Scopus İndeksli Yayınlar Koleksiyonu / Scopus Indexed Publications Collection
Permanent URI for this collectionhttps://hdl.handle.net/11147/7148
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Article Synthetic Memory: A Key Link Between Biocatalytically Synthesized Polyesters and Melt Electrowriting Performance(Taylor & Francis inc, 2025) Yıldız, Ümit Hakan; Yildiz, Umit Hakan; 01. Izmir Institute of Technology; 04. Faculty of Science; 04.01. Department of ChemistryThe biocatalytic synthesis of polycaprolactone (PCL) and its copolymers has garnered significant attention due to their reduced toxicity and enhanced 3D processability compared to metal-catalyzed alternatives. The objective of this study is to employ biocatalysts-citric acid (CA), glycolic acid (GA) and salicylic acid (SAA)-and explore their catalytic effects on the synthesis of poly(epsilon-caprolactone) (PCL) and poly(epsilon-caprolactone)-b-poly(delta-valerolactone) (PCL-b-PVL) block copolymers. Additionally, we aimed to examine the link between synthetic memory of resultant PCL and PCL-b-PVL polymers and their melt electrowriting performance. Nuclear magnetic resonance analysis confirms successful synthesis of copolymers by monitoring signals of hydrogens at 2.30 ppm. Differential scanning calorimetry results reveal shifts in thermal properties of copolymers upon varying biocatalysts CA-, SAA- and GA-catalyzed copolymers exhibit Tm values between similar to 52 and 54 degrees C. Melt electrowriting (MEW) results demonstrate that catalyst selection plays significant role in fiber morphology and scaffold architecture, with GA- and CA-catalyzed copolymers exhibiting finer fibers (5-8 mu m), while SAA led to thicker fibers (similar to 12 mu m) and reduced spacing. Moreover, precipitation solvents MeOH and acetonitrile (ACN) affect fidelity, with ACN-prepared scaffolds exhibiting more uniform fiber diameters. Atomic force microscopy imaging of electrowritten scaffolds made of ACN- and MeOH-precipitated PCL-b-PVL both exhibit large (>15 mu m) and smaller (<10 mu m) spherulitic structure as major topological features. These findings confirm that the synthetic memory of polyesters-governed by catalyst choice and processing conditions-directly influences their printability, making them promising candidates for MEW-based biomedical scaffolds in tissue engineering, where fine fiber morphology and architectural fidelity are essential for cell attachment and tissue regeneration.Article Free-Standing Three-Dimensional Graphene Scaffolds for Protease Functional Assay(Elsevier Science Sa, 2024) Ng, Zhi Kai; Yıldız, Ümit Hakan; Goyal, Garima; Gudlur, Sushanth; Kanagavel, Deepankumar; Yildiz, Umit Hakan; Teo, Edwin Hang Tong; 04.01. Department of Chemistry; 04. Faculty of Science; 01. Izmir Institute of TechnologyThree-dimensional graphene scaffolds (3d-GS) of high porosity possessing good fluorescence quenching properties are potential candidates for the development of optical biosensors. Herein, we demonstrate the feasibility of utilising intact and free-standing 3d-GS for sensitive detection of proteases, a class of disease diagnosis bio-markers of significant interest. Recombinant OmpT was employed as a model protease for validating the pro-posed methodology. A short (15-residue) peptide sequence encoding a specific recognition site for OmpT was end-labelled with a fluorescent dye (5-FAM) whose fluorescence is quenched when the peptide is anchored to 3d-GS. However, in the presence of OmpT, the peptide is cleaved and released from 3d-GS, resulting in a sig-nificant recovery in fluorescence. The functional assay described herein involves a single step fabrication process of anchoring the peptide to 3d-GS. The integrity of the 3d-GS is hypothesised to overcome the concern of dynamic requenching associated with the typical homogeneous assays based on graphene, yielding a limit of detection (LOD) of similar to 140 nM, which is over an order higher than homogeneous assays performed using the same composition of graphene in powdered form. To the best of our knowledge, this is the first report on utilising free-standing 3d-GS for facile assaying of proteases.