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Kayı, Hakan
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Hakan, Kayı
Kayi,H.
H.,Kayı
H.,Kayi
Kayı,H.
Hakan, Kayi
K., Hakan
K.,Hakan
Kayi, Hakan
H., Kayi
Kayı, Hakan
Kayi, H.
Kayi,H.
H.,Kayı
H.,Kayi
Kayı,H.
Hakan, Kayi
K., Hakan
K.,Hakan
Kayi, Hakan
H., Kayi
Kayı, Hakan
Kayi, H.
Job Title
Doktor Öğretim Üyesi
Email Address
hakan.kayi@atilim.edu.tr
Main Affiliation
Chemical Engineering
Status
Former Staff
Website
ORCID ID
Scopus Author ID
Turkish CoHE Profile ID
Google Scholar ID
WoS Researcher ID
Scholarly Output
30
Articles
21
Citation Count
101
Supervised Theses
8
21 results
Scholarly Output Search Results
Now showing 1 - 10 of 21
Article Citation - WoS: 4Citation - Scopus: 6Design of Novel Tellurium and Selenium Containing Semiconducting Polymers Using Quantum Mechanical Tools(Elsevier, 2017) Kaya, Birnur; Kayi, Hakan; Chemical EngineeringStructural, optical and electronic properties of the two novel donor-acceptor-donor type conjugated polymers based on 4,7-di(selenophen-2-yl)benzo[c][1,2,5]selenadiazole (SeSeSe) and 4,7-di(tellurophen-2-yl)benzo[c][1,2,5]telluradiazole (TeTeTe) are investigated by means of quantum chemical calculations utilizing conventional and long-range corrected hybrid functionals. The lowest energy structures of the SeSeSe and TeTeTe monomers and oligomers are revealed through conformational analysis, while their electronic properties are obtained from density functional theory (DFT) molecular orbital calculations and optical properties are obtained from the time dependent DFT (TD-DFT) calculations for UV-vis absorption spectra. Electronic band gaps that directly affect the semiconducting properties of these novel polymers are calculated by using linear regression analysis of DFT data, and also periodic boundary conditions calculations (PBC-DFT). Our results indicate that SeSeSe and TeTeTe polymers have considerably lower band gap values than that of their furan-, thiophene-, benzooxadiazole- and benzothiadiazole-based analogs. The novel SeSeSe and TeTeTe polymers with improved optical and electronic properties may have an important role in the near future, especially for the optoelectronic and photovoltaic applications. (C) 2016 Elsevier B.V. All rights reserved.Article A computational study on 4,7-di(furan-2-yl)benzo[c][1,2,5] thiadiazole monomer and its oligomers(Journal of Molecular Modeling, 2014) Kayı, Hakan; Chemical EngineeringThe energy gap, Eg, between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molec ular orbital (LUMO) energy levels that determines the elec tronic and optical properties of 4,7-di(furan-2- yl)benzo[c][1,2,5]thiadiazole (FSF) polymer is calculated by performing quantum chemical calculations. First, we theoret ically investigated the most stable conformers of FSF mono mer and its corresponding oligomers at the B3LYP/6-31G(d) and B3LYP/LANL2DZ levels of theory. We reveal the theoret ical molecular structure of this very recently synthesized novel monomer and its oligomers for the first time in the literature. Our results from the B3LYP/6-31G(d) calculations indicated that FSF polymer has a low HOMO-LUMO gap of 1.55 eV to be in good agreement with the experiments. Experimental design and synthesis of novel conjugated polymers require time-consuming and expensive procedures. The findings from this study are promising for the use of computational methods in the design of the novel conjugated polymers, and help to narrow the materials to be used in design and synthesis of conjugated polymers with desired properties.Article Citation - WoS: 10Citation - Scopus: 9A Computational Study on 4,7-Di(furan Monomer and Its Oligomers(Springer, 2014) Kayi, Hakan; Kayı, Hakan; Kayı, Hakan; Chemical Engineering; Chemical EngineeringThe energy gap, Eg, between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energy levels that determines the electronic and optical properties of 4,7-di(furan-2yl)benzo[c][1,2,5]thiadiazole (FSF) polymer is calculated by performing quantum chemical calculations. First, we theoretically investigated the most stable conformers of FSF monomer and its corresponding oligomers at the B3LYP/6-31G(d) and B3LYP/LANL2DZ levels of theory. We reveal the theoretical molecular structure of this very recently synthesized novel monomer and its oligomers for the first time in the literature. Our results from the B3LYP/6-31G(d) calculations indicated that FSF polymer has a low HOMO-LUMO gap of 1.55 eV to be in good agreement with the experiments. Experimental design and synthesis of novel conjugated polymers require time-consuming and expensive procedures. The findings from this study are promising for the use of computational methods in the design of the novel conjugated polymers, and help to narrow the materials to be used in design and synthesis of conjugated polymers with desired properties.Article Citation - WoS: 8Citation - Scopus: 9A Theoretical Investigation of 4,7-Di(furan Donor-Acceptor Type Conjugated Polymer(Elsevier, 2015) Kayi, Hakan; Elkamel, Ali; Chemical EngineeringQuantum chemical calculations are performed using density functional theory (DFT) to investigate the HOMO-LUMO energy gap of the 4,7-di(furan-2-yl)benzo[c][1,2,5]selenadiazole-based (FSeF) donor-acceptor type conjugated polymer which ascertains the optoelectronic properties and plays a crucial role, especially in polymeric solar cell applications. In this paper, the most stable conformers of the FSeF monomer and its corresponding oligomers are investigated at the B3LYP/Def2TZV and B3LYP/LANL2DZ levels of theory, and their molecular structures are revealed. The band gap of the polymer is determined by linear-fitting and extrapolation of the DFT data. This gap is found to be 1.44 eV and 1.45 eV by the B3LYP/Def2TZV, and B3LYP/LANL2DZ with PCM calculations, respectively. Our theoretical findings related to the band gap of the FSeF polymer (PFSeF) are in good agreement with other experimental studies in the literature and, hence, the theoretical methods used in this study are promising for the design of similar donor-acceptor type novel conjugated polymers. (C) 2014 Elsevier B.V. All rights reserved.Article Citation - WoS: 19Citation - Scopus: 18Deviations From Born-Oppenheimer Theory in Structural Chemistry: Jahn-Teller, Pseudo Jahn-Teller, and Hidden Pseudo Jahn-Teller Effects in C3h3< and C3h3<(Amer Chemical Soc, 2013) Kayi, H.; Garcia-Fernandez, P.; Bersuker, I. B.; Boggs, J. E.; Chemical EngineeringThe electronic structure and vibronic coupling in two similar molecular systems, radical C3H3 and anion C3H3-, in ground and excited states, are investigated in detail to show how their equilibrium structures, in deviation from the Born-Oppenheimer approximation, originate from the vibronic mixing of at least two electronic states, producing the Jahn-Teller UT), pseudo JT (PJT), and hidden PJT effects. Starting with the high-symmetry geometry D3h of C3H3, we evaluated its 2-fold degenerate ground electronic state 2E" and two lowest excited states 2A,' and 2E' and found that all of them contribute to the distortion of the ground state via the JT vibronic coupling problem E" e' and two PJT problems (E" + A(1)') circle star e" and (E" + E') circle times (a2" + e"); all the three active normal modes e'(1335 e"(1030 cm(-1)), and a2"(778 cm(-1)) are imaginary, meaning that all the three vibronic couplings are sufficiently strong to cause instability, albeit in different directions. The first of them, the ground state JT effect, enhances one of the C-C bonds (toward an ethylenic form with C-2v symmetry), while the two PJT effects produce, respectively, cis (a(2)" toward C-3v symmetry) and trans (e") puckering of the hydrogen atoms. As a result, C3H3 has two coexisting equilibrium configurations with different geometry. In the C3H3- anion, the ground electronic state in DA symmetry is an orbitally nondegenerate spin triplet (3)A(2)' with a group of close in energy singlet and triplet excited states in the order of (1)A(1),', (3)A(1)', E-1", E-3", and E-1'. This shows that two PJT couplings, (3A(2)' + (3)A(1)") circle times a(2)" and (3A2' + 3E") e", may influence the geometry of the equilibrium structure in the 3A2' state. Indeed, both vibrational modes, a(2)"(1034 cm(-1)) and e"(1284 cm(-1)), are imaginary in this state. Similar to the radical case, they produce, respectively, cis (a(2)") and trans (e") puckering of the hydrogen atoms, but no e' distortion of the basic C-3 triangle; the equilibrium configuration with Cs symmetry occurs along the stronger e" distortions. Another higher-in-energy triplet-state minimum with C-2v symmetry emerges as a result of a strong JTE in the excited 3E" electronic state. In addition to these APES minima with spin-triplet electronic states, the system has a coexisting minimum with a spin-singlet electronic state, which is shown to be due to the hidden PJT effect that couples two singlet excited states. The two lowest equilibrium configurations of the C3H3- anion with different geometry and spin realize a (common to all electronic e(2) configurations) magnetic and structural bistability accompanied by a spin crossover. Some general spectroscopic consequences are also noted. As a whole, this article is intended to demonstrate the efficiency of the vibronic coupling approach in rationalizing the origin of complicated structural features of molecular systems as due to a combination of nonadiabatic JT effects.Article Citation - WoS: 3Citation - Scopus: 3Correlations Between Hardness, Electrostatic Interactions, and Thermodynamic Parameters in the Decomposition Reactions of 3-Buten 3-Methoxy and Ethoxyethene(Springer/plenum Publishers, 2015) Hasanzadeh, Neda; Nori-Shargh, Davood; Kayi, Hakan; Javid, Nargess Rezaei; Chemical EngineeringDecomposition of the three isomeric compounds, 3-buten-1-ol (1), 3-methoxy-1-propene (2), and ethoxyethene (3), at two different (300 and 550 K) temperatures has been investigated by means of ab initio molecular orbital theory (MP2/6-311+G**//B3LYP/6-311+G**), hybrid-density functional theory (B3LYP/6-311+G**), the complete basis set, nuclear magnetic resonance analysis, and the electrostatic model associated with the dipole-dipole interactions. All three levels of theory showed that the calculated Gibbs free energy differences between the transition and ground state structures (Delta G (not equal)) increase from compound 1 to compound 3. The variations of the calculated Delta G (not equal) values can not be justified by the decrease of the calculated global hardness (eta) differences between the ground and transition states structures (i.e., Delta[eta(GS)-eta(TS)]). Based on the synchronicity indices, the transition state structures of compounds 1-3 involve synchronous aromatic transition structures, but there is no significant difference between their calculated synchronicity indices. The optimized geometries for the transition state structures of the decomposition reactions of compounds 1-3 consist in chair-like six-membered rings. The variation of the calculated activation entropy (Delta S (not equal)) values can not be justified by the decrease of Delta[eta(GS)-eta(TS)] parameter from compound 1 to compound 3. On the other hand, dipole moment differences between the ground and transition state structures [Delta(A mu (TS)-A mu (GS))] decrease from compound 1 to compound 3. Therefore, the electrostatic model associated with the dipole-dipole interactions justifies the increase of the calculated Delta G (not equal) values from compound 1 to compound 3. The correlations between Delta G (not equal), Delta[eta(GS)-eta(TS)], (Delta S (not equal)), k(T), electrostatic model, and structural parameters have been investigated.Article Citation - WoS: 3Citation - Scopus: 3Anticancer Investigation of Platinum and Copper-Based Complexes Containing Quinoxaline Ligands(Elsevier, 2022) El-Beshti, Hager Sadek; Yildizhan, Yasemin; Kayi, Hakan; Cetin, Yuksel; Adiguzel, Zelal; Gungor-Topcu, Gamze; Ozalp-Yaman, Seniz; Chemical EngineeringThis research focuses on synthesis and anticancer activity of trans-[(dichloro)bisdipyridlquinoxalino] and [(dichloro)bisdithienylquinoxalino]copper(II)/platinum(II) compounds as prodrug candidates. The binding interaction of these compounds with calf thymus DNA (CT-DNA) and human serum albumin (HSA) of the complexes were assessed with UV titration, thermal decomposition, viscometric, and fluorometric measurements. The nature of the binding of the complexes on DNA were revealed as electrostatic interaction between the cationic metal complexes ion and the negative phosphate groups of CT-DNA upon removal of the counter ion, chloride. In addition, our complexes induced a surface contact through the hydrophobic region of protein. Antitumor activity of the complexes against human glioblastoma A172, LN229, and U87 cell lines and human lung A549, human breast MDA-231, human cervix HeLa, and human prostate PC-3 cell lines were investigated by examining cell viability, oxidative stress, apoptosis, and migration/invasion. Cytotoxicity of the complexes was evaluated by MTT test. The U87 and HeLa cells were investigated as the cancer cells most sensitive to our complexes. The exerted cytotoxic effect of dipyridlquinoxalino and dithienylquinoxalino copper(II)/platinum(II) complexes was attributed to the formation of the reactive oxygen species in vitro. It is clearly demonstrated that trans-[(dichloro)bisdithenylquinoxalino]copper (II) (Cu(dtq)) has the highest DNA degradation potential and anticancer effect among the tested complexes by leading apoptosis. Wound healing and invasion analysis results also supported the anticancer activity of Cu(dtq). (C) 2021 Elsevier B.V. All rights reserved.Article Conformational Behaviors of Trans-2,3 and Trans-2,5 1,4-Diselenanes. a Complete Basis Set, Hybrid-Density Functional Theory Study and Natural Bond Orbital Interpretations(Journal of Molecular Modeling, 2014) Nori-shargh, Davood; Mousavı, Seiedeh Negar; Kayı, Hakan; Chemical EngineeringComplete basis set CBS-4, hybrid-density func tional theory (hybrid-DFT: B3LYP/6-311+G**) based methods and natural bond orbital (NBO) interpretations have been used to examine the contributions of the hyperconjugative, electrostatic, and steric effects on the con formational behaviors of trans-2,3-dihalo-1,4-diselenane [halo=F (1), Cl (2), Br (3)] and trans-2,5-dihalo-1,4- diselenane [halo = F (4), Cl (5), Br (6)]. Both levels of theory showed that the axial conformation stability, compared to its corresponding equatorial conformation, decreases from com pounds 1→3 and 4→6. Based on the results obtained from the NBO analysis, there are significant anomeric effects for compounds 1-6. The anomeric effect associated with the electron delocalization is in favor of the axial conformation and increases from compounds 1→3 and 4→6. On the other hand, dipole moment differences between the axial and equa torial conformations [Δ(μeq - μax)] decrease from compounds 1→3. Although Δ(μeq-μax) parameter decreases from com pound 1 to compound 3, the dipole moment values of the axial conformations are smaller than those of their corresponding equatorial conformations. Therefore, the anomeric effect as sociated with the electron delocalizations (for halogen-C-Se segments) and the electrostatic model associated with the dipole-dipole interactions fail to account for the increase of the equatorial conformations stability on going from com pound 1 to compound 3. Since there is no dipole moment for the axial and equatorial conformations of compounds 4-6, consequently, the conformational preferences in compounds 1-6 is in general dictated by the steric hindrance factor asso ciated with the 1,3-syn-axial repulsions. Importantly, the CBS-4 results show that the entropy difference (ΔS) between the equatorial axial conformations increases from compounds 1→3 and 4→6. This fact can be explained by the anomeric effect associated with the electron delocalization which affects the C2-Se bond orders and increase the rigidity of the corre sponding rings. The Gibbs free energy difference values be tween the axial and equatorial conformations (i.e. ΔGax-ax and ΔGeq-eq) of compounds 1 and 4, 2 and 5 and also 3 and 6 have been calculated. The correlations between the anomeric effect, electrostatic model, ΔGeq-ax, ΔGax-ax, ΔGeq-eq, bond orders, dipole-dipole interactions, structural parameters and confor mational behaviors of compounds 1-6 have been investigated.Article Theoretical Investigation of Carbon Dioxide Capture by Aqueous Boric Acid Solution: a Termolecular Reaction Mechanism(2018) Kayı, Hakan; Chemical EngineeringHitherto, boric is suggested and used as a promoter or catalyst for carbondioxide capture in various chemical absorption reactions, such as, absorptionby aqueous potassium carbonate solution to increase mass transfer rate. Butin this study, a single step termolecular reaction mechanism is suggested forthe chemical absorption of carbon dioxide directly by boric acid and water. Thereaction thermochemistry and reaction kinetics for termolecular mechanism areinvestigated by using density functional theory calculations at the B3LYP/6-31G(d)level of theory by taking into account of the implicit solvent effects of water throughthe polarizable continuum model and dispersion corrections. The findings obtainedfrom theoretical calculations indicate that it is possible to capture carbon dioxidewith boric acid in the form of B(OH)2OCOOH.Article Citation - WoS: 2Citation - Scopus: 3Experimental and Theoretical Investigation of the Reaction Between Co2 and Carbon Dioxide Binding Organic Liquids(Tubitak Scientific & Technological Research Council Turkey, 2016) Tankal, Hilal; Yuksel Orhan, Ozge; Alper, Erdogan; Ozdogan, Telhat; Kayi, Hakan; Chemical EngineeringThe reaction kinetics of CO2 absorption into new carbon dioxide binding organic liquids (CO(2)BOLs) was comprehensively studied to evaluate their potential for CO2 removal. A stopped-flow apparatus with conductivity detection was used to determine the CO2 absorption kinetics of novel CO(2)BOLs composed of DBN (1,5-diazabicyclo[4.3.0]non-5-ene)/1-propanol and TBD (1,5,7-triazabicyclo[4.4.0]dec-5-ene)/1-butanol. A modified termolecular reaction mechanism for the reaction of CO2 with CO(2)BOLs was used to calculate the observed pseudo-first order rate constant k(0) (s(-1)) and second-order reaction rate constant k(2) (m(3)/kmol.s). Experiments were performed by varying organic base (DBN or TBD) weight percentage in alcohol medium for a temperature range of 288-308 K. It was found that k(0) increased with increasing amine concentration and temperature. By comparing using two different CO2BOL systems, it was observed that the TBD/1-butanol system has faster reaction kinetics than the DBN/1-propanol system. Finally, experimental and theoretical activation energies of these CO2BOL systems were obtained and compared. Quantum chemical calculations using spin restricted B3LYP and MP2 methods were utilized to reveal the structural and energetic details of the single-step termolecular reaction mechanism.
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