Repositório DSpace :: Navegando por Autor "Custodio, Jean Marcos Ferreira"

Navegando por Autor "Custodio, Jean Marcos Ferreira"

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A novel dihydrocoumarin under experimental and theoretical characterization
(2017) Vaz, Wesley Fonseca; Custodio, Jean Marcos Ferreira; Rodrigues, Núbia Maria Nunes; Santin, Lauriane Gomes; Oliveira, S. S.; Gargano, Ricardo; Osorio, Francisco Aparecido Pinto; Aquino, Gilberto Lucio Benedito de; Camargo, Ademir João; Oliveira, M. S.; Napolitano, Hamilton Barbosa
Coumarins are natural and synthetic active ingredients widely applied in diverse types of medicinal treatments, such as cancer, inflammation, infection, and enzyme inhibition (monoamine oxidase B). Dihydrocoumarin compounds are of great interest in organic chemistry due to their structural versatilities and, as part of our investigations concerning the structural characterization of small molecules, this work focuses on crystal structure and spectroscopic characterization of the synthesized and crystallized compound 4-(4-methoxyphenyl)-3,4-dihydro-chromen-2-one (C16H14O3). Additionally, a theoretical calculation was performed using density functional theory to analyze the sites where nucleophilic or electrophilic attack took place and to examine the molecular electrostatic potential surface. Throughout all of these calculations, both density functional theory and Car–Parrinello molecular dynamics were performed by fully optimized geometry. The spectroscopic analysis indicated the presence of aromatic carbons and hydrogen atoms, and also the carbonyl and methoxy groups that were confirmed by the crystallographic structure. The C16H14O3 compound has a non-classical intermolecular interaction of type C–H⋅⋅⋅O that drives the molecular arrangement and the crystal packing. Moreover, the main absorbent groups were characterized throughout calculated harmonic vibrational frequencies. Also, natural bond orbital analysis successfully locates the molecular orbital with π-bonding symmetry and the molecular orbital with π* antibonding symmetry. Finally, the gap between highest occupied and lowest unoccupied molecular orbitals implies in a high kinetic stability and low chemical reactivity of title molecule.
Alternative mechanisms of action for the apoptotic activity of terpenoid-like chalcone derivatives
(2021) Custodio, Jean Marcos Ferreira; Vaz, Wesley Fonseca; Valeze, Aline Bernardes; Moura, Andrea Felinto; Oliver, Allen G.; Perjési, Pál; Noda Pérez, Caridad
Apoptosis is a defense mechanism against pre-cancerous and infected cells. Although the applicability of β-ionone against diverse cancer cell lines has been exhaustively investigated, the apoptotic activity of terpenoid-like chalcones, as well as their mechanisms of action, is not well understood. Here we present a new terpenoid-like chalcone derivative (I) and its biological potential against HL-60 (leukemia), HCT-116 (colon), and SNB-19 (glioblastoma) cancer cell lines. Compound I showed cytotoxicity against over 90% of the tested cell lines. However, I has an IC50 slightly higher than doxorubicin, a DNA-binding cancer drug, which motivated us to investigate an alternative mechanism of action for I other than DNA-mediated. We performed an in silico structure-based pharmacophoric screening against various proteins, which indicated mitogen-activated protein kinase 5 (MAP3K5) as a potential protein target. Compound I was docked within its active site and was predicted to bind MAP3K5 with a comparable affinity to IM6, a cocrystallized ligand. Finally, we describe the reaction of a reduced glutathione adduct (GSH) with compound I and previously published derivatives bearing the substitutions 4-chloro (II), 4-bromo (III), and 4-nitro (IV) using HPLC-MS. We show that these are rapid reactions and that the products are stable for up to 24 h. Here, we suggest two alternative mechanisms (MAP3K5 inhibition and thiol reactivity) for the biological potential of a series of terpenoid-like chalcone derivatives. We anticipate that these findings can be explored to design additional derivatives with even more robust apoptotic activity.
Chalcone as potential nonlinear optical material: a combined theoretical, structural, and spectroscopic study
(2019) Custodio, Jean Marcos Ferreira; D´Oliveira, Giulio Demetrius Creazzo; Gotardo, Fernando; Cocca, Leandro Henrique Zucolotto; De Boni, Leonardo; Noda Pérez, Caridad; Maia, Lauro June Queiroz; Valverde, Clodoaldo; Osorio, Francisco Aparecido Pinto; Napolitano, Hamilton Barbosa
In this work, we propose the synthesis of a novel bromine chalcone (E)-3-(2-bromophenyl)-1-(2-((phenylsulfonyl)amine))phenyl)prop-2-en-1-one (BRC) that has been crystallized by the slow evaporation technique. The second-order molecular optical scattering and two-photon absorption(2PA) spectrum of the BRC molecule dissolved in dimethyl sulfoxide (DMSO) were evaluated by using hyper-Rayleigh scattering and the femtosecond tunable Z-scan techniques. The first-order hyperpolarizability of BRC dissolved in DMSO was estimated by using a simplified two-level model, in which one- and two-photon absorption parameters were used as input information to the model. The BRC crystal was characterized from single-crystal X-ray diffraction (XRD) and spectroscopy analyzes. Also, the thermogravimetric analyses and the fluorescence spectra were obtained. In addition, an ab initio calculation method, which includes the Møller–Plesset perturbation theory (MP2) and the density functional theory (DFT) at the CAM-B3LYP level, was used to estimate the crystal linear refractive index and the third-order electric susceptibility. Also, the average first hyperpolarizability of BRC molecules dissolved in DMSO was calculated and compared with the experimental results. The obtained values are good and qualify the BRC crystal as a potential candidate for application in nonlinear optical devices.
A comprehensive study on crystal structure of a novel sulfonamide-dihydroquinolinone through experimental and theoretical approaches
(2019) Moreira, Cauã Apóstolo; Custodio, Jean Marcos Ferreira; Vaz, Wesley Fonseca; D´Oliveira, Giulio Demetrius Creazzo; Noda Pérez, Caridad; Napolitano, Hamilton Barbosa
Quinolinones and sulfonamides are moieties with biological potential that can be linked to form new hybrid compounds with improved potential. However, there are few hybrids of these molecules reported. In this sense, this work presents a structural description of a new sulfonamide-dihydroquinolinone (E)-2-(2-methoxyphenyl)-3-(3-nitrobenzylidene)-1-(phenylsulfonyl)-2,3 dihydroquinolin-4(1H)-one (DHQ). The molecular structure of DHQ was elucidated by X-ray diffraction, nuclear magnetic resonance and infrared spectroscopy, and both molecular packing and intermolecular interactions were analyzed by Hirshfeld surfaces and fingerprint maps. In addition, theoretical calculations on frontier orbitals, molecular electrostatic potential maps, and assignments were performed. The crystal packing of DHQ was found to be stabilized by a dimer through a weak C–H⋯O interaction along the c axis. Moreover, the structure is stabilized mainly by C–H⋯O and C–H⋯π interactions, since the interaction C25–H25⋯π contributes to a chain formation. The Hirshfeld normalized surface shows that the closest interactions are around the atoms linked to the dimer formation. The calculations indicate that DHQ possesses electrophilic sites near O atoms and depleted electrons around the H atoms. There is a band GAP of 3.29 eV between its frontier orbitals, which indicates that DHQ is more reactive than other analogues published.
Different reactivity to glutathione but similar tumor cell toxicity of chalcones and their quinolinone analogues
(2019-07-01) D´Oliveira, Giulio Demetrius Creazzo; Custodio, Jean Marcos Ferreira; Moura, Andrea Felinto; Napolitano, Hamilton Barbosa; Noda Pérez, Caridad; Moraes Filho, Manoel Odorico de; Prókai, László; Perjési, Pál
Non-enzyme catalyzed nucleophilic addition of reduced glutathione (GSH) onto two open-chain sulfonamide chalcones and two quinolinone-chalcone hybrids were studied to investigate the relationship between tumor cell cytotoxic activities and GSH-reactivities of the compounds. The consumption of the chalcones or the quinolinone-chalcone hybrids due to conjugation with GSH was evaluated by analytical high-performance liquid chromatography, and the formed diastereomeric adducts were identified by liquid chromatography–mass spectrometry. When the reaction was conducted with the open-chain chalcones, the equilibria were shifted towards formation of the respective GSH-conjugates. On the other hand, the cyclic chalcone derivatives with the quinolinone moiety were found to equilibrate to mixtures containing predominantly the reactants despite the strong electron withdrawing group present in the B-ring of the compounds. The observed opposite behavior can be rationalized by reduced thiol-reactivity of the quinolinone-chalcone hybrids and fast decomposition of their GSH-conjugates. A combined X-ray diffraction and theoretical approach were used to explain the observed difference in the reactivities towards GSH. However, structural differences did not influence tumor cell (SF-295, PC-3 and HCT-116) cytotoxicity of the evaluated compounds. Accordingly, the altered GSH-reactivity seems to be not a determining factor in the tested tumor cell cytotoxic activity of the investigated compounds.
Dihydroquinoline derivative as a potential anticancer agent: synthesis, crystal structure, and molecular modeling studies
(2021) Vaz, Wesley Fonseca; Custodio, Jean Marcos Ferreira; D´Oliveira, Giulio Demetrius Creazzo; Neves, Bruno Junior; Carvalho Júnior, Paulo de Sousa; Moreira Filho, José Teófilo; Andrade, Carolina Horta; Noda Pérez, Caridad; Lacerda, Elisângela de Paula Silveira; Napolitano, Hamilton Barbosa
Cancer is one of the leading causes of death worldwide and requires intense and growing research investments from the public and private sectors. This is expected to lead to the development of new medicines. A determining factor in this process is the structural understanding of molecules with potential anticancer properties. Since the major compounds used in cancer therapies fail to encompass every spectrum of this disease, there is a clear need to research new molecules for this purpose. As it follows, we have studied the class of quinolinones that seem effective for such therapy. This paper describes the structural elucidation of a novel dihydroquinoline by single-crystal X-ray diffraction and spectroscopy characterization. Topology studies were carried through Hirshfeld surfaces analysis and molecular electrostatic potential map; electronic stability was evaluated from the calculated energy of frontier molecular orbitals. Additionally, in silico studies by molecular docking indicated that this dihydroquinoline could act as an anticancer agent due to their higher binding affinity with human aldehyde dehydrogenase 1A1 (ALDH 1A1). Tests in vitro were performed for VERO (normal human skin keratinocytes), B16F10 (mouse melanoma), and MDA-MB-231 (metastatic breast adenocarcinoma), and the results certified that compound as a potential anticancer agent.
Enhanced nonlinear optics properties of a bromine chalcone from a novel polymorph
(2020) Custodio, Jean Marcos Ferreira; Noda Pérez, Caridad; Valverde, Clodoaldo; Osorio, Francisco Aparecido Pinto; Napolitano, Hamilton Barbosa
This work presents crystallization, structural elucidation and a thorough study on nonlinear optical (NLO) properties calculated at DFT/CAM-B3LYP/6-311++G(d,p) level of a new bromine chalcone monoclinic polymorph (BRC-m). Both linear polarizability and second hyperpolarizability associated to NLO process of the intensity dependent refractive index (IDRI) were calculated. The dynamic third-order NLO susceptibility (χ3-ω;ω,ω,-ω) for BRC-m are higher than obtained experimentally for other chalcone derivatives. Furthermore, the theoretical results for BRC-m were compared with triclinic bromine chalcone (BRC-t); and the change of crystalline state (BRC-t to BRC-m) enhanced the third-order NLO susceptibility from 0.257×10-20m2/V2 to 2.48×10-20m2/V2 at 1064 nm, respectively. This observation shows that future research on crystallization process of known NLO materials is a promising way to improve even more their potential optical application and improve the crystal quality.
Experimental and molecular modeling study of a novel arylsulfonamide chalcone
(2019) Duarte, Vitor Santos; D´Oliveira, Giulio Demetrius Creazzo; Custodio, Jean Marcos Ferreira; Oliveira, Solemar Silva; Noda Pérez, Caridad; Napolitano, Hamilton Barbosa
Chalcones have been reported to present biological activities that are potentialized when a sulfonamide group is attached. A comprehensive structural study was performed for arylsulfonamide chalcone N-(2-(3–4-methoxyphenyl-propanoyl)-phenyl)-benzene-sulfonamide in order to describe its supramolecular arrangement and its physicochemical properties. The molecular packing arrangement was described by X-ray diffraction and Hirshfeld surfaces (HS). Theoretical calculations were performed using density functional theory (DFT), molecular electrostatic potential (MEP) mapping, ab initio Car-Parrinelo molecular dynamics (CPMD) and the quantum theory of atoms in molecules (QTAIM). The solid-state arrangement is stabilized by C– H⋯O and C–H⋯π interactions observed on HS and MEP map. The topological analysis was evaluated by QTAIM.
Hirshfeld surfaces and nonlinear optics on two conformers of a heterocyclic chalcone
(2018) Custodio, Jean Marcos Ferreira; Moreira, Cauã Apóstolo; Valverde, Clodoaldo; Aquino, Gilberto Lúcio Benedito de; Baseia, Basilio
Heterocyclic chalcones have been prominent in the scientific community due to various biological activities reported for these compounds. The structural knowledge of heterocyclic chalcones can help in the understanding of their mechanism of action. The Hirshfeld surfaces were used to study the supramolecular arrangement of two conformers present into asymmetric unit of the heterocyclic chalcone (2E)-3-(4-methylphenyl)-1-(pyridin-3-yl)-prop-2-en-1-one on crystalline state. In addition, the linear polarizability (α), the first hyperpolarizability (β||z), and the second hyperpolarizability (γ) of the conformers were calculated to get a better insight on the linear and nonlinear optical behaviors of these structures in presence of solvent medium, as well as their band-gap energies. The Hirshfeld surfaces confirmed the presence of C−H···N, C−H···O and C−H···C interactions in packaging stabilization. Finally, the 2D fingeprint plot was used to the quantification of contacts and indicated that there are both π···π and C−H···π interactions present in the compound.
In silico-driven identification and structural analysis of nitrodihydroquinolinone pesticide candidates with antifungal activity
(2021) Vaz, Wesley Fonseca; Neves, Bruno Junior; Custodio, Jean Marcos Ferreira; Silva, Lucas Leonardo da; D´Oliveira, Giulio Demetrius Creazzo; Lemes, Josiel Araújo; Lacerda, Bruno Francisco Cardoso de; Santos, Solange Xavier dos; Noda Pérez, Caridad; Napolitano, Hamilton Barbosa
In this paper, we performed an in silico-driven design model to synthesize compounds with biological activity. This rational design has the advantage of decreasing the time and the need for experimental tests and, consequently, the cost related to the search for different candidates. In this way, there is a necessity for more studies that look for new molecules or compounds that may be alternatives to replace the most harmful chemicals for safer options. To contribute to filling this gap, we started an investigation looking for molecules with bioactive potential using a previously developed machine learning model. Leading us to the synthesis, spectroscopic and structural characterization of (E)-2-(4-chlorophenyl)-3-(4-nitrobenzylidene)-1-(phenylsulfonyl)-2,3-dihydroquinolin-4(1H)-one. Furthermore, considering the predicted biological profile, one of its isomers was incorporated in this study and submitted to experimental validation. The in vitro results indicated that the compounds have antifungal activity against Aspergillus niger in the same range of positive controls. Moreover, both compounds crystallized in the P21/n space group, and their packing is mainly ruled by C–H⋯O interactions. Lastly, we hope that findings can be used as a starting point for new studies where the structural and biological knowledge of dihydroquinolinones leads to the designing of less toxic or nontoxic analogs antifungal agents by changing undesirable fragments by desirable ones in the molecular skeleton.
Insights into chalcone analogues with potential as antioxidant additives in diesel–biodiesel blends
(2022) Borges, Igor Dalarmelino; Faria, Eduardo Coelho da Mata; Custodio, Jean Marcos Ferreira; Duarte, Vitor Santos; Fernandes, Fernanda de Sousa; Alonso, Christian Gonçalves; Silva, Valter Henrique Carvalho; Oliveira, Guilherme Roberto de; Napolitano, Hamilton Barbosa
Biodiesel production is one of the promising strategies to reduce diesel consumption and an important contribution to climate change. However, biodiesel stability remains a challenging problem in biofuel use in the global energy matrix. In this context, organic additives have been investigated to minimize these problems and reduce harmful emissions to comply with fuel requirement standards. In this study, we discuss a comprehensive structural description, a behavior of B15 [85% volume of diesel and 15% volume of biodiesel (B100)] stability in the presence of antioxidants (chalcone analogues), and a theoretical calculation to pave the way for clarifying and expanding the potential of title compounds as an antioxidant additive for diesel–biodiesel blends. Finally, a systematic description of the oxidation stability was undertaken using a specialized machine learning computational pySIRC platform.
Molecular modelling and optical properties of a novel fluorinated chalcone
(2020) Custodio, Jean Marcos Ferreira; Guimarães Neto, J. J. A.; Awad, R.; Queiroz, J. E.; Verde, G. M. V.; Mottin, Melina; Neves, Bruno Junior; Andrade, Carolina Horta; Aquino, Gilberto Lúcio Benedito de; Valverde, Clodoaldo; Osorio, Francisco Aparecido Pinto; Baseia, Basilio; Napolitano, ‪Hamilton Barbosa
Chalcones exhibit a broad spectrum of biological activities, mainly due to a,bunsaturated ketone, and are precursors of the biosynthesis of flavonoids present in plants. These compounds have been shown to be useful in the biological approach, proven by the broad spectrum of biological activities reported, and also in the technological approach, considering their potential as nonlinear optic (NLO) material. In this context, this work aimed to examine the crystallization and characterization of fluorinated chalcone (E)-1-(4-fluorophenyl)-3-(4-isopropylphenyl)prop-2-e n-1-one (DFC). A comprehensive structural study of DFC was carried out to understand the process of stabilizing the crystalline lattice through X-ray diffraction, infrared spectroscopy, and molecular modeling studies. Finally, the electrical properties of DFC were calculated by using the supermolecule method (SM). DFC molecules are connected by means of CAH O and CAH F intermolecular contacts, forming dimers which play an important role in the stabilization of crystal packing. Molecular modeling studies indicated that this compound could act as an anti-tuberculosis ligand because of its high binding affinity with the M. tuberculosis enoyl-acyl carrier protein, InhA. On the other hand, theoretical calculations were performed to evaluate the NLO properties of DFC and indicated that it showed good potential.
Molecular structure of hybrid imino-chalcone in the solid state: x-ray diffraction, spectroscopy study and third-order nonlinear optical properties
(2019) Custodio, Jean Marcos Ferreira; Santos, Florisberto Garcia dos; Vaz, Wesley Fonseca; Cunha, Carlos Eduardo Peixoto da; Silveira, Rafael Gomes da; Anjos, Murilo Machado dos; Campos, Carlos Eduardo Maduro de; Oliveira, Guilherme Roberto de; Martins, Felipe Terra; Silva, Cameron Capeletti da; Valverde, Clodoaldo; Baseia, Basilio
A comprehensive structural study of the compound (2E)-1-((E)-4-(4-methoxybenzylideneamino)phenyl)-3-(4-methoxyphenyl)prop-2-en-1-one was carried out in this work. Single crystal X-ray diffraction (SCXRD), X-ray powder diffraction (XRPD), NMR, Raman and Infrared spectroscopies, and DFT calculations were performed for characterization of this iminochalcone hybrid. Intermolecular interactions were described by Hirshfeld surface analysis derived from crystal structure. Reactivity and intramolecular charge transfer were investigated using the frontier molecular orbitals and molecular electrostatic potential. In addition, we have calculated the Nonlinear Optical Properties at the CAM-B3LYP/6–311+g(d) level of theory in the presence of different solvents (gas-phase, acetone, chloroform, dichloromethane, dimethyl sulfoxide, ethanol, methanol, and water), being found meaningful NLO parameters for our compound. At last, there is a good agreement between calculated and experimental IR spectrum, allowing the assignment of some of normal vibrational modes of the iminochalcone hybrid.
A new quinolinone-chalcone hybrid with potential antibacterial and herbicidal properties using in silico approaches
(2022) Duarte, Vitor Santos; Paula, Renata Layse Gonçalves de; Custodio, Jean Marcos Ferreira; D´Oliveira, Giulio Demetrius Creazzo; Borges, Leonardo Luiz; Noda Pérez, Caridad; Perjesi, Pal; Oliver, Allen G.; Napolitano, Hamilton Barbosa
Quinolinone-chalcones are hybrid compounds consisting of chalcone and quinolone moieties with biological activity related to their hybrid structure. This work seeks to describe the structural and theoretical parameters related to the physicochemical properties and biological activity of a new quinolinone-chalcone. The synthesis, structural characterization by X-ray diffraction, molecular topology by Hirshfeld surfaces and QTAIM, molecular electronic calculations, and pharmacophore analysis were described. The weak interactions C–H…O, C–H…π, and C–H…Br were responsible for crystal growth and stabilized the crystalline state. The DFT analysis shows that the sulfonamide group region is susceptible to observed interactions, and the frontier molecular orbitals indicate high kinetic stability. Also, pharmacophore analysis revealed potential antibacterial and herbicidal activity; by docking within the active site of TtgR, a transcription regulator for the efflux pump TtgABC from the highly resistant Pseudomonas putida (P. putida) strain DOT-TIE, we showed that the activation of TtgR relies upon the binding of aromatic-harboring compounds, which plays a crucial role in bacterial evasion. In this context, a new quinolinone-chalcone has a higher binding affinity than tetracycline, which suggests it might be a better effector for TtgR.
A novel potential anticancer chalcone: synthesis, crystal structure and cytotoxic assay
(2018) Michelini, Lidiane Jorge; Castro, Mirian Rita Carrilho de; Custodio, Jean Marcos Ferreira; Naves, Luiz Felipe Nunes; Vaz, Wesley Fonseca; Sanz Lobón, Germán; Martins, Felipe Terra; Noda Pérez, Caridad; Napolitano, Hamilton Barbosa
Recently, a wide number of bioactivities has been discovered for chalcones. These applications depend on structural features such as planarity, electronic delocalization paths and substitution pattern on aromatic rings. This work aimed the structural analysis of a novel nitroaminochalcone (C15H12N2O3, NAC) through single crystal X-ray diffraction technique and assessment of its cytotoxicity against tumor cells. NAC is almost completely planar, as evidenced by the low angle formed between its phenyl rings [4.40 (12)°], which enables the π-electron delocalization through whole molecule. A resonance-assisted hydrogen bond (RAHB) is another interesting intramolecular feature of NAC, which is assembled between the amino and carbonyl groups into a cyclic S (6) motif. The crystal packing is featured by the formation of dimers stabilized by a (16) motif engaging the carbonyl group and nitrobenzene. These dimers are organized in a 2D layer onto (010) through Csingle bondH⋯O interactions involving the nitro e amine groups in a motif. Furthermore, Hirshfeld surface analysis showed the crystal packing of NAC is also stabilized by both Csingle bondH⋯π and π⋯π interactions. The compound showed high cytotoxicity against human tumor cells.
On the in silico and in vitro anticancer activity of sulfonamide chalcones: potential JNKK3 inhibitors
(2020) Custodio, Jean Marcos Ferreira; Moura, Andrea Felinto; Moraes Filho, Manoel Odorico de; Noda Pérez, Caridad; Napolitano, Hamilton Barbosa
Science is constantly looking for new strategies to combat tumor progression and improve patient care due to increasing cancer incidence and high mortality. Although many chalcone analogues have been synthesized and studied because of their activity against tumor cell growth, the use of hybrid compounds containing both sulfonamides and chalcone moieties for this purpose is still scarce. Hereby, this work proposes a series of sulfonamide chalcones presenting biological potential against this disease. After being experimentally tested, these compounds showed cytotoxicity against tumor cell lines SF-295 and PC-3, which motivated us to investigate the possible structural bases for this action. Topological analyses were carried out through Hirshfeld analysis to assign intermolecular interaction sites important for protein–ligand analysis. To identify potential targets, the synthesized compounds were submitted to a structure-based pharmacophoric screening, which suggest strong potential activity as mitogen-activated protein kinase 10 (JKN3) inhibitors. Considering these results, these compounds were docked within the JKN3 active site. Our hypothesis that these compounds achieve their biological potential by inhibiting the JKN3 protein is reinforced when their energies of ligand–protein interaction were compared to co-crystallized ligands: they showed similar or even lower binding energies. Finally, the energy of the different conformations (solid phase, aqueous phase and within the protein active site) of these sulfonamide chalcones was investigated using theoretical calculations. Our findings enable further studies on more sulfonamide chalcone analogues toward the development of new anticancer drugs.
On the potential as nonlinear optical material of a new chalcone derivative and its crystal and topological analysis
(2020) Custodio, Jean Marcos Ferreira; Vaz, Wesley Fonseca; Faria, Eduardo Coelho da Mata; Anjos, Murilo Machado dos; Campos, Carlos Eduardo Maduro de; Oliveira, Guilherme Roberto de; Silva, Cameron Capeletti da; Valverde, Clodoaldo; Osorio, Francisco Aparecido Pinto; Baseia, Basilio; Napolitano, Hamilton Barbosa
We report a study of the structural and the linear and nonlinear optical and electrical properties of a new chalcone. Using the Møller-Plesset Perturbation and the Density Functional approaches, the dipole moment, linear polarizability and second hyperpolarizabilities were calculated in static and dynamic electric fields. The supermolecule approach was used to simulate the crystalline environment of our crystal and the linear refractive index. Lorentz local field correction factor and third order macroscopic susceptibility were calculated, and the effects of solvent media on the non-linear optical properties are also taken into account through the Polarizable Continuum Model. This chalcone is almost planar, except for slight rotations in its open-chain which allows electron delocalization. This is also confirmed by an intramolecular hydrogen bond formed between the carbonyl and amine groups. Interestingly, a good third order macroscopic susceptibility value of 13.31 × 10−22m2V−2 was calculated, which is even higher than those reported for related chalcone derivatives.
Relating the crystal structure and third-order nonlinear susceptibility of a new neolignan derivative
(2022) Custodio, Jean Marcos Ferreira; Fernandes, Fernanda de Sousa; Vaz, Wesley Fonseca; Oliver, Allen G.; Valverde, Clodoaldo; Osorio, Francisco Aparecido Pinto; Oliveira, Guilherme Roberto de; Fonseca, Tertius Lima da
Theoretical results for electronic properties of a synthesized nitro chalcone with a neolignan moiety (NOPP) whose crystal structure was elucidated by using Single Crystal X-ray Diffraction (SCXRD) are presented. The NOPP crystal structure suggests that its potential for nonlinear applications is related to the chalcone moiety planarity and that the lamellar NOPP crystal packing along with dimer formation maximize the electronic properties. The in-crystal absorption spectrum and static and dynamic electric properties were determined by applying a supermolecule approach in combination with an iterative electrostatic scheme, in which the surrounding molecules are represented by point charges. It is found that the environment polarization effect is mild for absorption spectrum and linear polarizability, but it is marked for second hyperpolarizability of NOPP molecule. Estimates of macroscopic quantities from the results of an explicit unit cell of crystal, including environment polarization effect and partially the exchange and dispersion effects, are presented. The results illustrate the role played by these interactions on the third-order nonlinear susceptibility of the NOPP crystal, and a theoretical (λ = 532 nm) prediction of 2.81 × 10−20 (m/V)2 for χ(3)(−ω;ω,ω,ω) suggests that the NOPP crystal is a very promising NLO material.
Remarkable nonlinear properties of a novel quinolidone derivative: joint synthesis and molecular modeling
(2022) Valverde, Clodoaldo; Vinhal, Rafael de Siqueira; Naves, Luiz Felipe Nunes; Custodio, Jean Marcos Ferreira; Baseia, Basilio; Oliveira, Heibbe Cristhian Benedito de; Perez, Caridad Nóda; Napolitano, Hamilton Barbosa; Osorio, Francisco Aparecido Pinto
A novel 4(1H) quinolinone derivative (QBCP) was synthesized and characterized with single crystal X-ray diffraction. Hirshfeld surfaces (HS) analyses were employed as a complementary tool to evaluate the crystal intermolecular interactions. The molecular global reactivity parameters of QBCP were studied using HOMO and LUMO energies. In addition, the molecular electrostatic potential (MEP) and the UV-Vis absorption and emission spectra were obtained and analyzed. The supermolecule (SM) approach was employed to build a bulk with 474,552 atoms to simulate the crystalline environment polarization effect on the asymmetric unit of the compound. The nonlinear optical properties were investigated using the density functional method (DFT/CAM-B3LYP) with the Pople’s 6-311++G(d,p) basis set. The quantum DFT results of the linear polarizability, the average second-order hyperpolarizability and the third-order nonlinear susceptibility values were computed and analyzed. The results showed that the organic compound (QBCP) has great potential for application as a third-order nonlinear optical material.
Second-order nonlinear optical properties of two chalcone derivatives: insights from sum-over-states
(2021) Custodio, Jean Marcos Ferreira; D´Oliveira, Giulio Demetrius Creazzo; Gotardo, Fernando; Cocca, Leandro Henrique Zucolotto; De Boni, Leonardo; Noda Pérez, Caridad; Napolitano, Hamilton Barbosa; Osorio, Francisco Aparecido Pinto; Valverde, Clodoaldo
In this study, a combined experimental and theoretical study of the nonlinear optical properties (NLO) of two chalcone derivatives, (E)-3-(2-methoxyphenyl)-1-(2-(phenylsulfonylamine)phenyl)prop-2-en-1-one (MPSP) and (E)-3-(3-nitrophenyl)-1-(2-(phenylsulfonylamine)phenyl)prop-2-en-1-one (NPSP), in DMSO is reported. The single crystal structures of the compounds, which differ only by the type and position of one substituent, were grown using the slow evaporation technique, and the main structural differences are discussed. The two-photon absorption and first-order hyperpolarizability measurements were performed via the Z-scan technique and hyper-Rayleigh scattering experiment in DMSO. The theoretical calculations were performed using the Density Functional Theory (DFT) at the CAM-B3LYP/6-311++G(d,p) level, and the sum-over-states (SOS) approach in both static and dynamic cases. Besides the electron conjugation achieved by the aromatic rings, olefins, and carbonyl groups, both compounds have a nearly flat chalcone backbone, which is believed to contribute to the nonlinear optical properties. MPSP and NPSP have different positions, even though they have roughly the same conformation and form C–H⋯O interactions. For several studied frequencies, the HRS first hyperpolarizability values for MPSP are greater than those for NPSP, indicating that in most cases the NLO properties of MPSP are better. The comparison among the theoretical and experimental HRS first hyperpolarizability results showed a good agreement. In addition, the two-dimensional second order nonlinear optical spectra obtained from the sum-over-states model indicate good second-order NLO responses of the two chalcone derivatives under external fields. Our findings are important not only to show the potential nonlinear optical application of the two new compounds but also to gain an insight into how different chemical compositions might affect the crystal structures and physico-chemical properties.

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