Development of semiconductor nanocrystals for biotechnological applications

Thesis (Master)--İzmir Institute of Technology, Chemistry, İzmir, 2008Includes bibliographical references (leaves: 71-77).Text in English; Abstract: Turkish and Englishxii, 77 leavesSemiconductor nanocrystals are very useful tools in biological applications because of their unique optical properties. In this study, synthesis and characterization of CdTe / CdS and CdSexS1-x nanocrystals were carried out. CdSexS1-x nanocrystals were synthesized by a modified two phase method. Highly luminescent (Quantum yied . %80) , monodisperse and face centered cubic CdSexS1-x nanocrystals were obtained in toluene. The size of nanoparticles varies from 3.5 to 3.7 nm Ligand exchange was performed on CdSexS1-x nanocrystals and luminescent water soluble CdSexS1-x nanocrystals were obtained. CdTe / CdS nanocrystals were synthesized in one step and and one pot by a modified method. Face centered cubic, luminescent (Quantum yield . 30%) and monodisperse CdTe / CdS nanocrystals with different sizes in a size range from 4.7 to 9.3 nm were obtained in water. Toxicity of CdTe / CdS nanocrystals was determined by MTT test. The lethal concentrations were respectively 1.0 and 15 .g/ml for PC3 and MCF7 cells. Confocal microscopy shows that the nanoparticles enter to the cytoplasm of cells

Disturbed excitation energy transfer in Arabidopsis thaliana mutants lacking minor antenna complexes of photosystem II.

Abstract Minor light-harvesting complexes (Lhcs) CP24, CP26 and CP29 occupy a position in photosystem II (PSII) of plants between the major light-harvesting complexes LHCII and the PSII core subunits. Lack of minor Lhcs in vivo causes impairment of PSII organization, and negatively affects electron transport rates and photoprotection capacity. Here we used picosecond-fluorescence spectroscopy to study excitation-energy transfer (EET) in thylakoid membranes isolated from Arabidopsis thaliana wild-type plants and knockout lines depleted of either two (koCP26/24 and koCP29/24) or all minor Lhcs (NoM). In the absence of all minor Lhcs, the functional connection of LHCII to the PSII cores appears to be seriously impaired whereas the "disconnected" LHCII is substantially quenched. For both double knock-out mutants, excitation trapping in PSII is faster than in NoM thylakoids but slower than in WT thylakoids. In NoM thylakoids, the loss of all minor Lhcs is accompanied by an over-accumulation of LHCII, suggesting a compensating response to the reduced trapping efficiency in limiting light, which leads to a photosynthetic phenotype resembling that of low-light-acclimated plants. Finally, fluorescence kinetics and biochemical results show that the missing minor complexes are not replaced by other Lhcs, implying that they are unique among the antenna subunits and crucial for the functioning and macro-organization of PSII

Development of semiconductor nanocrystals for biotechnological applications

Thesis (Master)--İzmir Institute of Technology, Chemistry, İzmir, 2008Includes bibliographical references (leaves: 71-77).Text in English; Abstract: Turkish and Englishxii, 77 leavesSemiconductor nanocrystals are very useful tools in biological applications because of their unique optical properties. In this study, synthesis and characterization of CdTe / CdS and CdSexS1-x nanocrystals were carried out. CdSexS1-x nanocrystals were synthesized by a modified two phase method. Highly luminescent (Quantum yied . %80) , monodisperse and face centered cubic CdSexS1-x nanocrystals were obtained in toluene. The size of nanoparticles varies from 3.5 to 3.7 nm Ligand exchange was performed on CdSexS1-x nanocrystals and luminescent water soluble CdSexS1-x nanocrystals were obtained. CdTe / CdS nanocrystals were synthesized in one step and and one pot by a modified method. Face centered cubic, luminescent (Quantum yield . 30%) and monodisperse CdTe / CdS nanocrystals with different sizes in a size range from 4.7 to 9.3 nm were obtained in water. Toxicity of CdTe / CdS nanocrystals was determined by MTT test. The lethal concentrations were respectively 1.0 and 15 .g/ml for PC3 and MCF7 cells. Confocal microscopy shows that the nanoparticles enter to the cytoplasm of cells

Developing a facile 1 method for highly luminescent colloidal CdSxSe1_x ternary nanoalloys†

We report a facile method to synthesize highly luminescent colloidal CdSxSe1 xternary nanoalloys. The synthesis is achieved exactly in one-step, one-pot and at low temperature, by applying the two-phase thermal approach. The optical and structural properties of the nanoalloys were characterized by various techniques. Photoluminescence of the nanoalloys is tunable from 435 to 545 nm by either the size or the composition of the nanoalloys. Highly luminescent nanoalloys having quantum yields up to 90% were prepared. The hydrodynamic size of the nanoalloys can be varied from 1.4 to 10.0 nm by the reaction time. DLS measurements showed that the size distribution of the nanoalloys is monodispersed. TEM images confirmed the size and the size distribution of the nanoalloys. The sulfur fraction in the nanoalloy composition, measured by XRD and verified by EDX, is modulated from 0.17 to 0.95 by increasing the amount of thiourea in the chalcogenide mixture. The sulfur-rich nanoalloys are formed when the initial mole ratio of the chalcogenide (S : Se) is equal or higher than eleven-fold. The gradient and homogeneous internal structures are revealed by analysis of the alloy composition as a function of the growth time. We propose that the two-phase approach, a non-injection technique, is a facile and versatile method to develop highly luminescent CdSxSe1 x nanoalloys without an inorganic coating layer

Development of highly luminescent water-insoluble carbon dots by using calix[4]pyrrole as the carbon precursor and their potential application in organic solar cells

Carbon dots (CDs) are carbon-based fluorescent nanomaterials that are of interest in different research areas due to their low cost production and low toxicity. Considering their unique photophysical properties, hydrophobic/amphiphilic CDs are powerful alternatives to metal-based quantum dots in LED and photovoltaic cell designs. On the other hand, CDs possess a considerably high amount of surface defects that give rise to two significant drawbacks: (1) causing decrease in quantum yield (QY), a crucial drawback that limits their utilization in LEDs, and (2) affecting the efficiency of charge transfer, a significant factor that limits the use of CDs in photovoltaic cells. In this study, we synthesized highly luminescent, water-insoluble, slightly amphiphilic CDs by using a macrocyclic compound, calix[4]pyrrole, for the first time in the literature. Calix[4]pyrrole-derived CDs (CP-DOTs) were highly luminescent with a QY of over 60% and size of around 4-10 nm with graphitic structure. The high quantum yield of CP-DOTs indicated that they had less amount of surface defects. Furthermore, CP-DOTs were used as an additive in the active layer of organic solar cells (OSC). The photovoltaic parameters of OSCs improved upon addition of CDs. Our results indicated that calix[4]pyrrole is an excellent carbon precursor to synthesize highly luminescent and water-insoluble carbon dots, and CDs derived from calix[4]pyrrole are excellent candidates to improve optoelectronic devices

Controlling spontaneous emission of CdSe nanoparticles dispersed in electrospun fibers of polycarbonate urethane

Luminescent fibrous composite films consisting of submicrometer diameter fibers were prepared by electrospinning of segmented polycarbonate urethane (PCU) in dimethyl formamide and tri-n-octylphosphine oxide (TOPO)-capped CdSe nanocrystals (5 nm in diameter) in toluene. Using a pair of conductive electrodes separated with an air gap, we successfully produced randomly deposited and uniaxially aligned electrospun fibers. The surface structure of the electrospun fibers was studied using atomic force microscopy (AFM) and was compared to the corresponding film prepared by casting. In cast film, tapping mode AFM imaging suggests that hard urethane segments organize into rodlike morphology dispersed in soft polycarbonate. When PCU/ CdSe dispersions were subjected to electrospinning, copolymer domains were forced to arrange into lamella along the fiber axis due to elongational flow and high stretching. Molecular orientation in the domains of the composite fibers was confirmed by polarized infrared spectroscopy. We demonstrated that formation of the oriented domains by electrospinning develops a hierarchical structure, which consequently modifies spectral properties because new multiple sharp lines appeared in the photoluminescence (PL) spectra of the fibers. In contrast to randomly deposited fibers, the PL intensity of uniaxially aligned fibers was found to be angle dependent. We propose that the elongated internal structure within the fibers controls the spontaneous emission of CdSe nanoparticles dispersed throughout the electrospun mat. A discussion on the nature of the controlled spontaneous emission is provided

CROHN HASTALIĞI ZEMİNİNDE GELİŞEN ADENOKANSER VAKASI

GİRİŞCrohn hastalığı, aktivite ve remisyon dönemleri olan,bozulmuş bir immün yanıtla ilişkili etiyolojisi bilinmeyen kronik inflamatuarbağırsak hastalığıdır. Ağızdan anüse kadar tüm mide-bağırsak sisteminietkileyebilen yamalı ve transmural lezyonlarla karakterizedir. En sık görülensemptomlar karın ağrısı ve ishaldir ve hastaların yaşam kalitesini ciddi şekildeetkileyebilir. Komplikasyon riskini azaltmak için, birinci basamak hekimleri vegastroenterologlar, hastalığın yönetimine aşina olmalıdır. Crohn hastalığı olanlarda kolorektal kanser riski genelpopülasyona göre artar.(3)Biz de Crohn hastalığı yönünden tetkik ettiğimiz vekolon kanseri tanısını koyduğumuz olguyu sunduk.OLGU37 yaşında komorbiditesi olmayan erkek hasta acil servise halsizlikve ishal şikayetiyle başvurmuş olup laboratuvar değerlerindeHgb:5,5g/dL olan demir eksikliği anemisi ile uyumlu olan hastaya 2 ünite eritrositreplasmanı yapılarak taburcu edilmiş ve etiyolojisi araştırmak içingastroenteroloji polikliniğine yönlendirilmiş. Hasta dış merkezde cerrahi kliniktekolonoskopik görüntülemesinde crohn hastalığı düşünülerek polikliniğimize başvurdu.Değerlendirmesinde 7-8 aydır günde 10-15 kez kanlıishal şikayeti ve 2 ayda 35kg kaybı olması, muayanesinde servikallenfadenopatileri(LAP) olması ve laboratuvar incelemesinde CRP:4mg/dL Wbc:8,8103/uLHgb:8,3g/dL Plt:443&nbsp;103/uL Ferritin:1,3 ng/mL olması üzerine tetkik amaçlıgastroenteroloji servisine yatırıldı. Hastaya tarafımızca yapılan kolonoskopisinde rektumkorunmuş, hepatik fleksuraya kadar multipl villöz polipoid pseudopoliplerineşlik ettiği, arada normal mukozalar olduğu görüldü.Yeni tanı Crohn hastalığı vekolonik darlık görülerek biyopsiler alındı.Hastaya siprofloksasin 2x400mg,metronidazol 3x500mg ve metilprednizolon 60mg başlandı.BilgisayarlıTomografi’de(BT) servikal zincirde, mediastende 18mm ulaşan patolojikgörünümlü lenf nodları ve tüm kolonik segmentlerde submukozal heterojenite ve hepatikfleksurada asimetrik duvar kalınlık artışı saptandı.HastanınLAP’larının olması nedeniyle hematoloji tarafından değerlendirildi ve hematolojikmalignite düşünülmedi.Serviste ishali gerileyen hasta metilprednizolonazaltılarak kesildi ve biyolojik ajan tedavisinin patoloji sonucuna görebaşlanması önerilerek taburcu edildi.Taburculuğunun 13.gününde kontrole gelen ve kolon biyopsisonucu adenokarsinom olarak raporlanan hasta, 2 gündür gaz-gaitaçıkışı olmaması ile ileus düşünülerek acil servise yönlendirildi.Çekilen BT’dehepatik fleksurada 4cm'lik segmentte duvar kalınlaşması yapan kitlesi olanhastaya sağ hemikolektomi+uç ileostomi yapıldı. Postoperatif durumu iyiolan hasta taburcu edildi.GÖRSELLER:<img 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