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Publication Open Access Emergence of near-infrared photoluminescence via ZnS shell growth on the AgBiS2 nanocrystals(American Chemical Society, 2024) Department of Chemistry; Department of Electrical and Electronics Engineering; Önal, Asım; Kaya, Tarık Safa; Metin, Önder; Nizamoğlu, Sedat; Department of Chemistry; Department of Electrical and Electronics Engineering; Graduate School of Sciences and Engineering; College of Sciences; College of EngineeringAgBiS2 nanocrystals (NCs), composed of nontoxic, earth-abundant materials and exhibiting an exceptionally high absorption coefficient from visible to near-infrared (>105 cm(-1)), hold promise for photovoltaics but have lack of photoluminescence (PL) due to intrinsic nonradiative recombination and challenging shell growth. In this study, we reported a facile wet-chemical approach for the epitaxial growth of ZnS shell on AgBiS2 NCs, which triggered the observation of PL emission in the near-infrared (764 nm). Since high quality of the core is critical for epitaxial shell growth, we first obtained rock-salt structured AgBiS2 NCs with high crystallinity, nearly spherical shape and monodisperse size distribution (<6%) via a dual-ligand approach reacting Ag-Bi oleate with elemental sulfur in oleylamine. Next, a zincblende ZnS shell with a low-lattice mismatch of 4.9% was grown on as-prepared AgBiS2 NCs via a highly reactive zinc (Zn(acac)(2)) precursor that led to a higher photoluminescence quantum yield (PLQY) of 15.3%, in comparison with a relatively low reactivity precursor (Zn(ac)(2)) resulting in reduced PLQY. The emission from AgBiS2 NCs with ultrastrong absorption, facilitated by shell growth, can open up new possibilities in lighting, display, and bioimaging.Publication Open Access Rotational-state-changing collisions between N-2(+) and Rb at low energies(American Physical Society (APS), 2020) Doerfler, A. D.; Villarreal, P.; Gonzalez-Lezana, T.; Gianturco, F. A.; Willitsch, S.; Department of Chemistry; Yurtsever, İsmail Ersin; Faculty Member; Department of Chemistry; College of Sciences; 7129We present a theoretical study of rotationally elastic and inelastic collisions between molecular nitrogen ions and Rb atoms in the sub-Kelvin temperature regime prevalent in ion-atom hybrid trapping experiments. The cross sections for rotational excitation and de-excitation collisions were calculated using quantum-scattering methods on ab initio potential energy surfaces for the energetically lowest singlet electronic channel of the system. We find that the rotationally inelastic collision rates are at least an order of magnitude smaller than the charge-exchange rates found in this system, rendering inelastic processes a minor channel under the conditions of typical hybrid trapping experiments.Publication Open Access Development of highly luminescent and cytocompatible near-IR-emitting aqueous Ag2S quantum dots(Royal Society of Chemistry (RSC), 2012) Çizmeciyan, M. Natali; Erdem, Rengin; Özen, Can; Kurt, Adnan; N/A; Department of Physics; Department of Chemistry; Hocaoğlu, İbrahim; Sennaroğlu, Alphan; Acar, Havva Funda Yağcı; PhD Student; Faculty Member; Department of Physics; Department of Chemistry; Graduate School of Sciences and Engineering; College of Sciences; N/A; 23851; 178902Colloidally stable and highly luminescent near-IR emitting Ag2S quantum dots (NIRQDs) were prepared by a very simple aqueous method using 2-mercaptopropionic acid (2MPA) as a coating. Emission of Ag2S-2MPA NIRQDs can be tuned between 780 and 950 nm. These NIRQDs have photoluminescence quantum yields (PLQY) around 7–39% and exhibit excellent cytocompatibility even at 600 mg mL 1 in NIH/3T3 cells. With such improved properties, Ag2S-2MPA NIRQDs have a great potential in practical bio-applications.Publication Open Access Comparison of x-ray absorption spectra between water and ice: New ice data with low pre-edge absorption cross-section(American Institute of Physics (AIP) Publishing, 2014) Sellberg, Jonas A.; Segtnan, Vegard H.; Chen, Chen; Tyliszczak, Tolek; Ogasawara, Hirohito; Nordlund, Dennis; Pettersson, Lars G. M.; Nilsson, Anders; Department of Chemistry; Kaya, Sarp; Faculty Member; Department of Chemistry; College of Sciences; 116541The effect of crystal growth conditions on the O K-edge x-ray absorption spectra of ice is investigated through detailed analysis of the spectral features. The amount of ice defects is found to be minimized on hydrophobic surfaces, such as BaF2(111), with low concentration of nucleation centers. This is manifested through a reduction of the absorption cross-section at 535 eV, which is associated with distorted hydrogen bonds. Furthermore, a connection is made between the observed increase in spectral intensity between 544 and 548 eV and high-symmetry points in the electronic band structure, suggesting a more extended hydrogen-bond network as compared to ices prepared differently. The spectral differences for various ice preparations are compared to the temperature dependence of spectra of liquid water upon supercooling. A double-peak feature in the absorption cross-section between 540 and 543 eV is identified as a characteristic of the crystalline phase. The connection to the interpretation of the liquid phase O K-edge x-ray absorption spectrum is extensively discussed.Publication Open Access One-step aqueous synthesis of anionic and cationic AgInS2 quantum dots and their utility in improving the efficacy of ALA-based photodynamic therapy(American Chemical Society (ACS), 2022) Loizidou, Marilena; MacRobert, Alexander J.; Department of Chemistry; Acar, Havva Funda Yağcı; Hashemkhani, Mahshid; PhD Student; Department of Chemistry; College of Sciences; Graduate School of Sciences and Engineering; 178902; N/ASilver-indium-sulfide quantum dots (AIS QDs) have potential applications in many areas, including biomedicine. Their lack of regulated heavy metals, unlike many commercialized QDs, stands out as an advantage, but the necessity for alloyed or core-shell structures and related costly and sophisticated processes for the production of stable and high quantum yield aqueous AIS QDs are the current challenges. The present study demonstrates the one-step aqueous synthesis of simple AgInS2 QD compositions utilizing for the first time either a polyethyleneimine/2-mercaptopropionic acid (AIS-PEI/2MPA) mixture or only 2-mercaptopropionic acid (AIS-2MPA) as the stabilizing molecules, providing a AgInS2 portfolio consisting of cationic and anionic AIS QDs, respectively, and tuneable emission. Small AIS QDs with long-term stability and high quantum yields (19-23%) were achieved at a molar ratio of Ag/In/S 1/10/10 in water without any dopant or a semiconductor shell. The theranostic potential of these cationic and anionic AIS QDs was also evaluated in vitro. Non-toxic doses were determined, and fluorescence imaging potential was demonstrated. More importantly, these QDs were electrostatically loaded with zwitterionic 5-aminolevulinic acid (ALA) as a prodrug to enhance the tumor availability of ALA and to improve ALA-induced porphyrin photodynamic therapy (PDT). This is the first study investigating the influence of nanoparticle charge on ALA binding, release, and therapeutic efficacy. Surface charge was found to be more critical in cellular internalization and dark toxicity rather than drug loading and release. Both QDs provided enhanced ALA release at acidic pH but protected the prodrug at physiological pH, which is critical for tumor delivery of ALA, which suffers from low bioavailability. The PDT efficacy of the ALA-loaded AIS QDs was tested in 2D monolayers and 3D constructs of HT29 and SW480 human colon adenocarcinoma cancer cell lines. The incorporation of ALA delivery by the AIS QDs, which on their own do not cause phototoxicity, elicited significant cell death due to enhanced light-induced ROS generation and apoptotic/necrotic cell death, reducing the IC50 for ALA dramatically to about 0.1 and 0.01 mM in anionic and cationic AIS QDs, respectively. Combined with simple synthetic methods, the strong intracellular photoluminescence of AIS QDs, good biocompatibility of especially the anionic AIS QDs, and the ability to act as drug carriers for effective PDT signify that the AIS QDs, in particular AIS-2MPA, are highly promising theranostic QDs.Publication Open Access Transition from static to kinetic friction in a model lubricated system(American Institute of Physics (AIP) Publishing, 1998) Granick, S.; Department of Chemistry; Demirel, Adem Levent; Faculty Member; Department of Chemistry; College of Sciences; 6568Molecularly thin confined fluids were deformed in shear faster than structural relaxations in response to shear could be accomplished, such that with increasing deformation the systems passed from the rest state to sliding. The response of these systems-two atomically smooth mica sheets separated by a fluid comprised of globularly shaped molecules [octamethylcyclotetrasiloxane]-was studied as a function of film thickness of the fluid (from 80 to 10 Angstrom, i.e, from similar to 8 to similar to 1 molecular dimensions), as a function of normal pressure, and as a function of deformation rate, using a modified surface forces apparatus. Whereas the linear response was always liquid-like provided that the deformation rate was sufficiently slow, a "stick-slip" transition from the rest state to sliding was observed when the deformation rate was large, provided that the oscillatory frequency sufficiently exceeded the inverse intrinsic relaxation time of the confined fluid. This transition was monotonic and reversible without hysteresis for relatively thick films but for thinner films was discontinuous with hysteresis. For films thicker than 3 molecular layers (ML), two length scales in deformation were observed; the films showed nonlinear force-deformation response beginning at a deformation amplitude of 3 iq but in general showed stick slip only when the deformation was larger than this. The critical deformation at the point of stick slip decreased from 9 to 3 Angstrom with increasing normal pressure, indicating diminished plasticity of the confined structures with increasing normal pressure. The critical film thickness of 3 ML correlates with the possibility of one rather than more slip planes. The thinnest films under the highest compressive pressures showed moderate increase of the viscous shear force with increasing effective sliding velocity, but in general the viscous force reached a plateau in which force showed almost no dependence on sliding rate. In interpreting the results in the context of friction, static friction was identified with the elastic stress at rupture and kinetic friction was identified with the limiting maximum observed level of viscous force. After normalizing friction and normal forces by the contact area, the static friction coefficient was found to be 0.44 and the kinetic friction coefficient;to be 0.14, In other words, as the normal pressure increased, the elastic force needed to rupture the system increased more rapidly than the limiting shear stress. The magnitude of the limiting shear stress increased exponentially with decreasing film thickness with a decay length of 1 molecular dimension, This decay length correlates well with the known exponential decay of oscillations in the static force-distance profile, The critical shear amplitude of 3 Angstrom, relative to the molecular dimension of approximate to 9 Angstrom, is reminiscent of early estimates by Frenkel of the point of instability when planes of atoms slide over one another. (C) 1998 American Institute of Physics. [S0021-9606(98)52540-8].Publication Open Access Formation of anionic c, n-bearing chains in the interstellar medium via reactions of h- with hcxn for odd-valued x from 1 to 7(American Astronomical Society (AAS), 2017) Gianturco, F. A.; Satta, M.; Wester, R.; Department of Chemistry; Yurtsever, İsmail Ersin; Faculty Member; Department of Chemistry; College of Sciences; 7129Study Design: A retrospective study investigating decrease in the nucleus pulposus signal intensity or disc height on magnetic resonance imaging (MRI) and disc degeneration. Purpose: Although a degenerated disc cannot self- regenerate, distraction or stabilization may provide suitable conditions for rehydration and possible regeneration. This study aimed to evaluate clinical outcomes and disc regeneration via MRI in a series of patients with degenerative disc disease (DDD) who underwent lumbar stabilization with a dynamic stabilization system (DSS). Overview of Literature: A dynamic system provides rehydration during early DDD. Methods: Fifty- nine patients (mean age, 46.5 years) who undedwent stabilization with DSS for segmental instability (painful black disc) between 2004 and 2014 were retrospectively evaluated. All patients underwent MRI preoperatively and 12 months postoperatively. Intervertebral disc (IVD) degeneration grades at the implanted segment were categorized using the Pfirrmann classification system. Patients were followed for a mean of 6.4 years, and clinical outcomes were based on visual analog scale (VAS) and Oswestry disability index (ODI) scores. Results: Significant improvements in back pain VAS and ODI scores from before surgery (7 and 68%, respectively) were reported at 6 (2.85 and 27.4%, respectively) and 12 months postoperatively (1.8 and 16.3%, respectively). Postoperative IVD changes were observed in 28 patients. Improvement was observed in 20 patients (34%), whereas progressive degeneration was observed in eight patients (13.5%). Thirty- one patients (52.5%) exhibited neither improvement nor progression. Single Pfirrmann grade improvements were observed in 29% of the patients and two- grade improvements were observed in 5%. Conclusions: Our observations support the theory that physiological movement and a balanced load distribution are necessary for disc regeneration. We conclude that DSS may decelerate the degeneration process and appears to facilitate regeneration.Publication Open Access Self-assembled poly(2-ethyl-2-oxazoline) fibers in aqueous solutions(Royal Society of Chemistry (RSC), 2012) N/A; Department of Chemistry; Güner, Pınar Tatar; Miko, Annamaria; Schweinberger, Florian F.; Demirel, Adem Levent; Teaching Faculty; Teaching Faculty; Faculty Member; Department of Chemistry; Graduate School of Sciences and Engineering; College of Sciences; 188227; N/A; N/A; 6568Poly(2-ethyl-2-oxazoline) (PEOX) formed self-assembled fibers in aqueous solutions above the cloud point temperature (T-c) through a slow crystallization process. The fiber formation above T-c happened both in pure water and in the presence of salting-in (SCN-) and salting-out (CH3COO-) ions. The crystal structure and the melting temperature of the PEOX fibers were determined.Publication Open Access A new class of porous materials for efficient CO2 separation: ionic liquid/graphene aerogel composites(Elsevier, 2021) Department of Chemical and Biological Engineering; N/A; Department of Chemistry; Zeeshan, Muhammad; Yalçın, Kaan; Keskin, Seda; Uzun, Alper; Öztuna, Feriha Eylül Saraç; Ünal, Uğur; PhD Student; Faculty Member; Faculty Member; Department of Chemical and Biological Engineering; Department of Chemistry; Koç University Tüpraş Energy Center (KUTEM) / Koç Üniversitesi Tüpraş Enerji Merkezi (KÜTEM); Koç University Surface Science and Technology Center (KUYTAM) / Koç Üniversitesi Yüzey Teknolojileri Araştırmaları Merkezi (KUYTAM); Graduate School of Sciences and Engineering; College of Engineering; College of Sciences; N/A; N/A; 40548; 59917; N/A; 42079Here, we report a new post-synthesis modification strategy for functionalizing reduced graphene aerogels (rGAs) towards an exceptional CO2 separation performance. 1-N-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]) was impregnated on a rGA, prepared by reducing GA at 700 degrees C, at various ionic liquid (IL) loadings of 5, 10, 30, and 50 wt%. The resulting composites were characterized in deep detail by X-ray photoelectron spectroscopy, X-ray diffraction, N-2 physical adsorption measurements, scanning electron microscopy, Fourier transform infrared and Raman spectroscopies, and thermogravimetric analysis. Results indicated the presence of interactions between the rGA surface and the anion of the IL, potentially improving the CO2 affinity. Volumetric gas adsorption measurements using these materials showed that the deposition of [BMIM][PF6] on rGA surface at an IL loading of 50 wt% boosts the CO2/CH4 selectivity by more than 20-times, exceeding an absolute value of 120, a remarkably higher CO2/CH4 selectivity compared to that of other functionalized materials under similar operating conditions. Tunability of both the IL structure and the surface characteristics of rGA offer a tremendous degree of flexibility for the rational design of these IL/rGA composites towards high performance in gas separation applications.Publication Open Access Energy landscapes of ion clusters in isotropic quadrupolar and octupolar traps(American Institute of Physics (AIP) Publishing, 2012) Calvo, F.; Wales, D.C.; Department of Chemistry; Yurtsever, İsmail Ersin; Faculty Member; Department of Chemistry; College of Sciences; 7129The energy landscapes of ion clouds confined in isotropic quadrupolar and octupolar traps are characterized for several representative cluster sizes. All clusters exhibit stable multishell structures that belong to separate funnels. Quadrupolar confinement leads to more homogeneous clusters and denser distributions of isomers than octupolar confinement. Statistical analysis of the transition states indicates that the barriers associated with intrashell motion are lower but more asymmetric and more cooperative compared to intershell motion. The relaxation between low-energy funnels with different arrangements of shells mostly exhibits Arrhenius kinetics, with a weak variation of the activation energy at higher temperatures.