Mariela Martins Nolasco

Mariela Martins Nolasco
University of Aveiro | UA · CICECO - Centre for Research in Ceramics and Composite Materials

PhD

About

50
Publications
19,296
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1,517
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January 2017 - January 2022
University of Aveiro
Position
  • Research Assistant

Publications

Publications (50)
Article
The effect of water on the physicochemical properties of deep eutectic solvents (DES) is a trending research topic. In this work, inelastic neutron scattering (INS) spectroscopy, was used to probe intermolecular interactions in the water-deep eutectic solvent mixtures for the cases of choline chloride (the hydrogen bond acceptor) and three differen...
Article
Full-text available
The structure and dynamics of crystalline 4-(dimethylamino) benzaldehyde, 4DMAB, are assessed through INS spectroscopy combined with periodic DFT calculations. The excellent agreement between experimental and calculated spectra is the basis for a reliable assignment of INS bands. The external phonon modes of crystalline 4DMAB are quite well describ...
Article
Full-text available
The dynamics of 2-methoxybenzaldehyde, 4-methoxybenzaldehyde, and 4-ethoxybenzaldehyde in the solid state are assessed through INS spectroscopy combined with periodic DFT calculations. In the absence of experimental data for 4-ethoxybenzaldehyde, a tentative crystal structure, based on its similarity with 4-methoxybenzaldehyde, is considered and ev...
Article
Full-text available
Bacterial nanocellulose (BC)-based composites containing poly(2-hydroxyethyl methacrylate) (PHEMA), poly(methacroylcholine chloride) (PMACC) or poly(methacroylcholine hydroxide) (PMACH) were characterized by inelastic neutron scattering (INS) spectroscopy, combined with DFT (density functional theory) calculations of model systems. A reasonable mat...
Article
Solid‐state light‐emitting diodes (LEDs) are driving the lighting industry towards efficient and environmentally friendly lighting and displays. Current challenges encompass efficient and low‐cost down‐shifting phosphors with tuned emission colors. Green light lies on the low‐loss optical transmission window in plastic optical fibers and plays a sp...
Article
Full-text available
The present work emphasizes the value of periodic density functional theory (DFT) calculations in the assessment of the vibrational spectra of molecular crystals. Periodic calculations provide a nearly one-to-one match between the calculated and observed bands in the inelastic neutron scattering (INS) spectrum of crystalline 4-phenylbenzaldehyde, t...
Article
Visible‐light excited Eu 3+ ‐complexes have received much attention due to the rapidly increasing demand for less‐harmful biomarkers and low‐voltage driven emitters. Nevertheless, these complexes usually exhibit poor emission quantum yields, contrarily to the ones excited in the ultraviolet spectral region. To address this challenge, a series of co...
Article
The present work aims at exploiting a polyelectrolyte nanocomposite based on poly(4-styrene sulfonic acid) (PSSA) and bacterial cellulose (BC) as an eco-friendly proton-exchange membrane (PEM) for application in microbial fuel cells (MFCs). The PSSA/BC-based PEM was confirmed as a true nanocomposite by inelastic neutron scattering (INS) vibrational...
Article
There is a lack of fundamental knowledge on deep eutectic solvents, even for the most extensively studied mixtures, such as the mixture of cholinium chloride and urea, that prevents a judicious choice of components to prepare new solvents. The objective of this work is to study and understand the fundamental interactions between cholinium chloride...
Article
A thorough vibrational portrait of 4-fluorobenzaldehyde is presented, covering Infrared (Mid- and Far-), Raman and Inelastic Neutron Scattering (INS) spectra. Periodic DFT calculations (CASTEP) of a model 4FB crystal proved useful for vibrational assignment, yielding estimates of experimental spectra with near one-to-one correspondence – including...
Article
Montelukast (MLK), an oral antiasthmatic drug with growing use, requires special care in formulation and storage to avoid its degradation by action of light and/or water. This work investigates the increase in the stability of montelukast as the effect of molecular encapsulation with gamma-cyclodextrin (γ-CD) by means of a solvent-free method, cogr...
Article
Widespread microplastic pollution is raising growing concerns as to its detrimental effects upon living organisms. A realistic risk assessment must stand on representative data on the abundance, size distribution and chemical composition of microplastics. Raman microscopy is an indispensable tool for the analysis of very small microplastics (<20 μm...
Article
This work presents a comprehensive spectroscopic analysis of crystalline isoniazid, one of the main drugs in tuberculosis chemotherapy, using a blend of spectroscopic and computational methods. Mid- and far-infrared, Raman, and inelastic neutron scattering spectroscopies, with contribution of isotopic substitution are combined with discrete and per...
Article
A thorough vibrational spectroscopy and molecular modeling study on poly(ethylene 2,5-furandicarboxylate) (PEF) explores its conformational preferences, in the amorphous and crystalline regions, while clarifying structure–property correlations. Despite the increasing relevance of PEF as a sustainable polymer, some of its unique characteristics are...
Article
Photoluminescent isotypical phosphonate-based Metal-Organic Frameworks, [Ln(H5btp)]∙2H2O [Ln3+ = Tb3+ (1), Gd3+ (2), H8btp = [1,1’-biphenyl]-3,3’,5,5’-tetrayltetrakis(phosphonic acid)] prepared under solvo(hydro)thermal conditions exhibit a three-dimensional supramolecular structure built up from phosphonate linkers bridging Ln3+ ions. Single-cryst...
Article
The solids choline chloride and urea, mixed in a 1:2 molar proportion, form the iconic deep eutectic solvent “Reline”. A combination of computational and vibrational spectroscopy tools, including inelastic neutron scattering (INS), have been used to probe intermolecular interactions in the eutectic mixture. Reline’s experimental spectra were estima...
Chapter
Full-text available
This chapter presents an overview of the application of Raman spectroscopy in the characterization of microplastics, opening with a brief description of the principles of Raman spectroscopy and some of its experimental apparatus, and discussing the main advantages and limitations of the technique. Particular attention is given to the location of pl...
Article
The photophysical properties of a new alternating copolymer containing fluorene, terpyridine, and complexed sites with trivalent europium (Eu(3+)) ions (LaPPS66Eu) were investigated, using the non-complexed backbone (LaPPS66) and a low molecular weight compound of similar chemical structure of the ligand/Eu(3+) site (LaPPS66M) as a model compound....
Article
A series of europium Eu- and La-doped complexes with two different crystal structures, namely, EuxLa1–x(phen)2(NO3)3 [phen = 1,10-phenanthroline, x = 1.0 (1), 0.88 (2), 0.73 (3), and 0.52 (4)] and {[EuxLa1–x(phen)2(H2O)2(NO3)2](NO3)·2(phen)(H2O)} [x = 0.28 (5) and 0.0 (6)], were synthesized in aqueous solution by using different Eu/La ratios.The co...
Article
Lanthanide-based coordination compounds of molecular formula [Ln(keto)3(H2O)], where Ln=Gd, Eu and keto=ketoprofen, were synthesized and their photoluminescence features were detailed in the 12-300K interval. The emission spectra of [Eu(keto)3(H2O)] reveal a strong dependence with the temperature, well-illustrated by an unusual large blue-shift (~1...
Article
Full-text available
The α-substituted β-diketonate [Ln(3Cl-acac)3(H2O)2] [Ln = Tb, Gd] complexes (with 3Cl-acac– being 3-chloro-2,4-pentanedionate) were characterized by elemental analysis, infrared, ultraviolet (UV)-visible and photoluminescence spectroscopies. For comparison purposes regarding photoluminescence, the well-known [Tb(acac)3(H2O)2] complex was also synt...
Article
The regular MCM-41 type mesostructured silica material was used as a support for the incorporation of the highly luminescent tris(beta-diketonate) complex Eu(tta)3ephen yielding the hybrid MCM-Eu material. Suitable characterization by powder X-ray diffraction (XRD), thermogravimetric analyses (TGA), diffuse reflectance infrared Fourier transform sp...
Article
The suitability of the computer package LUMPAC to calculate the photoluminescence properties of metal–organic frameworks was assessed by considering three systems based on the ditopic 1,4-phenylenebis(methylene)diphosphonic acid (H4pmd) ligand and Ln3+ ions, namely, [Eu(Hpmd)(H2O)] (1), [La2(H2pmd)(pmd)(H2O)2] (2) and [La2(H2pmd)3(H2O)12] (3, previ...
Article
Full-text available
The combination of the glycine-derivative supramolecular salt 4,6-bis(carboxymethylamino)-2-oxo-2,3-dihydro-1,3,5-triazin-1-ium chloride (H2bodt·HCl) and lanthanide(III) chloride hydrates under hydrothermal conditions (120 °C, 48 h) led to the formation of a family of isotypical materials formulated as [Ln(bodt)(Hbodt)] [where Ln3+ = La3+ (1), (La0...
Article
The reaction of [MoO2Cl2(pzpy)] (1) (pzpy = 2-[3(5)-pyrazolyl]pyridine) with water in an open reflux system (16 h), in a microwave synthesis system (120 °C, 2 h), or in a Teflon-lined stainless steel digestion bomb (100 °C, 19 h) gave the molybdenum oxide/pyrazolylpyridine polymeric hybrid material [Mo3O9(pzpy)]n (2) as a microcrystalline powder in...
Article
The inelastic neutron scattering (INS) spectra of cyclopentanone were obtained for pure and 50% CCl4 solution forms. Spectra are compared with infrared and Raman data, and with DFT calculated eigenvectors. This exercise aims to find spectroscopic evidence in the neutron spectra for the presence of C–H⋯O hydrogen bonds. These are weak interactions w...
Article
Following a computational-experimental approach, a highly luminescent β-diketonate-europium(III) complex containing 2-thenoyltrifluoracetonate (tta−) and 5,6-epoxy-5,6-dihydro-[1,10] phenanthroline (ephen) ligands, Eu(tta)3ephen (II), was theoretically studied by DFT/TD-DFT calculations, synthesized from Eu(tta)3(H2O)2(I) and fully characterized by...
Article
Europium (t-Eu) and gadolinium (t-Gd) β-diketonate complexes with photoactive t-bpete ligand, [Ln(btfa)3(t-bpete)(MeOH)] (Ln = Eu, Gd), where btfa– and t-bpete are 4,4,4-trifluoro-1-phenyl-1,3-butanedionate and trans-1,2-bis(4-pyridyl)ethylene, respectively, were synthesized, characterized by vibrational, absorption (reflectance) and photoluminesce...
Article
Luminol, one of the most popular electrochemiluminescence systems used in forensic chemistry, proved to be a suitable system to study the importance of cooperativity in hydrogen-bond chains. The computational pairwise approach PiMM was applied to the system and a thorough band assignment was accomplished. Hydrogen-bond and hydrogen-bond cooperativi...
Article
The complete vibrational spectra assignment of dihydrocoumarin is performed through a combined vibrational spectroscopy and DFT calculations approach. To provide effective information, vibrational analysis was also performed for α-pyrone and coumarin related systems. The presence of extra components in the νCO band profile can only be understood by...
Article
In many Eu(III) -based materials, the presence of an intermediate energy level, such as ligand-to-metal charge transfer (LMCT) states or defects, that mediates the energy transfer mechanisms can strongly affect the lifetime of the (5) D(0) state, mainly at near-resonance (large transfer rates). We present results for the dependence of the (5) D(0)...
Article
Full-text available
Density functional theory/time-dependent density functional theory (DFT/TD-DFT) calculations were performed on a series of europium(III) complexes of 4,7-disubstituted-1,10-phenanthroline ligands (phen-X) of general formula Eu(TTA)(3)(phen-X) (where TTA stands for thenoyltrifluoroacetonato and X = H, CH(3), OCH(3), Cl, Br, CO(2)Et, C(6)H(5), C(4)HO...
Article
The dioxomolybdenum(VI) complexes [MoO(2)Cl(2)(PzPy)] (1) and [MoO(2)(OSiPh(3))(2)(PzPy)] (5) (PzPy = 2-[3(5)-pyrazolyl]pyridine) were synthesized and characterized by vibrational spectroscopy, with assignments being supported by DFT calculations. Complex 5 was additionally characterized by single crystal X-ray diffraction. Recrystallization of 1 u...
Article
Spectroscopic evidence for C-H...O hydrogen bonding in chloroform...acetone [Cl(3)CH...O=C(CH(3))(2)] mixtures was obtained from vibrational inelastic neutron scattering (INS) spectra. Comparison between the INS spectra of pure samples and their binary mixtures reveals the presence of new bands at about 82, 130 and 170 cm(-1). Assignment of the 82...
Article
In this work, the usefulness of the Pairs in Molecular Materials (PiMM) approach to elucidate unknown structures of molecular crystals is assessed. This methodology aims to assist the prediction of probable crystal structures from the vibrational spectra, through the identification of the most relevant motifs in the potential energy landscape of th...
Article
The inclusion compounds of α-, β- and γ-cyclodextrins (α-CD, β-CD and γ-CD) with trans-cinnamic acid (t-CIA), 3-hydroxy-trans-cinnamic acid (t-3OHCIA), 4-hydroxy-trans-cinnamic acid (t-4OHCIA) and 3,4-dihydroxy-trans-cinnamic acid (t-3,4OHCIA) were prepared and characterized, in the solid state, by means of thermogravimetry and Raman spectroscopy....
Article
A computationally-assisted methodology to assign the vibrational spectra of molecular materials (PiMM) has been successfully applied to the Raman and infrared (IR) spectra of trans-cinnamic acid (t-CIA) in the solid state. The effects of molecular association through OH···O hydrogen-bonding in both the wavenumber and the intensity of the bands are...
Article
FT-Raman spectroscopy turns out to be a powerful technique to evaluate the amount of polymorphic and pseudopolymorphic forms in crystalline samples—which is particularly relevant in pharmaceutical sciences. This paper presents a methodology that allows successful quantitative evaluation of the solid-state hydration and dehydration processes, using...
Article
Full-text available
Inclusion complexes comprising niobocene dichloride, Cp2NbCl2, and either native β-cyclodextrin (β-CD) or permethylated β-CD (TRIMEB) were prepared with a host:guest molar ratio of 1:1. The adducts were characterized in the solid state by powder X-ray diffraction (XRD), thermogravimetric analysis (TGA), 13C{1H} CP/MAS NMR, FTIR, and FT Raman spectr...
Article
Theophylline is known to undergo vapor phase induced hydrate-anhydrate pseudopolymorphic transformations, which can affect its bioavailability. In this work, the kinetics of the pseudopolymorphic transitions of theophylline crystals in different storage conditions is studied using a vibrational spectroscopic technique. While the hydration is a sing...
Article
Organic-inorganic mesoporous materials of the MCM-41 type are important materials that can be prepared by either post-synthesis or one-pot synthesis procedures. A complete control of the characteristics at a local level is of the utmost importance in view of the applications of such materials. However, there are not many studies relating such featu...
Article
Full-text available
Dioxomolybdenum(VI) complexes of general formula [MoO2X2L2] (X=Cl, OSiPh3; L2=2-(1-butyl-3-pyrazolyl)pyridine, ethyl[3-(2-pyridyl)-1-pyrazolyl]acetate) were prepared and characterised by 1H NMR, IR and Raman spectroscopy. The assignment of the vibrational spectra was supported by ab initio calculations. A single crystal X-ray diffraction study of t...
Article
A new computationally-assisted methodology (PiMM), which accounts for the effects of intermolecular interactions in the crystal, is applied to the complete assignment of the Raman and infrared vibrational spectra of room temperature forms of crystalline caffeine, theobromine, and theophylline. The vibrational shifts due to crystal packing interacti...
Article
The crystal structure of 4-phenyl-benzaldehyde reveals the presence of a dimer linked by the C=O and C9-H groups of adjacent molecules. In the liquid phase, the presence of C-H...O bonded forms is revealed by both vibrational and NMR spectroscopy. A DeltaH value of -8.2 +/- 0.5 kJ mol(-1) for the dimerisation equilibrium is established from the tem...
Article
C-H...O hydrogen bonds in liquid 2-cyclohexen-1-one are studied to assess the vibrational spectroscopic behavior of the Csp2-H and Csp3-H donors. The presence of a pseudo-isosbestic point in the vC = O region supports the assignment of the two observed bands to two species in equilibrium, considered to be the free and 1:1 associated forms. The valu...

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Projects (3)
Archived project
Identify the spectroscopic evidences of C-H...O hydrogen bonds
Project
The chapter starts with a presentation of the theory and practice of Raman spectrsocopy. The strengths and limitations of this technique in the identification of microplastics are illustrated with selected examples from the literature. The current body of work in raman characterization of microplastics is reviewed and best practices are highlighted.