Article
Biochemistry & Molecular Biology
Victor N. Nemykin, Jared R. Sabin, Brian W. Kail, Anup Upadhyay, Michael P. Hendrich, Partha Basu
Summary: The EPR investigation of mononuclear cis- and trans-(L1O)MoOCl2 complexes reveals a difference in their spin Hamiltonian parameters due to the different ligand fields created by the heteroscorpionate donor atoms. DFT calculations were used to determine the values and orientations of the g and A tensors in various isomeric mononuclear oxo-molybdenum(V) complexes. The results showed that the use of a hybrid exchange-correlation functional with 25% of the Hartree-Fock exchange provided the best agreement between theory and experiment. The influence of ligand fields on the energies and contributions of molybdenum d orbitals to the g and A tensors and their relative orientations were analyzed using a simplified ligand-field approach.
JOURNAL OF INORGANIC BIOCHEMISTRY
(2023)
Article
Chemistry, Physical
Ying Sun, Jialin Sun, Zhenming Yin
Summary: Two 2-(4-hydroxylphenyl)-azopyrrole compounds were synthesized and characterized. The properties of azopyrrole can be drastically tuned by slight changes in the substituent on the pyrrole N atom. Compound 1 self-assembled into a pillar structure through hydrogen bonds, while compound 2 formed a double-strand helical and tube structure. UV-Vis spectra studies showed that the cistrans conversion rate of compound 2 is solvent dependent, with protic and polar solvents promoting the conversion.
JOURNAL OF MOLECULAR STRUCTURE
(2023)
Article
Spectroscopy
Yurong Guo, Mengqi Wang, Zibo Wu, Yanan Shi, Ye Wang, Song Zhang, Bing Jin, Shen Cui, Guangjiu Zhao
Summary: In this study, the potential UV protection mechanism of natural compounds hydroxy resveratrol and pterostilbene was investigated using theoretical calculations and femtosecond transient absorption spectra (FTAS). The UV absorption spectra showed that these compounds had strong absorption properties and were highly photostable. The results revealed that both molecules reached the S-1 state or higher excited states after UV exposure, and underwent adiabatic trans-cis isomerization process before returning to the ground state. Furthermore, the FTAS data indicated that the trans-cis isomerization of these molecules occurred within a time scale of about 10 ps, suggesting fast energy relaxation. This work provides theoretical guidance for the development of new sunscreen molecules from natural stilbene.
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
(2023)
Article
Biochemistry & Molecular Biology
Vahidreza Darugar, Mohammad Vakili, Maria E. Manzur, Silvia Antonia Brandan
Summary: In this research, the structural and vibrational properties of cis-trans isomers of insecticide allethrin were studied in different solvent environments. The results showed that the properties of the isomers were influenced by the permittivity of the solvent, with higher dipole moments and solvation energies observed in water compared to ethanol. Vibrational assignments of both isomers were determined using experimental IR spectra and quantum mechanical force field methodology. The stability of the isomers was analyzed using Natural Bond Orbital (NBO) calculations and Atoms in Molecules (AIM) studies. The findings demonstrated the importance of solvent effects on the properties and stability of allethrin isomers.
JOURNAL OF MOLECULAR MODELING
(2022)
Article
Biochemistry & Molecular Biology
Fernando Nainggolan
Summary: The molecular structure properties of the cis and trans form of azobenzene molecule from HMNA were investigated using the DFT method. The trans-HMNA has a molecular size of 9.0 t1 and exhibits a p → p* type electronic transition driven by an azo bond. The cis-HMNA has a molecular size of 6.6 t1 and exhibits an n → p* type electronic transition with respect to the non-bonding electrons of oxygen and nitrogen atoms. The study suggests that the mechanism pathway of HMNA from trans to cis form is feasible to undergo at the inversion pathway in the ground state.
JOURNAL OF MOLECULAR MODELING
(2023)
Article
Polymer Science
Zhiqiang Wan, Lei Pu, Yuan Zhang, Xiaojuan Shen, Maiyong Zhu, Songjun Li
Summary: This study proposes an intelligent polymer catalyst with photo-mediated catalytic ability. By controlling the conformation of azobenzene, the accessibility to internal catalytic sites can be altered, thus influencing the catalytic ability. This catalyst exhibits different catalytic abilities under different light conditions, which is of great importance for optically modulating catalytic processes.
JOURNAL OF INORGANIC AND ORGANOMETALLIC POLYMERS AND MATERIALS
(2022)
Article
Chemistry, Physical
D. L. M. Vasconcelos, C. B. Silva, A. M. R. Teixeira, P. T. C. Freire
Summary: This study investigated the structural, electronic, and vibrational spectroscopic properties of cis and trans isomeric forms of the captopril molecule in gas phase and aqueous solution. It was found that the molecule exhibited better reactivity in aqueous solution and Raman and infrared spectroscopy were effective techniques for identifying the isomeric form.
JOURNAL OF MOLECULAR STRUCTURE
(2021)
Article
Chemistry, Physical
J. Carlos Jimenez-Cruz, Ramon Guzman-Mejia, Pedro Navarro-Santos, Stephanie Garcia-Zavala, Rafael Herrera-Bucio, Hugo A. Garcia-Gutierrez, Judit A. Avina-Verduzco
Summary: This work describes the synthesis and structural characterization of two palladium (II) complexes using various analytical techniques. The study focuses on a chiral complex derived from L-proline amino acid and a complex derived from glycine methyl ester. The structural features and reactivity properties of these complexes were explored using experimental and computational methods.
JOURNAL OF MOLECULAR STRUCTURE
(2023)
Article
Chemistry, Physical
Tanusree Ganguly, Poulami Pal, Dinesh Maity, Sujoy Baitalik
Summary: An array of styrylphenyl-conjugated Ru(II)-terpyridine complexes were designed and their photophysical and electrochemical characteristics were investigated. The compounds exhibited aggregation-induced emission quenching and enhancement due to the presence of polyaromatic units. Styrylphenyl units allowed the photoisomerization from trans-trans to trans-cis in both free and aggregated forms of the complexes under visible light, which could be reverted back by UV light. The rate constant and quantum yield of photoisomerization decreased with the extent of aggregation. Theoretical analysis using density functional theory (DFT) and time-dependent DFT methods was also performed for band assignment and understanding of the photoisomerization process.
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
(2023)
Article
Chemistry, Physical
Antonio Raiol, Antonio R. da Cunha, Vinicius Manzoni, Tarciso Andrade-Filho, Rodrigo Gester
Summary: This work utilizes a sequential Monte Carlo/Quantum Mechanics procedure to investigate the impact of specific solute-solvent interactions and photoinduced cis-trans isomerization on the nonlinear optical response of an azo-azomethine dye. The findings suggest that the trans isomerization increases the number of solvent molecules around the solute and promotes the formation of hydrogen-bonded structures with solvent molecules. Additionally, the solute polarization significantly influences electronic properties, with the trans structure showing a notable increase in first and second-hyperpolarizability compared to vacuum conditions.
JOURNAL OF MOLECULAR LIQUIDS
(2021)
Article
Chemistry, Physical
Tanusree Ganguly, Poulami Pal, Animesh Paul, Sujoy Baitalik
Summary: A new series of stilbene-appended terpyridine systems have been designed to exhibit multiple controllable photo-switching behaviors under divergent conditions. These compounds undergo trans-* cis isomerization upon visible light treatment, with potential for emission switching upon successive light exposure.
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
C. Karthika, R. Praveena, K. Sadasivam
Summary: The influence of external electrical field on the trans and cis isomers of azobenzene has been investigated up to the molecular orbital level using density functional theory. The response of the molecules to the applied field is studied through frontier molecular orbital analysis and electrostatic potential mapping. Analysis of dipole moment variations reveals the extent of polarization in the molecule due to the field. Natural bond orbital analysis predicts possible charge transfer paths within the molecule. Drastic charge redistribution is observed at an electric field strength of 0.15 V/angstrom, establishing a threshold for organic molecular conductance. These theoretical investigations provide insights into the impact of molecular conformation on a molecule's conductivity in the presence of an external electrical field.
INDIAN JOURNAL OF CHEMISTRY SECTION A-INORGANIC BIO-INORGANIC PHYSICAL THEORETICAL & ANALYTICAL CHEMISTRY
(2021)
Article
Biochemical Research Methods
Heng Zhu, Iftikhar Ali, Hidayat Hussain, Manzoor Hussain, Xing-Bao Wang, Xiangyun Song, Ge Luo, Zhenfang Zhang, Zhigang Wang, Daijie Wang
Summary: The study successfully separated alpha- and beta-asarone from Acorus tatarinowii extract using silver ion coordination complexation high-speed counter-current chromatography. By optimizing the parameters of accelerated solvent extraction, the target compounds with high purity were obtained and identified by mass spectrometry and NMR techniques.
JOURNAL OF CHROMATOGRAPHY A
(2021)
Article
Physics, Atomic, Molecular & Chemical
R. F. Likerov, R. M. Eremina, I. V. Yatsyk, K. B. Konov, V. A. Shustov, Yu. D. Zavartsev, S. A. Kutovoi
Summary: The scandium orthosilicate monocrystal (Sc2SiO5)-Si-28 (SSO) doped with V-51 isotope in small concentrations (0.005% at.) was studied using CW and pulsed electron spin resonance (ESR) methods. The anisotropy of the hyperfine interaction of vanadium ions and the isotropic nature of the Zeeman interaction were determined. The charge state of vanadium ions was found to be V4+. The phase memory and spin-lattice relaxation time were measured, and it was discovered that the phase memory time remains in the microseconds range even at low temperatures (T = 30 K).
APPLIED MAGNETIC RESONANCE
(2023)
Article
Food Science & Technology
Neha Baliyan, Antim Kumar Maurya, Anil Kumar, Vijai Kant Agnihotri, Rakshak Kumar
Summary: This study isolated probiotic strains from raw cow milk of the Lahaul valley capable of producing cis-9, trans-11 CLA isomer, and exhibiting antioxidant and food formulation abilities. Genome sequencing revealed the presence of antibiotic-resistance and virulence genes in Enterococcus faecalis LJM:05. The strain Latilactobacillus curvatus LGM:16 was used to develop curdled milk with superior probiotic features, antioxidant activity, and CLA-producing ability.
LWT-FOOD SCIENCE AND TECHNOLOGY
(2023)
Article
Physics, Atomic, Molecular & Chemical
Ilenia Serra, Ines Garcia Rubio, Sabine Van Doorslaer
Summary: This study systematically investigates the impact of various factors on the EPR spectrum of myoglobin, focusing on the use of high-pH buffers to induce alkaline transition. The findings show that specific pairs of buffers and cryoprotectants can significantly alter the sample's pH, with ethylene glycol being more effective than glycerol as a cryoprotectant. Additionally, the effect of experimental factors is enhanced at cryogenic temperatures, highlighting the importance of careful selection in EPR studies of metalloproteins.
APPLIED MAGNETIC RESONANCE
(2022)
Article
Construction & Building Technology
Georgios Pipintakos, Hilde Soenen, H. Y. Vincent Ching, Christophe Vande Velde, Sabine Van Doorslaer, Filip Lemiere, Aikaterini Varveri, Wim Van den Bergh
Summary: This study focused on identifying the intermediate and final oxygenated products of binders from different crude sources after short- and long-term laboratory ageing. Analyzing the results from FTIR, EPR, H-1 NMR, and TOF-SIMS, it was found that the increase of sulfoxide and carbonyl functional groups, as well as organic carbon-centered radicals, were related to the ageing process and binder characteristics.
CONSTRUCTION AND BUILDING MATERIALS
(2021)
Article
Chemistry, Multidisciplinary
Andrea Hamza, Daniel Moock, Christoph Schlepphorst, Jacob Schneidewind, Wolfgang Baumann, Frank Glorius
Summary: This study investigates the active form and reaction mechanism of the chiral ruthenium(ii)bis-SINpEt complex in the hydrogenation of 2-methylbenzofuran. The flexible carbene ligands in the complex lead to the formation of a chiral pocket that interacts with the substrate in a lock-and-key fashion, controlling enantioselectivity. The findings provide insights for the rational design of chiral catalysts.
Article
Chemistry, Multidisciplinary
Yu Zhang, Shaowei Qin, Nathalie Claes, Waldemar Schilling, Prakash Kumar Sahoo, H. Y. Vincent Ching, Aleksander Jaworski, Filip Lemiere, Adam Slabon, Sabine Van Doorslaer, Sara Bals, Shoubhik Das
Summary: In this study, a metal-free heterogeneous photocatalyst was developed for the direct hydroxylation of tertiary benzylic C(sp(3))-H bonds using oxygen as the key reagent. The gram-scale reaction was achieved with high product yield using direct solar energy. The high stability of the catalyst was proven through catalyst recycling and spectroscopic analyses, and a possible mechanism was proposed based on experimental evidence.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Correction
Electrochemistry
Sander Neukermans, Mohammad Samanipour, H. Y. Vincent Ching, Jonas Hereijgers, Sabine Van Doorslaer, Annick Hubin, Tom Breugelmans
Article
Chemistry, Inorganic & Nuclear
Tibor Csupasz, Norbert Lihi, Zsuzsa Fekete, Antonia Nagy, Richard Botar, Viktoria Forgacs, Dezso Szikra, Nora Veronika May, Gyula Tircso, Ferenc Krisztian Kalman
Summary: In this study, two Cu(ii) complexes formed from the CB-15aneN(5) ligand and its bifunctional derivative were thoroughly characterized. The results showed that these Cu(ii) chelates have high thermodynamic stability, fast complexation, and moderate inertness under harsh conditions. The radiolabeling experiments demonstrated the fast complexation even at low concentrations. Based on these findings, the CB-15aneN(5) ligand family is an excellent platform for Cu(ii) complexation in radiotheranostics.
INORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Analytical
Liselotte Neven, Hanan Barich, H. Y. Vincent Ching, Shahid U. Khan, Christopher Colomier, Hemantbhai H. Patel, Sergiu M. Gorun, Sammy Verbruggen, Sabine Van Doorslaer, Karolien De Wael
Summary: Electron-withdrawing perfluoroalkyl peripheral groups grafted on phthalocyanine macrocycles improve their properties for catalytic applications, with a high degree of fluorination enhancing reducibility and potentially altering singlet oxygen photoproduction. The use of a specific solvent mixture was found to dissolve perfluorinated complexes and minimize aggregation, while solid-state studies showed potential for developing efficient sensors based on these complexes. The most efficient generator of singlet oxygen was determined to be F52PcZn, highlighting the importance of the value of n and structural features in their applications.
ANALYTICAL CHEMISTRY
(2022)
Article
Chemistry, Physical
Tatsiana V. Petrasheuskaya, Ferenc Kovacs, Gabriella Spengler, Nora V. May, Eva Frank, Eva A. Enyedy
Summary: The effects of complexation of 2-aminophenol and 2-aminoestradiol with divalent metal ions on their physico-chemical and biological properties were investigated. It was found that complexation with Cu(II) ions resulted in higher stability and increased cytotoxicity against cancer cells. Moreover, complexation with Cu(II) ions also enhanced antioxidant activity and percentage of apoptotic cells.
JOURNAL OF MOLECULAR STRUCTURE
(2022)
Article
Oncology
Vivien Posa, Alessia Stefanelli, Julia H. Bormio Nunes, Sonja Hager, Marlene Mathuber, Nora May, Walter Berger, Bernhard K. Keppler, Christian R. Kowol, Eva A. Enyedy, Petra Heffeter
Summary: In addition to zinc, iron and copper also play a role in the mode of action and resistance development of COTI-2 and its derivatives. COTI-NMe2 is discovered to be a new drug candidate with improved anticancer activity and resistance profile. The study reveals that COTI-2 forms stable complexes with copper and glutathione, making it a substrate for the resistance efflux transporter ABCC1. Furthermore, the interaction of COTI-2 and its derivatives with iron, copper, and zinc ions is characterized, and their activities against drug-resistant cancer cells are investigated.
Article
Biochemistry & Molecular Biology
Daniel Schmidt, Nikolaus Falb, Ilenia Serra, Marzia Bellei, Vera Pfanzagl, Stefan Hofbauer, Sabine Van Doorslaer, Gianantonio Battistuzzi, Paul G. Furtmuller, Christian Obinger
Article
Chemistry, Inorganic & Nuclear
Roberta Sgammato, Niels Van Brempt, Roy Aerts, Sabine Van Doorslaer, Sylvia Dewilde, Wouter Herrebout, Christian Johannessen
Summary: Protoglobin from Methanosarcina acetivorans (MaPgb) is a dimeric globin belonging to the same lineage as globin-coupled sensors. It has a putative role in scavenging reactive nitrogen and oxygen species. Through various spectroscopic techniques, the unusual reaction of ferric MaPgb with nitrite was revealed. Unlike other globins, nitrite did not induce the formation of a nitriglobin form in MaPgb. Instead, it led to the formation of a stable nitric-oxide ligated ferric form of the protein (MaPgb-NO) in mildly acidic pH. The changes in the optical and vibrational properties of MaPgb upon nitric-oxide ligation provide insights into its gas-binding mechanism.
DALTON TRANSACTIONS
(2023)
Article
Biochemistry & Molecular Biology
Tamas Pivarcsik, Vivien Posa, Hilda Kovacs, Nora May, Gabriella Spengler, Szonja P. Posa, Szilard Toth, Zeinab Nezafat Yazdi, Csilla Ozvegy-Laczka, Imre Ugrai, Istvan Szatmari, Gergely Szakacs, Eva A. Enyedy
Summary: This article investigates a novel 5-nitro-8-hydroxyquinoline-proline hybrid and its Rh(eta(5)-C5Me5) and Ru(eta(6)-p-cymene) complexes, which have excellent solubility in water and show inhibitory effects on sensitive and multidrug-resistant cells.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Biochemistry & Molecular Biology
Tatsiana Petrasheuskaya, Ferenc Kovacs, Nora Igaz, Andrea Ronavari, Balint Hajdu, Laura Bereczki, Nora May, Gabriella Spengler, Bela Gyurcsik, Monika Kiricsi, Eva Frank, Eva A. Enyedy
Summary: A series of novel estradiol-based salicylaldehyde (thio)semicarbazones and their Cu(II) complexes were synthesized and characterized. The Cu(II)-estradiol-semicarbazone complex structure was determined by X-ray crystallography. The Cu(II) complexes of estradiol-TSC and its N,N-dimethyl derivative showed high cytotoxicity against cancer cells and significant activity against Staphylococcus aureus bacteria strain. Estradiol-TSCs exhibited efficient antioxidant activity, which was decreased by complexation with Cu(II) ions. The exchange of estrone moiety to estradiol did not significantly affect the physicochemical and biological properties.
Article
Chemistry, Multidisciplinary
Andrea Hamza, Flora B. Nemeth, Adam Madarasz, Anton Nechaev, Petri M. Pihko, Pekka Peljo, Imre Papai
Summary: N-functionalized pyridinium frameworks derived from vitamers of vitamin B6 were computationally screened as negative electrode materials for aqueous organic flow batteries. A molecular database of related pyridinium derivatives was generated using a computational protocol combining semiempirical and DFT methods. The predicted reduction potentials of the pyridinium frameworks varied widely, but pyridoxal derivatives, especially those with electron withdrawing substituents, had potentials compatible with the stability of aqueous electrolytes. A new computational tool was used to analyze the stability of radicals formed upon one-electron reduction.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Nora May, Niloofar Bayat, Kende Attila Beres, Petra Bombicz, Vladimir M. Petrusevski, Gyorgy Lendvay, Attila Farkas, Laszlo Kotai
Summary: A hemipyridine solvate of bis(pyridine)silver(I) perchlorate was prepared and characterized by single crystal X-ray analysis and vibrational spectroscopy. The solvate structure is isomorphic with the analogous permanganate complex. The stoichiometric ratio of the monomer [Agpy(2)ClO(4)] and the solvent pyridine is 1:0.5, and the solvate pyridine occupies 18.0% of the volume of the unit cell.