TY - JOUR AU - Olasz, Balázs AU - Fiser, Béla AU - Szőri, Milán AU - Viskolcz, Béla AU - Owen, Michael Christopher TI - Computational Elucidation of the Solvent-Dependent Addition of 4-Hydroxy-2-nonenal (HNE) to Cysteine and Cysteinate Residues JF - JOURNAL OF ORGANIC CHEMISTRY J2 - J ORG CHEM VL - 87 PY - 2022 IS - 19 SP - 12909 EP - 12920 PG - 12 SN - 0022-3263 DO - 10.1021/acs.joc.2c01487 UR - https://m2.mtmt.hu/api/publication/33179219 ID - 33179219 AB - The lipid peroxidation end product, 4-hydroxy-2-nonenal (HNE), is a secondary mediator of oxidative stress due to its strong ability to form adducts to the side chains of lysine, histidine, and cysteine residues (Cys) at increasing reactivities. This reaction can take place in various cellular environments and may be dependent on solvent. Moreover, approximately 10% of cysteine residues within the cells exist as the negatively charged cysteinate, which may also have a distinct reactivity toward HNE. In this study, quantum chemical calculations are used to investigate the reactivity of HNE toward Cys and cysteinate in three distinct solvent environments to mimic the aqueous, polar, and hydrophobic regions within the cell. Water enhances the reactivity of HNE to cysteine compared to that of the polar and hydrophobic solvents, and the reactivity of HNE is further augmented when Cys is first ionized to cysteinate. This is also confirmed by the transition state rate constant calculations. This study reveals the role of solvent polarity in these reactions and how cysteinate can account for the seemingly high reactivity of HNE toward Cys compared to other amino acid residues and demonstrates how a strong nucleophile can enhance the reactivity of an antioxidant analogue of the Cys residue. LA - English DB - MTMT ER - TY - THES AU - Olasz, Balázs TI - Theoretical investigation of the dynamics and microhydration of the F‾ + CH3I Sn2 and proton-transfer reactions [A F‾ + CH3I Sn2 és proton-transzfer reakciók dinamikájának és mikrohidratációjának elméleti vizsgálata] PB - Szegedi Tudományegyetem (SZTE) PY - 2020 SP - 95 DO - 10.14232/phd.10205 UR - https://m2.mtmt.hu/api/publication/31391546 ID - 31391546 LA - English DB - MTMT ER - TY - JOUR AU - Czakó, Gábor AU - Győri, Tibor AU - Olasz, Balázs AU - Papp, Dóra AU - Szabó, István AU - Tajti, Viktor AU - Tasi, Domonkos Attila TI - Benchmark ab initio and dynamical characterization of the stationary points of reactive atom + alkane and S N 2 potential energy surfaces JF - PHYSICAL CHEMISTRY CHEMICAL PHYSICS J2 - PHYS CHEM CHEM PHYS VL - 22 PY - 2020 IS - 8 SP - 4298 EP - 4312 PG - 15 SN - 1463-9076 DO - 10.1039/c9cp04944d UR - https://m2.mtmt.hu/api/publication/31292867 ID - 31292867 N1 - Funding Agency and Grant Number: National Research, Development and Innovation Office-NKFIH [K-125317]; Ministry of Human Capacities, Hungary [20391-3/2018/FEKUSTRAT]; Momentum (Lendulet) Program of the Hungarian Academy of Sciences Funding text: We thank the National Research, Development and Innovation Office-NKFIH, K-125317, the Ministry of Human Capacities, Hungary grant 20391-3/2018/FEKUSTRAT, and the Momentum (Lendulet) Program of the Hungarian Academy of Sciences for financial support. We acknowledge KIFU for awarding us access to computational resources based in Hungary at Szeged, Debrecen, and Budapest. LA - English DB - MTMT ER - TY - JOUR AU - Olasz, Balázs AU - Czakó, Gábor TI - Uncovering the role of the stationary points in the dynamics of the F- + CH3I reaction JF - PHYSICAL CHEMISTRY CHEMICAL PHYSICS J2 - PHYS CHEM CHEM PHYS VL - 21 PY - 2019 IS - 3 SP - 1578 EP - 1586 PG - 9 SN - 1463-9076 DO - 10.1039/c8cp06207b UR - https://m2.mtmt.hu/api/publication/30436878 ID - 30436878 N1 - Cited By :11 Export Date: 20 September 2023 CODEN: PPCPF Correspondence Address: Czakó, G.; Interdisciplinary Excellence Centre, Béla tér 1, Hungary; email: gczako@chem.u-szeged.hu LA - English DB - MTMT ER - TY - JOUR AU - Olasz, Balázs AU - Czakó, Gábor TI - High-Level-Optimized Stationary Points for the F-(H2O) + CH3I System: Proposing a New Water-Induced Double-Inversion Pathway JF - JOURNAL OF PHYSICAL CHEMISTRY A J2 - J PHYS CHEM A VL - 123 PY - 2019 IS - 2 SP - 454 EP - 462 PG - 9 SN - 1089-5639 DO - 10.1021/acs.jpca.8b10630 UR - https://m2.mtmt.hu/api/publication/30436830 ID - 30436830 N1 - Cited By :10 Export Date: 3 November 2023 CODEN: JPCAF Correspondence Address: Czakó, G.; Interdisciplinary Excellence Centre, Rerrich Béla tér 1, Hungary; email: gczako@chem.u-szeged.hu AB - We report 29 stationary points for the F-(H2O) + CH3I reaction obtained by using the high-level explicitly correlated CCSD(T)-F12b method with the aug-cc-pVDZ basis set for the determination of the benchmark structures and frequencies and the aug-cc-pVQZ basis for energy computations. The stationary points characterize the monohydrated F-- and OH--induced Walden-inversion pathways and, for the first time, the front-side attack and F--induced double-inversion mechanisms leading to CH3F with retention as well as the novel H2O-induced double inversion retention pathway producing CH3OH. Hydration effectively increases the relative energies of the stationary points, but the monohydrated inversion pathways are still barrierless, whereas the front-side attack and double-inversion barrier heights are around 30 and 20 kcal/mol, respectively. LA - English DB - MTMT ER - TY - JOUR AU - Olasz, Balázs AU - Czakó, Gábor TI - Mode-Specific Quasiclassical Dynamics of the F – + CH 3 I S N 2 and Proton-Transfer Reactions JF - JOURNAL OF PHYSICAL CHEMISTRY A J2 - J PHYS CHEM A VL - 122 PY - 2018 IS - 41 SP - 8143 EP - 8151 PG - 9 SN - 1089-5639 DO - 10.1021/acs.jpca.8b08286 UR - https://m2.mtmt.hu/api/publication/30435440 ID - 30435440 N1 - Export Date: 10 December 2019 CODEN: JPCAF Correspondence Address: Czakó, G.; Department of Physical Chemistry and Materials Science, Institute of Chemistry, University of Szeged, Rerrich Béla tér 1, Hungary; email: gczako@chem.u-szeged.hu LA - English DB - MTMT ER - TY - JOUR AU - Martin, Stei AU - Eduardo, Carrascosa AU - Alexander, Dörfler AU - Jennifer, Meyer AU - Olasz, Balázs AU - Czakó, Gábor AU - Anyang, Li AU - Hua, Guo AU - Roland, Wester TI - Stretching vibration is a spectator in nucleophilic substitution JF - SCIENCE ADVANCES J2 - SCI ADV VL - 4 PY - 2018 IS - 7 SN - 2375-2548 DO - 10.1126/sciadv.aas9544 UR - https://m2.mtmt.hu/api/publication/3406699 ID - 3406699 N1 - Funding Agency and Grant Number: Austrian Science Fund (FWF) [P 25956-N20]; DOC Fellowship by the Austrian Academy of Sciences (OAW); Scientific Research Fund of Hungary [PD-111900, K-125317]; National Natural Science Foundation of China [21203259]; Air Force Office of Scientific Research [FA9550-15-1-0305] Funding text: This work is supported by the Austrian Science Fund (FWF) (project P 25956-N20). E.C. acknowledges the support from DOC Fellowship by the Austrian Academy of Sciences (OAW). G.C. thanks the Scientific Research Fund of Hungary (PD-111900 and K-125317) for the financial support and the National Information Infrastructure Development Institute for computer resources. A.L. acknowledges the National Natural Science Foundation of China (21203259), and H. G. acknowledges a grant from the Air Force Office of Scientific Research (FA9550-15-1-0305). LA - English DB - MTMT ER - TY - JOUR AU - Győri, Tibor AU - Olasz, Balázs AU - Paragi, Gábor AU - Czakó, Gábor TI - Effects of the Level of Electronic Structure Theory on the Dynamics of the F- + CH3I Reaction JF - JOURNAL OF PHYSICAL CHEMISTRY A J2 - J PHYS CHEM A VL - 122 PY - 2018 IS - 13 SP - 3353 EP - 3364 PG - 12 SN - 1089-5639 DO - 10.1021/acs.jpca.8b00770 UR - https://m2.mtmt.hu/api/publication/3363941 ID - 3363941 N1 - Department of Physical Chemistry and Materials Science, Institute of Chemistry, University of Szeged, Rerrich Béla tér 1, Szeged, H-6720, Hungary MTA-SZTE Biomimetic Systems Research Group, University of Szeged, Dóm tér 8, Szeged, H-6720, Hungary Cited By :21 Export Date: 25 September 2023 CODEN: JPCAF Correspondence Address: Czakó, G.; Department of Physical Chemistry and Materials Science, Rerrich Béla tér 1, Hungary; email: gczako@chem.u-szeged.hu LA - English DB - MTMT ER - TY - JOUR AU - Szabó, István AU - Olasz, Balázs AU - Czakó, Gábor TI - Deciphering Front-Side Complex Formation in S(N)2 Reactions via Dynamics Mapping JF - JOURNAL OF PHYSICAL CHEMISTRY LETTERS J2 - J PHYS CHEM LETT VL - 8 PY - 2017 IS - 13 SP - 2917 EP - 2923 PG - 7 SN - 1948-7185 DO - 10.1021/acs.jpclett.7b01253 UR - https://m2.mtmt.hu/api/publication/3262945 ID - 3262945 N1 - Department of Chemistry, King's College London, London, SE1 1DB, United Kingdom Department of Physical Chemistry and Materials Science, Institute of Chemistry, University of Szeged, Rerrich Béla tér 1, Szeged, H-6720, Hungary Cited By :18 Export Date: 10 December 2019 Correspondence Address: Szabó, I.; Department of Chemistry, King's College LondonUnited Kingdom; email: istvan.szabo@kcl.ac.uk AB - Due to their importance in organic chemistry, the atomistic understanding of bimolecular nucleophilic substitution (S(N)2) reactions shows exponentially growing interest. In this publication, the effect of front-side complex (FSC) formation is uncovered via quasi-classical trajectory computations combined with a novel analysis method called trajectory orthogonal projection (TOP). For both F- + CH3Y [Y = Cl,I] reactions, the lifetime distributions of the F-center dot center dot center dot YCH3 front-side complex revealed weakly trapped nucleophiles (F-). However, only the F- + CH3I reaction features strongly trapped nucleophiles in the front-side region of the prereaction well. Interestingly, both back-side and front-side attack show propensity to long-lived FSC formation. Spatial distributions of the nucleophile demonstrate more prominent FSC formation in case of the F- + CH3I reaction compared to F- + CH3Cl. The presence of front-side intermediates and the broad spatial distribution in the back-side region may explain the indirect nature of the F- + CH3I reaction. LA - English DB - MTMT ER - TY - JOUR AU - Olasz, Balázs AU - Szabó, István AU - Czakó, Gábor TI - High-level ab initio potential energy surface and dynamics of the F- + CH3I SN2 and proton-transfer reactions JF - CHEMICAL SCIENCE J2 - CHEM SCI VL - 8 PY - 2017 IS - 4 SP - 3164 EP - 3170 PG - 7 SN - 2041-6520 DO - 10.1039/C7SC00033B UR - https://m2.mtmt.hu/api/publication/3188572 ID - 3188572 N1 - Funding Agency and Grant Number: Scientific Research Fund of Hungary [PD-111900]; Janos Bolyai Research Scholarship of the Hungarian Academy of Sciences Funding text: G.C. thanks the Scientific Research Fund of Hungary (PD-111900) and the Janos Bolyai Research Scholarship of the Hungarian Academy of Sciences for financial support. We acknowledge the National Information Infrastructure Development Institute for awarding us access to resource based in Hungary at Debrecen and Szeged. LA - English DB - MTMT ER -