After the investigation of the electrochemical, optical and thermal properties of the obtained polymeric materials, studies for the industrial and technological applications (electrochromic devices and light emitting diodes (LEDs)) will be done at Atılım University and METU by experienced teams in the last two years of the project. When the materials designed in the project are moved successfully to the industrial fields such as electrochromic devices and LED applications, it will be brought to a solution to an industrial problem by using carborane chemicals. As a result, it will be the primary purpose and goal of our project to overcome the problem faced by industrial areas (electrochromic devices and LEDs) with the products based on special carboranes, which can be synthesized in our country.Research Project Synthesis and Polymerization of Monomers possessing Chemiluminescence Properties and Their Application AreasChemical EngineeringA novel class of chemiluminescence (KL) compounds was designed, synthesized and characterized; 2,3-dihydro-thieno[3,4-d]pyridazine-1,4-dione (T-Lum), 2,3-dihydro-furo[3,4-d]pyridazine-1,4-dione (FLum) and 2,3-dihydro-pyrrolo[3,4-d]pyridazine-1,4-dione (P-Lum). The KL reaction of the compounds in alkali medium was examined by using hydrogen peroxide and potasium permanganate oxidants and a possible KL mechanism was investigated. Synthesized compounds are especially sensitive to Fe+3 ion and this property makes them amenable to use as iron sensors. Also, the sensitivity of these materials towards iron makes them a promising candidate in forensic area to detect trace amount of blood at crime scene. Compounds are also sensitive both iron and blood samples even at lower concentration. By using the sensitivity of compounds towards hydrogen peroxide, the detection of many analytes will be possible. Beside the KL property, the electrochemiluminescence (EKL) property of the materials makes them very precious. Since the oxidation of pyridazine ring occurs before the aromatic rings, electropolymerization of the functionalized pyrrole, furan and thiophene compounds with pyridazine rings were not possible. To overcome this problem, new compounds, which have lower oxidation potential than that of pyridazine ring, were designed, synthesized and characterized; 5,7-di-tthiophen-2-yl-2,3-dihydro-thieno[3,4- d]pyridazine-1,4-dione (TTT-Lum) and 5,7-di-ethylenedioxythiophene-2-yl-2,3-dihydro-thieno[3,4- d]pyridazine-1,4-dione (ETE-Lum). The materials synthesized in the form of donor-acceptor-donor exhibit both KL and EKL properties, which makes them promising candidates in the analytical chemistry and forensic science. Compounds were polymerized successfully without oxidizing pyridazine ring via electrochemical polymerization (only neat BF3-Et2O solution or 0.1 M LiClO4 or 0.1 M tetrabutylammonium perchlorate dissolved in acetonitrile containing 5% of BF3-Et2O by volume ) and the electrochemical and optical properties were investigated. Electroactive and electrochromic polymeric materials, exhibiting reversible redox behaviours, have lower band gaps between 1.6 and 1.7 eV. Also, the polymer films are very stable; the electroactivity and the EKL properties were remain unchangeable after many cycles. Furthermore, the soluble polymer films in alkali medium with their KL properties will attract many attention in the academic areas.Research Project Synthesis of Electroactive Chemiluminescent Compounds and Polymers for Blood Detection in ForensicChemical EngineeringCombination of pyridazine based and chemiluminescent units with electroactive compounds and conjugated polymers have been taken place recently. These compounds and conjugated polymers have been reported to be used instead of luminol in order to detect blood traces in forensic science. These studies resulted in the birth of a new series of compounds so-called “luminol-type compounds”. In this study, a new series of chemiluminescent and conjugated trimeric compounds bearing pyridazine ring (Scheme 1) and their polymers will be synthesized and characterized structurally. Then, their chemiluminescent properties and forensic applications (blood detection) will be scrutinized. Scheme 1. Chemical structure of the compounds bearing redox active terminals and chemiluminescent pyridazine units In order to achieve this aim, phthalic anhydride will be utilized to synthesize the target molecules in three steps. This will be advantageous when compared the synthesis of some luminol derivatives which require multiple steps. After the completion of the structural characterization of the compounds, the chemiluminescent reactions of the compounds in basic medium will be tested firstly in the presence of only hydrogen peroxide and then together with various metal cations as catalyst by using a photomultiplier tube. If iron ion is found to exhibit a catalytic role in the chemiluminescent process, the application of blood trace detection in forensic will be studied. First of all, hemin as a hemoglobin analogue will be used to get a standard curve and then the blood samples will be studied. Obtained data will be compared with luminol and its derivatives and also the effect of the substituents (electron donating units: furan, thiophene and selenophene) of the compounds on the chemiluminescent process will be investigated. Next step will be the electrochemical polymerization of the compounds. The structural analyses of the polymers will be studied by using voltammetric and spectroscopic methods (cyclic voltammetry, NMR, FTIR, UV-vis, SEM, GPC, etc.). Chemiluminescent properties and forensic applications of their polymers will also be studied. Furthermore, since the polymers can be obtained as films via electrochemical polymerization, the electrochemiluminescent properties of these polymers will also be investigated. In addition to the polymers’ structural characterization, their electrochemical and optical properties will be studied to search for their possible opto-electronic applications. When the project has reached to its aims, a new series of the chemiluminescent compounds will be synthesized after only a few steps by starting with a cheap compound called phthalic anhydride. Unfortunately, the interest of the present luminol type compounds in the literature is limited since they are synthesized in multiple steps. A new series of the compounds will be obtained for the family of luminol type compounds when the syntheses of the compounds are realized. Due to the systematic synthesis of the compounds (Group 6A: O (furan), S (thiophene), Se (selenophene) atoms used for the same template compound), the effect of the electron donating units will be investigated on the chemiluminescent property. In conclusion, new compounds that are alternative to the luminol used in forensic application will be brought into the literature.Research Project : Synthesis of Electroactive Chemiluminescent Compounds and Polymers for Blood Detection in Forensic/Adli-Tıpta Kan Teşhisi için Elektroaktif Kemilüminesans Bileşiklerin ve Polimerlerin SenteziChemical EngineeringProject Summary Combination of pyridazine based and chemiluminescent units with electroactive compounds and conjugated polymers have been taken place recently. These compounds and conjugated polymers have been reported to be used instead of luminol in order to detect blood traces in forensic science. These studies resulted in the birth of a new series of compounds so-called “luminol-type compounds”. In this study, a new series of chemiluminescent and conjugated trimeric compounds bearing pyridazine ring (Scheme 1) and their polymers will be synthesized and characterized structurally. Then, their chemiluminescent properties and forensic applications (blood detection) will be scrutinized. Scheme 1. Chemical structure of the compounds bearing redox active terminals and chemiluminescent pyridazine units In order to achieve this aim, phthalic anhydride will be utilized to synthesize the target molecules in three steps. This will be advantageous when compared the synthesis of some luminol derivatives which require multiple steps. After the completion of the structural characterization of the compounds, the chemiluminescent reactions of the compounds in basic medium will be tested firstly in the presence of only hydrogen peroxide and then together with various metal cations as catalyst by using a photomultiplier tube. If iron ion is found to exhibit a catalytic role in the chemiluminescent process, the application of blood trace detection in forensic will be studied. First of all, hemin as a hemoglobin analogue will be used to get a standard curve and then the blood samples will be studied. Obtained data will be compared with luminol and its derivatives and also the effect of the substituents (electron donating units: furan, thiophene and selenophene) of the compounds on the chemiluminescent process will be investigated. Next step will be the electrochemical polymerization of the compounds. The structural analyses of the polymers will be studied by using voltammetric and spectroscopic methods (cyclic voltammetry, NMR, FTIR, UV-vis, SEM, GPC, etc.). Chemiluminescent properties and forensic applications of their polymers will also be studied. Furthermore, since the polymers can be obtained as films via electrochemical polymerization, the electrochemiluminescent properties of these polymers will also be investigated. In addition to the polymers’ structural characterization, their electrochemical and optical properties will be studied to search for their possible opto-electronic applications. When the project has reached to its aims, a new series of the chemiluminescent compounds will be synthesized after only a few steps by starting with a cheap compound called phthalic anhydride. Unfortunately, the interest of the present luminol type compounds in the literature is limited since they are synthesized in multiple steps. A new series of the compounds will be obtained for the family of luminol type compounds when the syntheses of the compounds are realized. Due to the systematic synthesis of the compounds (Group 6A: O (furan), S (thiophene), Se (selenophene) atoms used for the same template compound), the effect of the electron donating units will be investigated on the chemiluminescent property. In conclusion, new compounds that are alternative to the luminol used in forensic application will be brought into the literature.