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Publication Open Access An integrated computational-experimental hierarchical approach for the rational design of an IL/UiO-66 composite offering infinite CO2 selectivity(Wiley, 2022) Department of Chemical and Biological Engineering; Department of Chemistry; Zeeshan, Muhammad; Gülbalkan, Hasan Can; Durak, Özce; Haşlak, Zeynep Pınar; Ünal, Uğur; Keskin, Seda; Uzun, Alper; 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); College of Engineering; College of Sciences; Graduate School of Sciences and Engineering; N/A; N/A; N/A; N/A; 42079; 40548; 59917Owing to the possibility of generating theoretically unlimited numbers of ionic liquid (IL)-metal-organic framework (MOF) combinations, experimental studies on IL/MOF composites for gas separation applications are mostly conducted on a trial-and-error basis. To address this problem, an integrated computational-experimental hierarchical approach is presented for selecting the best IL-MOF combination for a target gas separation application. For this purpose, UiO-66 and pyrrolidinium-based ILs are chosen as the parent MOF and IL family, respectively, and three powerful computational tools, Conductor-like Screening Model for Realistic Solvents calculations, density functional theory calculations, and grand canonical Monte Carlo simulations, are integrated to identify the most promising IL-UiO-66 combination as 1-n-butyl-1-methylpyrrolidinium dicyanamide/UiO-66, [BMPyrr][DCA]/UiO-66. Then, this composite is synthesized, characterized in deep detail, and tested for CO2/N-2, CO2/CH4, and CH4/N-2 separations. Results demonstrate that [BMPyrr][DCA]/UiO-66 offers an extraordinary gas separation performance, with practically infinite CO2 and CH4 selectivities over N-2 at 15 degrees C and at low pressures. The integrated hierarchical approach proposed in this work paves the way for the rational design and development of novel IL/MOF composites offering exceptional performance for any desired gas separation application.Publication Open Access Balanced intersystem crossing in iodinated silicon-fluoresceins allows new class of red shifted theranostic agents(American Chemical Society (ACS), 2021) Elmazoğlu, Zübeyir; Karaman, Osman; Günbaş, Görkem; Department of Chemistry; Çetin, Sultan; Kölemen, Safacan; Gündüz, Hande; PhD Student; Faculty Member; Researcher; Department of Chemistry; Koç University Surface Science and Technology Center (KUYTAM) / Koç Üniversitesi Yüzey Teknolojileri Araştırmaları Merkezi (KUYTAM); Koç University Tüpraş Energy Center (KUTEM) / Koç Üniversitesi Tüpraş Enerji Merkezi (KÜTEM); Koç University Boron and Advanced Materials Application and Research Center (KUBAM) / Koç Üniversitesi Bor ve İleri Malzemeler Uygulama ve Araştırma Merkezi (KUBAM); Graduate School of Sciences and Engineering; College of Sciences; N/A; 272051; N/AIodination of the silicon-fluorescein core revealed a new class of highly cytotoxic, red-shifted and water-soluble photosensitizer (SF-I) which is also fairly emissive to serve as a theranostic agent. Singlet oxygen generation capacity of SF-I was evaluated chemically, and up to 45% singlet oxygen quantum yield was reported in aqueous solutions. SF-I was further tested in triple negative breast (MDA MB-231) and colon (HCT-116) cancer cell lines, which are known to have limited chemotherapy options as well as very poor prognosis. SF-I induced efficient singlet oxygen generation and consequent photocytotoxicity in both cell lines upon light irradiation with a negligible dark toxicity while allowing cell imaging at the same time. SF-I marks the first ever example of a silicon xanthene-based photosensitizer and holds a lot of promise as a small-molecule-based theranostic scaffold.Publication Open Access Bosonic helium droplets with cationic impurities: onset of electrostriction and snowball effects from quantum calculations(American Institute of Physics (AIP) Publishing, 2007) Coccia, E.; Bodo, E.; Marinetti, F.; Gianturco, F. A.; Yıldırım, E.; Yurtsever, M.; Department of Chemistry; Yurtsever, İsmail Ersin; Faculty Member; Department of Chemistry; College of Sciences; 7129Variational Monte Carlo and diffusion Monte Carlo calculations have been carried out for cations such as Li(+), Na(+), and K(+) as dopants of small helium clusters over a range of cluster sizes up to about 12 solvent atoms. The interaction has been modeled through a sum-of-potential picture that disregards higher order effects beyond atom-atom and atom-ion contributions. The latter were obtained from highly correlated ab initio calculations over a broad range of interatomic distances. This study focuses on two of the most striking features of the microsolvation in a quantum solvent of a cationic dopant: electrostriction and snowball effects. They are discussed here in detail and in relation with the nanoscopic properties of the interaction forces at play within a fully quantum picture of the cluster features.Publication Open Access Cationic [6]helicenes: tuning (chir)optical properties up to the near infra-red(Elsevier, 2022) Labrador, Geraldine M.; Jacquemin, Denis; Lacour, Jerome; Department of Chemistry; Bosson, Johann; Department of Chemistry; College of SciencesThe intramolecular condensation of ortho substituents of triaryl carbenium ions can lead to the formation of cationic helicenes. These chiral and configurationally stable molecules exhibit extended optical properties reminiscent of their parent methylium ions. Among them, cationic [6]helicenes are particularly interesting as orthogonal late-stage functionalization strategies allow the introduction of a variety of auxochromes with different regiochemistry. Intense chiroptical properties can thus be tailored in the far red and up to the near infra-red (NIR) spectral windows. A wealth of applications can be foreseen, in particular in material sciences.Publication Open Access Collisional relaxation kinetics for ortho and para NH2- under photodetachment in cold ion traps(Royal Society of Chemistry (RSC), 2018) Gianturco, Francesco A.; Lakhmanskaya, Olga Y.; Vera, Mario Hernandez; Wester, Roland; Department of Chemistry; Yurtsever, İsmail Ersin; Faculty Member; Department of Chemistry; College of Sciences; 7129The collisional cooling of the internal rotational states of the nonlinear anion NH2- ((1)A(1)), occurring at the low temperature of a cold ion trap under helium buffer gas cooling, is examined via quantum dynamics calculations and ion decay rate measurements. The calculations employ a novel ab initio potential energy surface that describes the interaction anisotropy and range of action between the molecular anions and the neutral He atoms. The state changing integral cross sections are employed to obtain the state-to-state rate coefficients, separately for the ortho- and the para-NH2- ions. These rates are in turn used to compute the state population evolution in the trap for both species, once photodetachment by a laser is initiated in the trap. The present work shows results for the combined losses of both species after the photodetachment laser is switched on and analyzes the differences of loss kinetics between the two hyperfine isomers.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 Hydrogen-bonded multilayers of micelles of a dually responsive dicationic block copolymer(Royal Society of Chemistry (RSC), 2012) Tuncer, Cansel; Bütün, Vural; Department of Chemistry; Erel-Göktepe, İrem; Karahan, Hüseyin Enis; Demirel, Adem Levent; PhD Student; Faculty Member; Department of Chemistry; College of Sciences; N/A; N/A; 6568We report the fabrication of hydrogen-bonded multilayers of micelles of a dually responsive, dicationic block copolymer, poly[2-(N-morpholino)ethyl methacrylate-block-2-(diisopropylamino)ethyl methacrylate] (PMEMA-b-PDPA). By taking advantage of the difference in the hydrophilicity of PMEMA and PDPA blocks, micelles with a PMEMA-corona and a PDPA-core were obtained above pH 6.5 and were assembled layer-by-layer at the surface with tannic acid (TA) at pH 7.4 through hydrogen bonding interactions between morpholino units of PMEMA and hydroxyl groups of TA. Destruction of PMEMA-b-PDPA micelles/TA films could be controlled at both acidic and basic conditions. At basic pH (pH = 8.75), multilayers disintegrated due to ionization of TA and disruption of hydrogen bonding interactions between layers of micelles and TA. At moderately acidic pH values, partially dissolved PMEMA-b-PDPA micelles and monomers underwent a restructuring with TA molecules and remained adsorbed at the surface. Complete dissolution of the multilayers occurred at around pH 3.6 due to further protonation of the tertiary amino groups on both blocks of PMEMA-b-PDPA, resulting in a charge imbalance between PMEMA-b-PDPA and TA layers followed by disintegration of the films. We have also encapsulated pyrene in the micellar cores and found that pyrene released from PMEMA-b-PDPA micelles/TA films increased 1.5- and 2.5-fold when the pH was decreased from 7.5 to 6 and 5, respectively. Such an increase in the amount of pyrene released was due to pH-controlled dissolution of the micellar cores. We have also found that at pH 7.5, increasing the temperature to 40 degrees C enhanced the release of pyrene by approximately 2-fold. Such an increase is due to lower critical solution temperature (LCST) behaviour of coronal PMEMA chains leading to temperature-induced conformational changes on the coronal chains, facilitating the release of pyrene through the coronal chains into the solution. Hydrogen bonded multilayers of micelles of a dicationic block copolymer are interesting due to the response of both multilayers and micellar cores at different pH paving the way for multiple pH-controlled delivery of functional molecules from surfaces.Publication Open Access Locked and loaded: ?-galactosidase activated photodynamic therapy agent enables selective imaging and targeted treatment of glioblastoma multiforme cancer cells(American Chemical Society (ACS), 2022) Elmazoğlu, Z.; Atakan, G.; Kepil, D.; Aykent, G.; Günbaş, G.; Department of Chemistry; Kölemen, Safacan; Almammadov, Toghrul; Faculty Member; Researcher; Department of Chemistry; Koç University Surface Science and Technology Center (KUYTAM) / Koç Üniversitesi Yüzey Teknolojileri Araştırmaları Merkezi (KUYTAM); Koç University Boron and Advanced Materials Application and Research Center (KUBAM) / Koç Üniversitesi Bor ve İleri Malzemeler Uygulama ve Araştırma Merkezi (KUBAM); College of Sciences; 272051; N/ASelective detection and effective therapy of brain cancer, specifically, the very aggressive glioblastoma multiforme (GBM), remains one of the paramount challenges in clinical settings. While radiotherapy combined surgery is proposed as the main treatment course, it has several drawbacks such as complexity of the operation and common development of recurrent tumors in this course of patient care. Unique opportunities presented by photodynamic therapy (PDT) offer promising, effective, and precise therapy against GBM cells along with simultaneous imaging opportunities. However, activatable, theranostic molecular systems in PDT modality for GBM remained scarce. Specifically, even though elevated fi-galactosidase (fi-gal) activity in glioblastoma cells is well-documented, targeted, activatable therapeutic PDT agents have not been realized. Herein, we report a fi-galactosidase (fi-gal) activatable phototheranostic agent based on an iodinated resorufin core (RB-1) which was realized in only three steps with commercial reagents in 29% overall yield. RB-1 showed very high singlet oxygen (1O2) quantum yield (54%) accompanied by a remarkable turn-on response in fluorescence upon enzymatic activation. RB-1 was tested in different cell lines and revealed selective photocytotoxicity in U-87MG glioblastoma cells. Additionally, thanks to almost 7% fluorescence quantum yield (phi F) despite extremely high 1O2 generation yield, RB-1 was also demonstrated as a successful agent for fluorescence imaging of U-87MG cells. Due to significantly lower (fi-gal) activity in healthy cells (NIH/3T3), RB-1 stayed in a passive state and showed minimal photo and dark toxicity. RB-1 marks the first example of a fi- gal activatable phototheranostic agent toward effective treatment of glioblastoma.Publication Open Access N2+(2Σg) and Rb(2S) in a hybrid trap: modeling ion losses from radiative association paths(Royal Society of Chemistry (RSC), 2019) Gianturco, F. A.; Dorfler, A. D.; Willitsch, S.; Gonzalez-Lezana, T.; Villarreal, P.; Department of Chemistry; Yurtsever, İsmail Ersin; Faculty Member; Department of Chemistry; College of Sciences; 7129By employing ab initio computed intermolecular potential energy surfaces we calculate the radiative association probabilities and rates for two different associative mechanisms involving trapped molecular ions N 2 + ( 2 Σ g ) interacting either directly with ultracold Rb atoms or undergoing charge-exchange (CE) processes leading to the formation of complexes of the strongly exothermic products N 2 (X 1 Σ g ) plus Rb + ( 1 S 0 ). The two processes are expected to provide possible paths to ion losses in the trap within the timescale of experiments. The present calculations suggest that the associative rates for the 'vibrational' direct process are too small to be of any significant importance at the millikelvin temperatures considered in the experiments, while the 'vibronic' path into radiatively associating the CE products has a probability of occurring which is several orders of magnitude larger. However the reaction rate constants attributed to non-adiabatic CE [F. H. J. Hall and S. Willist, Phys. Rev. Lett., 2012, 109, 233202] are in turn several orders of magnitude larger than the radiative ones calculated here, thereby making the primary experimental process substantially unaffected by the radiative losses channel.Publication Open Access pH-responsive layer-by-layer films of zwitterionic block copolymer micelles(Royal Society of Chemistry (RSC), 2014) Yusan, Pelin; Tuncel, İrem; Bütün, Vural; Erel-Goktepe, İrem; Department of Chemistry; Demirel, Adem Levent; Faculty Member; Department of Chemistry; College of Sciences; 6568We report a strategy to incorporate micelles of poly[3-dimethyl (methacryloyloxyethyl) ammonium propane sulfonate]-block-poly[2-(diisopropylamino) ethyl methacrylate] (beta PDMA-b-PDPA) into electrostatic layer-by-layer (LbL) films. We obtained micelles with pH-responsive PDPA-cores and zwitterionic bPDMA-coronae at pH 8.5 through pH-induced self-assembly of bPDMA-b-PDPA in aqueous solution. To incorporate bPDMA-b-PDPA micelles into LbL films, we first obtained a net electrical charge on bPDMA-coronae. Negative charges of the zwitterionic units were screened through complexation of bPDMA-b-PDPA micelles and poly(allylamine hydrochloride) (PAH). Positively charged micellar complexes were then self-assembled at the surface using poly(sodium 4-styrenesulfonate) (PSS). The pH-stability of the multilayers was examined by exposing the films to decreasing pH values. Despite the disintegration of micellar complexes below pH 7, no change in film thickness was recorded between pH 8.5 and 3.5. Only similar to 20% of the film released at pH < 3.5. Moreover, we demonstrated that when multilayers were exposed to decreasing pH at a temperature below the upper critical solution temperature (UCST) of betainized coronal chains, the film thickness increased by 20% between pH 4.5 and 3. This is probably due to phase separation of the corona block and formation of voids within the film, probably entrapping water molecules within the multilayers. Decreasing temperature also shifted the critical disintegration pH (onset of multilayer dissolution) to a slightly lower pH. By taking advantage of the pH-responsive cores, we showed that multilayers were capable of releasing functional molecules under moderately acidic conditions. Important biological properties of polybetaines, higher loading capacity of zwitterionic block copolymer micelles than linear polybetaines and pH-response of the multilayers at physiologically related pH values make such films promising for biomedical applications.