Chemistry / Kimya
Permanent URI for this collectionhttps://hdl.handle.net/11147/4072
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Conference Object Citation - WoS: 3Citation - Scopus: 3Halloysite Nanotube Loaded Polyamide Nanocomposites: Structural, Morphological, Mechanical, Thermal and Processing Behaviors(American Institute of Physics, 2023) Akar, Alinda Öykü; Yıldız, Ümit Hakan; Tayfun, ÜmitIn this study, the polyamide 6 (PA) matrix was reinforced with the purified, fine ground and amino-silane treated halloysite nanotubes (HNT) at different concentrations. The preparation of composites was carried out using a lab-scale twin-screw micro-compounder with loading ratios at 0.5, 1, 3, and 20% by weight, and the test samples were prepared by the injection-molding process. According to mechanical test results, additions of HNT to the PA matrix caused slight improvements in tensile strength and Youngs' modulus parameters. The optimum concentrations for all of the additives used were estimated by comparison of mechanical test data. The addition of aminosilane-modified HNT resulted in a higher impact performance at high loading levels up to 3% concentrations. Further addition of HNT caused a reduction in the mechanical parameters of composites. Thermal studies revealed that the glass transition temperature of PA shifted to higher values after HNT mineral inclusions. Thermo-mechanical results showed that storage moduli of PA exhibited improvement with an increase in HNT content. The distributions of HNT clay into the PA phase were visualized with SEM images. Based on these observations, a high level of dispersion homogeneity was achieved for lower filling ratios. According to melt-flow and force measurements, composites filled with 20% of HNT displayed a remarkable increase in exerted force during melt-blending. © 2023 Author(s).Article Citation - WoS: 4Citation - Scopus: 4Colorimetric Assaying of Exosomal Metabolic Biomarkers(MDPI, 2023) Yan, Evelias; Goyal, Garima; Yıldız, Ümit Hakan; Boehm, Bernhard O.; Palaniappan, AlagappanExosomes released into the extracellular matrix have been reported to contain metabolic biomarkers of various diseases. These intraluminal vesicles are typically found in blood, urine, saliva, breast milk, cerebrospinal fluid, semen, amniotic fluid, and ascites. Analysis of exosomal content with specific profiles of DNA, microRNA, proteins, and lipids can mirror their cellular origin and physiological state. Therefore, exosomal cargos may reflect the physiological processes at cellular level and can potentially be used as biomarkers. Herein, we report an optical detection method for assaying exosomal biomarkers that supersedes the state-of-the-art time consuming and laborious assays such as ELISA and NTA. The proposed assay monitors the changes in optical properties of poly(3-(4-methyl-3'-thienyloxy) propyltriethylammonium bromide) upon interacting with aptamers/peptide nucleic acids in the presence or absence of target biomarkers. As a proof of concept, this study demonstrates facile assaying of microRNA, DNA, and advanced glycation end products in exosomes isolated from human plasma with detection levels of ~1.2, 0.04, and 0.35 fM/exosome, respectively. Thus, the obtained results illustrate that the proposed methodology is applicable for rapid and facile detection of generic exosomal biomarkers for facilitating diseases diagnosis.Conference Object Citation - WoS: 1Citation - Scopus: 1Biomimetic Peptide-Conjugated Membranes for Developing an Artificial Cornea(IEEE, 2022) Sunal, Gülşah; Pulat, Günnur; Akgün, İsmail Hakkı; Güven, Sinan; Yıldız, Ümit Hakan; Karaman, Ozan; Horzum, NesrinThe corneal endothelium is composed of a single layer of specialized endothelial cells, protecting, and nourishing the inner surface of the cornea. Corneal endothelial cells do not proliferate after birth and their number decrease with age. Trauma, inflammation, or surgical intervention can cause cell loss. When damage is extensive and the density of corneal endothelial cells decreases to a critical level, it results in corneal edema and vision loss. Besides them, when corneal endothelium has irreversible damage, the only treatment way is corneal transplantation. But there are some drawbacks such as finding donors, immune reactions, and the number of patients waiting on the transplantation lists for years. Tissue engineering approaches can provide promising alternatives for the regeneration of corneal endothelium tissue. Peptides can be used to modify and functionalize the scaffolds, allowing for the production of bioactive and biomimetic surfaces. Peptide-modified scaffold surfaces might direct and enhance the behaviors of cells. In this study, the aim was to functionalize the polycaprolactone (PCL) membranes with tissue-specific peptides and to characterize the peptide-conjugated membranes by Fourier-Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), and X-ray Photoelectron Spectroscopy (XPS) analysis. The synthesized peptides were successfully conjugated on the PCL biomembranes.Article Citation - WoS: 1Citation - Scopus: 1Gadolinium and Polythiophene Functionalized Polyurea Polymer Dots as Fluoro-Magnetic Nanoprobes(MDPI, 2022) Karabacak, Soner; Palaniappan, Alagappan; Tony, Tsang Siu Hon; Edwin, Teo Hang Tong; Gulyás, Balázs; Padmanabhan, Parasuraman; Yıldız, Ümit HakanA rapid and one-pot synthesis of poly 3-thiopheneacetic acid (PTAA) functionalized pol-yurea polymer dots (Pdots) using polyethyleneimine and isophorone diisocyanate is reported. The one-pot mini-emulsion polymerization technique yielded Pdots with an average diameter of ~20 nm. The size, shape, and concentration of the surface functional groups could be controlled by al-tering the synthesis parameters such as ultrasonication time, concentration of the surfactant, and crosslinking agent, and the types of isocyanates utilized for the synthesis. Colloidal properties of Pdots were characterized using dynamic light scattering and zeta potential measurements. The spherical geometry of Pdots was confirmed by scanning electron microscopy. The Pdots were post-functionalized by 1,4,7,10 tetraazacyclododecane-1,4,7,10-tetraacetic acid for chelating gadolinium nanoparticles (Gd3+) that provide magnetic properties to the Pdots. Thus, the synthesized Pdots possess fluorescent and magnetic properties, imparted by PTAA and Gd3+, respectively. Fluorescence spectroscopy and microscopy revealed that the synthesized dual-functional Gd3+-Pdots ex-hibited detectable fluorescent signals even at lower concentrations. Magnetic levitation experiments indicated that the Gd3+-Pdots could be easily manipulated via an external magnetic field. These findings illustrate that the dua-functional Gd3+-Pdots could be potentially utilized as fluorescent reporters that can be magnetically manipulated for bioimaging applications.Article Citation - WoS: 2Citation - Scopus: 2Transition-Metal Direct C-H Arylation of Thiophene in Aqueous Media Via Potassium Peroxymonosulfate(John Wiley and Sons Inc., 2019) Özenler, Sezer; Kaya, Hakan; Elmacı, Nuran; Yıldız, Ümit HakanThis study covers the use of potassium peroxymonosulfate (PPS) which, is a mild and inexpensive catalyst, for direct coupling of C-H/C-H for water soluble thiophene. The 3-(4-methyl-3 '- thienyloxy)propyltriethylammonium bromide (M1) has been selected as model monomer that reacted PPS in 2.0, 0.20 and 0.020 monomer to PPS ratio. The reaction has been monitored via NMR spectroscopy revealing the monomer consumption and formation of dimers to tetramers as well as completion of reaction within 15 minutes. Resultant product is easily collected without tedious work up steps. The computational calculation has optimized the regularity of the coupling as head to tail, tail to tail, head to tail (HT-TT-HT) for tetramer. The regularity of tetramer which is further satisfied via NMR analysis showing emergence of new peaks at 3.56 and 4.48. The shifts in the UV maximum of reactive species have been monitored by absorbance spectroscopy showing time dependent red shift corresponds to growing from monomer to tetramers. The reaction has self-stopped due to low solubility of moderate condensates (higher than trimer), however further experiments have performed in water-organic mixtures showed great promises to obtain higher condensates.Article Citation - WoS: 39Citation - Scopus: 37Flow-Through Colorimetric Assay for Detection of Nucleic Acids in Plasma(Elsevier, 2019) Ammanath, Gopal; Yeasmi, Sanjida; Srinivasulu, Yuvasri; Vats, Mukti; Cheema, Jamal Ahmed; Nabilah, Fairuz; Liedberg, Bo; Yıldız, Ümit HakanA flow-through colorimetric assay for detection of nucleic acids in plasma is reported. The proposed assay features an array of four polyvinylidene fluoride (PVDF) membranes impregnated with cationic poly (3-alkoxy-4-methylthiophene) (PT) as an optical reporter. The sensing strategy is based on monitoring the changes in optical properties of PT, upon complexation with target nucleic acids in the presence and in the absence of their corresponding complementary peptide nucleic acids (PNAs). As a proof of concept, the proposed methodology is validated using two biomarkers; lung cancer associated microRNA (mir21) and hepatitis B virus DNA (HBV-DNA). The flow-through colorimetric assay enabled detection of mir21 and HBV-DNA in plasma without requiring tedious sample pre-treatment and clean up protocols. Colorimetric responses for mir21 and HBV-DNA were obtained at nanomolar concentrations over five orders of magnitudes (from 1 nM to 10 mu M), with a limit of detection of -0.6 nM and -2 nM in DI water and plasma, respectively. A logic gate system was developed to utilize the colorimetric assay responses as inputs for discrimination of mir21 and HBV-DNA and subsequently to obtain a profile of nucleic acids in samples that exceed respective clinical threshold limits, thereby enabling rapid and point of care (POC) disease diagnosis. Furthermore, the proposed methodology can be utilized for detection of a large number of nucleic acids in plasma by extending the array of PT impregnated membranes incorporated with their corresponding complementary PNAs. (C) 2019 Elsevier B.V. All rights reserved.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: 17Citation - Scopus: 19Pixelated Colorimetric Nucleic Acid Assay(Elsevier, 2020) Aydın, Hakan Berk; Cheema, Jamal Ahmed; Arnmanath, Gopal; Toklucu, Cihan; Yücel, Müge; Özenler, Sezer; Yıldız, Ümit HakanConjugated polyelectrolytes (CPEs) have been widely used as reporters in colorimetric assays targeting nucleic acids. CPEs provide naked eye detection possibility by their superior optical properties however, as concentration of target analytes decrease, trace amounts of nucleic acid typically yield colorimetric responses that are not readily perceivable by naked eye. Herein, we report a pixelated analysis approach for correlating colorimetric responses of CPE with nucleic acid concentrations down to 1 nM, in plasma samples, utilizing a smart phone with an algorithm that can perform analytical testing and data processing. The detection strategy employed relies on conformational transitions between single stranded nucleic acid-cationic CPE duplexes and double stranded nucleic acid-CPE triplexes that yield distinct colorimetric responses for enabling naked eye detection of nucleic acids. Cationic poly[N,N,N-triethyl-3-((4-methylthiophen-3-yl)oxy)propan-1-aminium bromide] is utilized as the CPE reporter deposited on a polyvinylidene fluoride (PVDF) membrane for nucleic acid assay. A smart phone application is developed to capture and digitize the colorimetric response of the individual pixels of the digital images of CPE on the PVDF membrane, followed by an analysis using the algorithm. The proposed pixelated approach enables precise quantification of nucleic acid assay concentrations, thereby eliminating the margin of error involved in conventional methodologies adopted for interpretation of colorimetric responses, for instance, RGB analysis. The obtained results illustrate that a ubiquitous smart phone could be utilized for point of care colorimetric nucleic acids assays in complex matrices without requiring sophisticated software or instrumentation.Article Citation - WoS: 7Citation - Scopus: 7Fabrication of a Postfunctionalizable, Biorepellent, Electroactive Polyurethane Interface on a Gold Surface by Surface-Assisted Polymerization(American Chemical Society, 2020) Özenler, Sezer; Sözen, Yiğit; Şahin, Hasan; Yıldız, Ümit HakanThis study describes surface-assisted (SurfAst) urethane polymerization, providing a modular/postfunctionalizable, biorepellent, electroactive similar to 10 to 100 nm-thick polyurethane (PU) interface on a gold surface. SurfAst is a functionalization methodology based on sequential incubation steps of alkane diisocyanates and alkanediol monomers. The gold surface is functionalized by alkane diisocyanates in the first incubation step, and our theoretical calculations reveal that while the isocyanate group atoms (N, C, and O) at one end of the molecule exhibits strong interactions (similar to 900 meV) with surface atoms, the other end group remains unreacted. After the first incubation step, sequential alkanediol and alkane diisocyanate incubations provide formation of the PU interface. The extensive analysis of the PU interface has been conducted via X-ray photoelectron spectroscopy, and the chemical mapping verifies that the interface is made of PU moieties. The topographical analysis of the surface conducted by the atomic force microscopy shows that the PU interface consists of mostly a nanoporous texture with 150 nm total roughness. The adherence force mapping of the PU interface reveals that the nanoporous matrix exhibits an adhesion force of about 14 nN. The electrostatic force microscopy characterizing long-range electrostatic interactions (40 nm) shows that the PU interface has been attracted by positively charged species as compared to negative objects. Finally, it is demonstrated that the PU interface is readily postfunctionalizable by polyethylene glycol (PEG 1000), serving as a biorepellent interface and preserving electroactivity. We foresee that SurfAst polymerization will have potential for the facile fabrication of a postfunctionalizable and modular biointerface which might be utilized for biosensing and bioelectronic applications.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.
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