Chemistry / Kimya
Permanent URI for this collectionhttps://hdl.handle.net/11147/4072
Browse
35 results
Search Results
Article Citation - WoS: 6Citation - Scopus: 8Enhanced Spontaneous Emission Rate in a Low-Q Hybrid Photonic-Plasmonic Nanoresonator(American Chemical Society, 2019) Gökbulut, Belkıs; İnanç, Arda; Topçu, Gökhan; Ünlütürk, Seçil Sevim; Özçelik, Serdar; Demir, Mustafa Muammer; İnci, Mehmet NaciIn this paper, CdTe quantum dots (QDs)-doped single electrospun polymer nanofibers are partially coated with gold nanoparticles to form distinct hybrid photonic-plasmonic nanoresonators to investigate the critical role of the cavity-confined hybrid mode on the modification of the spontaneous emission dynamics of the fluorescent emitters in low-Q photonic cavities. A total enhancement factor of 11.2 is measured via a time-resolved experimental technique, which shows that there is an increase of about three times in the spontaneous emission rate for the QDs-doped gold nanoparticle-decorated nanofibers as they are compared with those uncoated ones. The physical mechanism affecting the spontaneous emission rate of the encapsulated QDs in such a hybrid photonic-plasmonic nanoresonator is explained to be due to regeneration of the mode field in the nanofiber cavity upon the interaction of the dipoles with the surface plasmons of distinctive gold nanoparticles that surround the outer surface of the nanofiber.Article Citation - WoS: 13Citation - Scopus: 13Single Chain Cationic Polymer Dot as a Fluorescent Probe for Cell Imaging and Selective Determination of Hepatocellular Carcinoma Cells(American Chemical Society, 2019) Özenler, Sezer; Yücel, Müge; Tüncel, Özge; Kaya, Hakan; Özçelik, Serdar; Yıldız, Ümit HakanThis letter describes formation of single chain cationic polymer dots (Pdots) made of poly[1,4-dimethy1-1-(34(2,4,5-trimethylthiophen-3-yl)oxy)propyl)piperazin-1-ium bromide] conjugated polyelectrolyte (CPE). The single chain Pdot formation relies on a simple process which is a rapid nanophase separation between CPE solution of ethylene glycol and water. Pdots show narrow monodisperse size distribution with a 3.6 nm in diameter exhibiting high brightness and excellent colloidal and optical stability. It has been demonstrated that photoluminescent Pdots provide selective nuclear translocation to hepatocellular carcinoma cells as compared to healthy liver cells. The Pdot labeling effectively discriminates cancer cells in the coculture media. Pdots hold great promise as a luminescent probe to diagnose cancer cells in histology and may guide surgeons during operations to precisely separate out cancerous tissue due to augmented fluorescence brightness.Article Citation - WoS: 21Citation - Scopus: 23Mass Spectrometry of Intact Proteins Reveals +98 U Chemical Artifacts Following Precipitation in Acetone(American Chemical Society, 2017) Güray, Melda Zeynep; Zheng, Shi; Doucette, Alan A.Protein precipitation in acetone is frequently employed ahead of mass spectrometry for sample preconcentration and purification. Unfortunately, acetone is not chemically inert; mass artifacts have previously been observed on glycine-containing peptides when exposed to acetone under acidic conditions. We herein report a distinct chemical modification occurring at the level of intact proteins when incubated in acetone. This artifact manifests as one or more satellite peaks in the MS spectrum of intact protein, spaced 98 u above the mass of the unmodified protein. Other artifacts (+84, +112 u) also appear upon incubation of proteins or peptides in acetone. The reaction is pH-sensitive, being suppressed when proteins are exposed to acetone under acidic conditions. The +98 u artifact is speculated to originate through an intermediate product of aldol condensation of acetone to form diacetone alcohol and mesityl oxide. A +98 u product could originate from nucleophilic attack on mesityl oxide or through condensation with diacetone alcohol. Given the extent of modification possible upon exposure of proteins to acetone, particularly following overnight solvent exposure or incubation at room temperature, an awareness of the variables influencing this novel modification is valued by proteomics researchers who employ acetone precipitation for protein purification.Article Citation - WoS: 35Citation - Scopus: 36Colloidal Nanodisk Shaped Plexcitonic Nanoparticles With Large Rabi Splitting Energies(American Chemical Society, 2019) Mert Balcı, Fadime; Sarısözen, Sema; Polat, Nahit; Balcı, SinanWhen plasmons supported by metal nanoparticles interact strongly with molecular excitons or excitons of semiconducting quantum dots, plexcitons are formed in the strong coupling regime. The hybrid plexcitonic nanoparticles with a wide range of sizes and shapes have been synthesized by using wet chemistry methods or have been fabricated on solid substrates by using lithographic techniques. In order to deeply understand plasmon-exciton interaction at the nanoscale dimension and boost the performance of nanophotonic devices made of plexcitonic nanoparticles, new types of plexcitonic nanoparticles with tunable optical properties and outstanding stability at room temperature are urgently needed. Herein, we for the first time report pure colloidal nanodisk shaped plexcitonic nanoparticles with very large Rabi splitting energies, i.e., more than 350 meV. We synthesize silver nanoprisms by using seed mediated synthesis and then convert nanoprisms to nanodisks at a high temperature. Localized plasmon resonance of the silver nanodisk in the visible spectrum can be effectively tuned by heating. Subsequently, self-assembly of J-aggregate dyes on plasmonic nanodisks produces plexcitonic nanoparticles. We envision that colloidal nanodisk shaped plexcitonic nanoparticles with very large Rabi splitting energies and outstanding stability at room temperature will enlarge the application of plexcitonic nanoparticles in a variety of fields such as polariton laser, biosensor, plasmon molecular nanodevices, and energy flow at nanoscale dimensions.Article Citation - WoS: 18Citation - Scopus: 19Hand-Held Volatilome Analyzer Based on Elastically Deformable Nanofibers(American Chemical Society, 2018) Yücel, Müge; Akın, Osman; Çayören, Mehmet; Akduman, İbrahim; Palaniappan, Alagappan; Liedberg, Bo; Hızal, Gürkan; İnci, Fatih; Yıldız, Ümit HakanThis study reports on a hand-held volatilome analyzer for selective determination of clinically relevant biomarkers in exhaled breath. The sensing platform is based on electrospun polymer nanofiber-multiwalled carbon nanotube (MWCNT) sensing microchannels. Polymer nanofibers of poly(vinylidene fluoride) (PVDF), polystyrene (PS), and poly(methyl methacrylate) (PMMA) incorporated with MWCNT exhibits a stable response to interferences of humidity and CO2 and provides selective deformations upon exposure of exhaled breath target volatilomes acetone and toluene, exhibiting correlation to diabetes and lung cancer, respectively. The sensing microchannels "P1" (PVDF-MWCNT), "P2" (PS-MWCNT), and "P3" (PMMA-MWCNT) are integrated with a microfluidic cartridge (μ-card) that facilitates collection and concentration of exhaled breath. The volatilome analyzer consists of a conductivity monitoring unit, signal conditioning circuitries and a low energy display module. A combinatorial operation algorithm was developed for analyzing normalized resistivity changes of the sensing microchannels upon exposure to breath in the concentration ranges between 35 ppb and 3.0 ppm for acetone and 1 ppb and 10 ppm for toluene. Subsequently, responses of volatilomes from individuals in the different risk groups of diabetes were evaluated for validation of the proposed methodology. We foresee that proposed methodology provides an avenue for rapid detection of volatilomes thereby enabling point of care diagnosis in high-risk group individuals.Article Citation - WoS: 32Citation - Scopus: 32Luminescent Device for the Detection of Oxidative Stress Biomarkers in Artificial Urine(American Chemical Society, 2018) Ammanath, Gopal; Yıldız, Ümit Hakan; Palaniappan, Alagappan; Liedberg, BoA luminescent paper-based device for the visual detection of oxidative stress biomarkers is reported. The device consists of a polyvinylidene fluoride membrane impregnated with poly(3-alkoxy-4-methylthiophene) (PT) for colorimetric detection. 8-hydroxy-2′-deoxyguanosine (8-OHdG), a biomarker associated with oxidative stress, is used as a model system for validating the proposed methodology. The detection strategy is based on monitoring the changes in optical properties of PT associated with its conformational changes upon interaction with an aptamer in the presence and in the absence of 8-OHdG. Fluorometric and colorimetric monitoring revealed linear responses for 8-OHdG concentrations between 50 pM and 500 nM (∼14 pg/mL to 140 ng/mL), with limits of detection of ∼300 pM and ∼350 pM, respectively for (n = 3). Colorimetric responses in artificial urine ascertained rapid, sensitive, and selective detection of 8-OHdG at clinically relevant (pM to nM) concentration levels. Furthermore, the proposed methodology enables point-of-care diagnostics for oxidative stress without requiring sophisticated instrumentation.Article Citation - WoS: 100Citation - Scopus: 97Novel Trimodal Maldi Imaging Mass Spectrometry (ims3) at 10 Μm Reveals Spatial Lipid and Peptide Correlates Implicated in Aß Plaque Pathology in Alzheimer's Disease(American Chemical Society, 2017) Kaya, İbrahim; Brinet, Dimitri; Michno, Wojciech; Başkurt, Mehmet; Zetterberg, Henrik; Blenow, Kaj; Hanrieder, Jo¨rgMultimodal chemical imaging using matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) can provide comprehensive molecular information in situ within the same tissue sections. This is of relevance for studying different brain pathologies such as Alzheimer's disease (AD), where recent data suggest a critical relevance of colocalizing Aβ peptides and neuronal lipids. We here developed a novel trimodal, high-resolution (10 μm) MALDI imaging MS (IMS) paradigm for negative and positive ion mode lipid analysis and subsequent protein ion imaging on the same tissue section. Matrix sublimation of 1,5-diaminonaphthalene (1,5-DAN) enabled dual polarity lipid MALDI IMS on the same pixel points at high spatial resolutions (10 μm) and with high spectral quality. This was followed by 10 μm resolution protein imaging on the same measurement area, which allowed correlation of lipid signals with protein distribution patterns within distinct cerebellar regions in mouse brain. The demonstrated trimodal imaging strategy (IMS3) was further shown to be an efficient approach for simultaneously probing Aβ plaque-associated lipids and Aβ peptides within the hippocampus of 18 month-old transgenic AD mice (tgArcSwe). Here, IMS3 revealed a strong colocalization of distinct lipid species including ceramides, phosphatidylinositols, sulfatides (Cer 18:0, PI 38:4, ST 24:0) and lysophosphatidylcholines (LPC 16:0, LPC 18:0) with plaque-associated Aβ isoforms (Aβ 1-37, Aβ 1-38, Aβ 1-40). This highlights the potential of IMS3 as an alternative, superior approach to consecutively performed immuno-based Aβ staining strategies. Furthermore, the IMS3 workflow allowed for multimodal in situ MS/MS analysis of both lipids and Aβ peptides. Altogether, the here presented IMS3 approach shows great potential for comprehensive, high-resolution molecular analysis of histological features at cellular length scales with high chemical specificity. It therefore represents a powerful approach for probing the complex molecular pathology of, e.g., neurodegenerative diseases that are characterized by neurotoxic protein aggregation.Article Citation - WoS: 51Citation - Scopus: 53Bodipy-Au(i): a Photosensitizer for Singlet Oxygen Generation and Photodynamic Therapy(American Chemical Society, 2017) Üçüncü, Muhammed; Karakuş, Erman; Kurulgan Demirci, Eylem; Sayar, Melike; Dartar, Suay; Emrullahoğlu, MustafaUpon complexation with Au(I), a photoinactive BODIPY derivative was transformed into a highly photoactive triplet sensitizer. Along with high efficiency in singlet oxygen generation (φδ = 0.84), the new BODIPY-Au(I) skeleton showed excellent photocytotoxic activity against cancer cell lines (EC50 = 2.5 nM).Article Citation - WoS: 31Citation - Scopus: 36Integration of Triboluminescent Eud4tea Crystals To Transparent Polymers: Impact Sensor Application(American Chemical Society, 2017) İncel, Anıl; Eanes, Mehtap; McMillen, Colin D.; Demir, Mustafa MuammerLanthanide-based organometallic materials are well-known candidate triboluminescent (TL) materials that can show bright emission when a mechanical force is applied. These materials are usually in the form of crystalline powders, and it is often useful to integrate these samples into a polymer matrix in order to achieve processability, enabling coating from a solution/molten state or fabrication as a complex-shaped matrix. In this work, micrometer-sized europium tetrakis (dibenzoylmethide) triethylammonium (EuD4TEA) crystals were synthesized and integrated with various transparent polymers (PMMA, PS, PVDF, and PU) using two approaches: (i) blending and (ii) surface impregnation. In the former method, the crystalline particles were molecularly dissolved; therefore, a TL response cannot be achieved. More than 10 wt % TL crystals in the composite is needed to obtain TL signals. However, TL signal was achieved at 2.5 wt % when a composite was prepared by the latter approach. TL intensity shows exponential decay with consecutive mechanical action. The TL emission of PU-based surface impregnated composite expires with long-lived emission, and maximum TL response with respect to applied force was measured between 2.45 and 42.0 N.Article Citation - WoS: 80Citation - Scopus: 82Electrophilic Cyanate as a Recognition Motif for Reactive Sulfur Species: Selective Fluorescence Detection of H2s(American Chemical Society, 2016) Karakuş, Erman; Üçüncü, Muhammed; Emrullahoğlu, MustafaAn ESIPT-based fluorescent dye, 3-hydroxyflavone, is chemically masked with an electrophilic cyanate motif in order to construct a fluorescent probe for cellular sulfur species. This novel probe structure, displays an extremely fast, highly sensitive and selective "turn-on" type fluorescent response toward H2S. We have also documented its utility for imaging of H2S in the living cells.