Professora Paula Homem-de-Mello

@article{Homem-de-Mello2025,

title = {DESIGN BIOINSPIRADO DE CORANTES},

author = {Paula Homem-de-Mello and Ana Clara Gonzalez de Souza and Diêgo U. Melo and Gabriel S. Mol and Jhonathan R. De Souza and Leonardo M. Carneiro and Maíra G. Nobrega and Mateus Zanotto and Raissa Lohanna G. Q. Corrêa and Hueder P. M. de Oliveira and Fernando H. Bartoloni and Yuri A. Aoto and Maurício Domingues Coutinho-Neto and Ednilsom Orestes},

url = {https://www.scielo.br/j/qn/a/RCr5ZtRt4bVGwZhp5nxGSjP/},

doi = {10.21577/0100-4042.20250047},

issn = {1678-7064},

year  = {2024},

date = {2024-09-09},

urldate = {2025-00-00},

journal = {Quim. Nova},

publisher = {Sociedade Brasileira de Quimica (SBQ)},

abstract = {The history of the discovery, use, and development of dyes is closely linked to the history of humanity itself. Among the first records of human civilization are cave paintings made from, e.g., fruits, plants, minerals, and insects. Over the centuries, using different techniques, colors have been given to all types of materials and products, from clothing to food. The chemicals responsible for colors are dyes - a vast collection of molecules of the most varied compositions, but which have in common the absorption of light within the visible window of the electromagnetic spectrum. This article aims not only to review the properties of some classes of natural dyes, their origins, and their applications but also to describe the various computational chemistry methods involved in designing new bio-inspired molecules.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Maringolo2024,

title = {Spectrophotometric determination of bisphenol A in beverages using multi-dispersion calibration.},

author = {Vivian Maringolo and Alexandre Z. Carvalho and Paula Homem-de-Mello and Mateus Zanotto and Fernanda C.O.L. Martins and Wanessa R. Melchert and Diogo L. Rocha},

url = {https://www.sciencedirect.com/science/article/pii/S0956713524005681},

doi = {10.1016/j.foodcont.2024.110851},

issn = {0956-7135},

year  = {2024},

date = {2024-09-00},

urldate = {2024-09-00},

journal = {Food Control},

publisher = {Elsevier BV},

abstract = {Bisphenol A (BPA) is an endocrine disruptor that may be present in plastics and coatings of food and beverage packages. In this regard, the World Health Organization recommends the maximum migration of BPA to foodstuffs as < 0.6 mg kg-1. Analytical BPA determination procedures have been based on chromatographic techniques, which generate waste with organic solvents. Alternatively, proposed spectrophotometric procedures have often shown high detection limits for foodstuffs analysis, requiring pre-concentration prior to determination. The analysis of beverages is susceptible to interferences because of their complex formulation comprising dyes and sugars, for example, that hinder spectrophotometric determinations. Multi-signal calibrations are powerful tools used to minimize matrix effects, and recently, they have proven efficient when performed in flow analysis systems, denominated as multi-dispersion calibration (MDC). This work proposes a multi-pumping flow system for the spectrophotometric determination of BPA based on the reaction with sulfanilamide (used for the first time) after diazotization to yield a compound with an absorption maximum at 446 nm. After the optimization of the main parameters, a linear response was observed between 0.25 and 10 mg L-1. The detection limit (by external calibration), coefficient of variation (n=20), and determination rate were estimated at 0.057 mg L-1, 4.0 %, and 33 h-1, respectively. The MDC was exploited to analyze beverage samples to minimize interferences, especially due to dyes and sucrose. The detection limit estimated for this method was 0.06 mg L-1. Recoveries from 84 to 114 % and the agreement of comparative analysis of the samples with the reference procedure (at the 95% confidence level) demonstrated the accuracy of the proposed procedure. Therefore, the developed alternative is reliable with proper sensitivity and minimum sample preparation for the spectrophotometric determination of BPA in beverages.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{DOSSANTOS2024127457,

title = {Kraft lignin-based polyurethanes: Bulk properties, stability and adhesion to native aluminum surfaces},

author = {Demetrio J. Santos and Lara B. Tavares and Leonardo D. Antonino and Rogerio R. Sousa Junior and Paula Homem-de-Mello and Cedric R. Leão},

url = {https://www.sciencedirect.com/science/article/pii/S0032386124007936},

doi = {https://doi.org/10.1016/j.polymer.2024.127457},

issn = {0032-3861},

year  = {2024},

date = {2024-01-01},

urldate = {2024-01-01},

journal = {Polymer},

volume = {309},

pages = {127457},

abstract = {Lignin as a byproduct from pulp and paper manufacturing has been extensively investigated as raw material for polymer developments. Although, fundamental topics related to the adhesion mechanisms of lignin-based reactive polyurethanes (LPU) still remain unclear. In this work, LPU thin films on native aluminum surface were prepared and characterized. Diluted in THF, employed as the solvent, reactive mixtures of 4,4′-methylene diphenyl isocyanate (4,4′-MDI) and the soluble fraction of three lignins (liquid hydroxypropylated Kraft lignin and two powder Kraft lignins with different pH) were used for LPU thin film deposition via spin coating on aluminum (PVD layer on silicon wafer). The resulting film thickness ranged from 8 nm to several micrometers. The chemical state of the three LPU compositions was assessed in bulk by infrared attenuated total reflectance (IR-ATR) and in the thin films by infrared external reflection absorption spectroscopy (IR-ERAS). Binding energies of 4,4′-methylene diphenyl diisocyanate with aliphatic and aromatic hydroxyl groups were estimated using Density Functional Theory (DFT) simulations. Thus, besides the elucidation of the bulk chemical state of LPUs, the relation to adhesion and stability of LPUs to a native aluminum surface was evaluated. In addition, film topography and homogeneity were monitored by SFM. All lignin types form uniform and homogeneous films. Results revealed a higher consumption of isocyanate groups (NCO) in the formulation with the alkaline Kraft lignin than with the acid one, despite its lower hydroxyl content. A gradient of unreacted NCO was observed in LPU thin films obtained with the powder Kraft lignin types. Residual NCO is also found in thicker films, while the thinnest films did not contain unreacted NCO anymore, indicating the activating effect of the native aluminum surface on LPU formation.},

keywords = {Hydroxypropylated lignin, Kraft lignin, Lignin-based polyurethane (LPU)},

pubstate = {published},

tppubtype = {article}

}

@article{doi:10.1021/acs.joc.3c02079,

title = {Chemiluminescence of a Firefly Luciferin Analogue Reveals that Formation of the Key Intermediate Responsible for Excited State Generation Occurs on a Fully Concerted Step},

author = {Diego Ulysses Melo and Henrique Bergonzini de Lima and Roberta Albino Reis and Andreia Boaro and Alexander Garreta Gonçalves Costa Pinto and Luiz Francisco Monteiro Leite Ciscato and Paula Homem-de-Mello and Fernando Heering Bartoloni},

url = {https://doi.org/10.1021/acs.joc.3c02079},

doi = {10.1021/acs.joc.3c02079},

year  = {2023},

date = {2023-12-19},

urldate = {2024-01-01},

journal = {The Journal of Organic Chemistry},

volume = {89},

number = {1},

pages = {345-355},

abstract = {The chemiluminescence (CL) reaction of eight different 2-(4-hydroxyphenyl)-4,5-dihydrothiazole-4-carboxylate esters with an organic superbase and oxygen was investigated through a kinetic and computational study. These esters are all analogues to the luciferin substrate involved in efficient firefly bioluminescence. The kinetic data obtained from CL emission and light absorption assays were used in the context of linear free energy relationships (LFER); we obtained the Hammett reaction constant ρ = +1.62 ± 0.09 and the Brønsted constant βlg = −0.39 ± 0.04. These observations from LFER, together with activation parameters obtained from Arrhenius plots, suggest that the formation of the high-energy intermediate (HEI) 1,2-dioxetanone occurs via a concerted mechanism during the rate-determining step of the reaction. Calculations performed using density functional theory support a late transition state for HEI formation within the reaction mechanism pathway, which was described considering geometric parameters, Wiberg bond indices from natural bond order analysis, and the atomic charges derived from the electrostatic potential.},

note = {PMID: 38113466},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{doi:10.1021/acs.jpcb.3c01707,

title = {Synergistic Interaction of Hyperbranched Polyglycerols and Cetyltrimethylammonium Bromide for Oil/Water Interfacial Tension Reduction: A Molecular Dynamics Study},

author = {James M. de Almeida and Conny Cerai Ferreira and Lucas Bandeira and Renato D. Cunha and Maurício Domingues Coutinho-Neto and Paula Homem-de-Mello and Ednilsom Orestes and Regina Sandra Veiga Nascimento},

url = {https://doi.org/10.1021/acs.jpcb.3c01707},

doi = {10.1021/acs.jpcb.3c01707},

year  = {2023},

date = {2023-10-23},

journal = {The Journal of Physical Chemistry B},

volume = {0},

number = {0},

pages = {null},

abstract = {Applying surfactants to reduce the interfacial tension (IFT) on water/oil interfaces is a proven technique. The search for new surfactants and delivery strategies is an ongoing research area with applications in many fields such as drug delivery through nanoemulsions and enhanced oil recovery. Experimentally, the combination of hyperbranched polyglycerol (HPG) with cetyltrimethylammonium bromide (CTAB) substantially reduced the observed IFT of oil/water interface, 0.9 mN/m, while HPG alone was 5.80 mN/m and CTAB alone IFT was 8.08 mN/m. Previous simulations in an aqueous solution showed that HPG is a surfactant carrier. Complementarily, in this work, we performed classical molecular dynamics simulations on combinations of CTAB and HPG with one aliphatic chain to investigate further the interaction of this pair in oil interfaces and propose the mechanism of IFT decrease. Basically, from our results, one can observe that the IFT reduction comes from a combination of effects that have not been observed for other dual systems: (i) Due to the CTAB-HPG strong interaction, a weakening of their specific and isolated interactions with the water and oil phases occurs. (ii) Aggregates enlarge the interfacial area, turning it into a less ordered interface. (iii) The spread of individual molecules charge profiles leads to the much lower interfacial tension observed with the CTAB+HPG systems.},

note = {PMID: 37871185},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Corrêa2023,

title = {Diving into the optoelectronic properties of Cu(II) and Zn(II) curcumin complexes: a DFT and wavefunction benchmark},

author = {Raissa Lohanna Gomes Quintino Corrêa and Matheus Morato Ferreira de Moraes and Kléber Thiago de Oliveira and Yuri Alexandre Aoto and Maurício Domingues Coutinho-Neto and Paula Homem-de-Mello},

doi = {10.1007/s00894-023-05560-1},

issn = {0948-5023},

year  = {2023},

date = {2023-05-00},

journal = {J Mol Model},

volume = {29},

number = {5},

publisher = {Springer Science and Business Media LLC},

keywords = {Catalysis, Computational Theory and Mathematics, Computer Science Applications, Inorganic Chemistry, Organic Chemistry, Physical and Theoretical Chemistry},

pubstate = {published},

tppubtype = {article}

}

@article{SOUZA2023108460,

title = {Benchmarking DFT functionals for photophysics of pyranoflavylium cations},

author = {Jhonathan R. Souza and Carles Curutchet and Yuri A. Aoto and Paula Homem-De-Mello},

url = {https://www.sciencedirect.com/science/article/pii/S109332632300058X},

doi = {https://doi.org/10.1016/j.jmgm.2023.108460},

issn = {1093-3263},

year  = {2023},

date = {2023-01-01},

journal = {Journal of Molecular Graphics and Modelling},

volume = {122},

pages = {108460},

abstract = {An intense absorption, phosphorescence, a long triplet excited state lifetime and singlet oxygen generation capabilities are characteristics of pyranoflavylium cations, analogues to pyranoanthocyanidins originated in the maturation process of red wine. Such properties make these compounds potential photosensitizers to be applied in photodynamic therapy. In this context, the photophysical processes underlying that treatment critically depend on the electronic structure of the pyranoflavylium molecules. When employing density functional theory to describe the electronic structure of molecules, the choice of the most suitable functional is not trivial, and benchmark studies are needed to orient practitioners in the field. In this work, a benchmark of seven of the most commonly used density functionals in addressing the photophysical properties of a set of eight pyranoflavylium cations is reported. Ground and excited state geometries, molecular orbitals, and absorption, fluorescence and phosphorescence transition energies were calculated using density functional theory approaches, and evaluated and compared to experimental data and monoreferential wave function-based methodologies. Statistical analysis of the results indicates that global-hybrid functionals allow an excellent description of absorption and emission energies, with errors around 0.05 eV, while range-separated variants led to somewhat larger errors in the range 0.1–0.2 eV. In contrast, range-separated functionals display excellent phosphorescence energies with errors close to 0.05 eV, in this case global-hybrids showing increased discrepancies around 0.5–0.1 eV.},

keywords = {Benchmark, Electronic structure, Excited-states, Photophysics, Photosensitizers, Time-dependent density functional theory (TD-DFT)},

pubstate = {published},

tppubtype = {article}

}