Dalva L.A. de Faria

Influence of the N-[methylpyridyl]acetamide ligands on the photoluminescent properties of Eu(III)-perchlorate complexes

Abstract This work reports the synthesis, characterization and spectroscopic studies of Eu(III)-perchlorate complexes with amide ligands derived from N -[ x -methylpyridyl]acetamide where x =3, 4 and 6. The Eu(ClO 4 ) 3 3( x -mpa) complexes were characterized by elemental analyses, molar conductance, TG analyses and vibrational spectroscopy. Raman and infrared data show that the perchlorate ion, (ClO 4 − ), is bonded to Eu(III) as a monodentate ligand and that in these three complexes water molecules are not coordinated to the rare earth ion. The profiles of the emission spectra of the complexes with 3- and 4-mpa ligands are very similar but they differ from the complex containing 6-mpa ligand. This spectroscopic behavior can be rationalized in terms of the Ω λ ( λ =2 and 4) and R 02 experimental intensity parameters. The values of Ω 2 (∼6.5×10 −20 cm 2 ) in these complexes are smaller than in Eu(III)-TTA compounds ( Ω 2 ∼35.0×10 −20 cm 2 ), indicating that in the former case the rare earth ion is in a chemical environment less polarizable. Lifetime and emission quantum efficiency measurements for the emitting level 5 D 0 were carried out and the results are discussed.

Characterization of corrosion products formed on steels in the first months of atmospheric exposure

The corrosion products of carbon steel and weathering steel exposed to three different types of atmospheres, at times ranging from one to three months, have been identified. The steels were exposed in an industrial site, an urban site (Sao Paulo City, Brazil), and a humid site. The effect of the steel type on the corrosion products formed in the early stages of atmospheric corrosion has been evaluated. The corrosion products formed at the various exposure locations were characterized by Raman microscopy, X-Ray diffraction (XRD) and their morphology was observed by Scanning Electron Microscopy (SEM). Three regions of different colours (yellow, black and red) have been identified over the steel coupons by Raman microscopy. Analysis carried out on each of these areas led to the characterization of the correspondent oxide/hydroxide phases. The main phases present were lepidocrocite (g-FeOOH) and goethite (a-FeOOH). Small amounts of magnetite (Fe3O4) were also eventually encountered.

Syntheses and spectroscopic characterization of fac-[Re(CO)3(phen)(L)]PF6, L=trans- and cis-1,2-bis(4-pyridyl)ethylene

The complex fac-[Re(CO)3(phen)(t-bpe)]PF6 (t-bpe=trans-1,2-bis(4-pyridyl)ethylene, phen=1,10-phenanthroline) was synthesized, purified and characterized by UV–Vis, 1H NMR, Raman and IR spectroscopy. 1H NMR resonance spectrum of fac-[Re(CO)3(phen)(t-bpe)]+ reveals a clear electronic communication of the metal center across the coordinated t-bpe with upfield shift of the ligand signals upon complexation. The CO stretching frequencies are in accord with facial geometry of the rhenium complex. The photochemical behavior of free trans-1,2-bis(4-pyridyl)ethylene and of its protonated form is also reported. The quantum yield for the trans→cis photoinduced isomerization of free ligand in methanolic solutions at 313 nm irradiation is 0.17±0.03. The average values for the photoisomerization of the protonated ligand (pH 1.9) are 0.19±0.02 and 0.15±0.01, respectively at 313 and 334 nm excitation. The photoassisted trans→cis isomerization of t-bpe in the fac-[Re(CO)3(phen)(t-bpe)]+ complex was achieved with higher quantum yields at lower energy irradiation by exploiting the red shifted absorption upon formation of the complex. The photoproducts cis-1,2-bis(4-pyridyl)ethylene and fac-[Re(CO)3(phen)(c-bpe)]PF6 were synthesized and identified by UV–Vis, 1H NMR and luminescence properties.

Mechanism of automotive clearcoat damage by dragonfly eggs investigated by surface enhanced Raman scattering

Dragonflies are attracted by the reflection of sunlight on car surfaces and lay their eggs on the clearcoat resin. Considering that the surface can reach up to 93°C and that during the egg hardening process (sclerotization) H2O2 is released, cysteine and cystine residues present in the egg protein can be oxidized to sulfinic and sulfonic acids. These are strong acids which, like acid rain, can hydrolyze the acrylic/melamine resin causing damage where the eggs were laid. Confocal Raman spectroscopy revealed that the spectra obtained from damaged and intact portions of the clearcoat were similar, in agreement with infrared absorption spectroscopy data. These data demonstrate that the attack by eggs, H2SO4 and cysteine/H2O2 only promotes solubilization of resin through acid hydrolysis of the resin ester and amide moieties. Furthermore, surface enhanced Raman scattering (SERS) spectra obtained from dragonfly eggs and cysteine/H2O2 reaction products treated with a silver colloid were very similar, thus confirming the presence of sulfinic and sulfonic acids.

Spectroscopic Studies on the Interaction of Tetramethylpyridylporphyrins and Cationic Clays

In the present work, the interaction between5,10,15,20-tetrakis(1-methyl-4-pyridyl)-21H,23H-porphine (TMPyP) and its metallated form(CoTMPyP) with three cationic clays was investigatedby X-ray diffraction (XRD), UV-VIS and resonance Ramanspectroscopies. Sodium montmorillonites K10 and KSFand a synthetic fluorohectorite (FHT) containingdifferent macrocycle loadings, were prepared by an ionexchange reaction. In nonsaturated KSF and FHT, theCoTMPyP molecule assumes a flat orientation, relativeto the host layers, giving rise to at least twoabsorption bands in the Soret region (ca. 445 and 465 nm)assigned to adsorbed and intercalated CoTMPyP,respectively. For the delaminated K10 sample, a broadband centered around 456 nm, indicates a majorcontribution from the metalloporphyrin on the clayexternal surfaces. The electronic spectra of FHTsamples containing increasing amounts of CoTMPyPshow bands red shifted even when a small amount ofporphyrin is used, suggesting that the electroniclevels of the macrocycle are more affected by theinteraction with the clay than by the metalloporphyrindistortion inside the galleries. The resonance Ramanspectra obtained for all CoTMPyP samples presentedonly minor shifts in peak positions and band width,with the exception of the FHT saturated sample, wherethe bands are clearly broader when compared to otherloadings, suggesting that porphyrin aggregation isoccurring. In the case of TMPyP, the bands at ca. 430and 468 nm were assigned to nonprotonated andprotonated molecules, respectively. This assignment issupported by resonance Raman spectroscopy, which alsoshowed the ν2 mode (ca. 1550 cm-1) to bethe most sensitive peak to protonation.

Ability of laser fluorescence device associated with fluorescent dyes in detecting and quantifying early smooth surface caries lesions.

A laser fluorescence (LF) device is a portable tool, but it does not measure minor mineral changes. Our in vitro study aim is to propose the association of an LF with two fluorescent dyes and to evaluate the performance in detecting and quantifying early demineralization. Artificial caries lesions are created in 40 primary canine teeth using a demineralizing solution (pH=4.8) for 12, 24, 48, and 96 h. LF measurements are performed with DIAGNOdent after demineralization in these samples and in 20 sound primary teeth. Measurements with LF with 0.2-mM tetrakis(N-methylpyridyl)porphyrin (LF TMPyP) and with 4-mM protoporphyrin IX (LF PPIX) are made. The amount of calcium loss is determined by atomic emission spectrometry. A correlation between LF and LF with dyes and mineral loss and receiver operating characteristics analysis are performed, as well as comparisons of sensitivity, specificity, and accuracy values. Significant correlation is obtained with LF TMPyP and mineral loss of lesions demineralized for 24, 48, and 96 h. Better performance is achieved with LF TMPyP for all parameters than with LF alone. LF PPIX does not present good results. In conclusion, LF TMPyP provides good performance in detecting and quantifying very early enamel caries lesions.

CLAY-PORPHYRIN SYSTEMS: SPECTROSCOPIC EVIDENCE OF TMPyP PROTONATION, NON-PLANAR DISTORTION AND MESO SUBSTITUENT ROTATION

The interaction of the water-soluble 5,10,15,20-tetrakis(l -methyl-4-pyridyl)-21H,23H-porphine (TMPyP) with different 2:1 phyllosilicates was examined by Raman and UV-visible spectroscopies. The clay samples were saturated with the tetracationic porphyrin and isolated from the aqueous suspension. A red shift of the Soret band was observed for all the clay-TMPyP systems in the order vermiculite < Laponite < mica-smectite (Syn-1) < montmorillonite (SWy-2). Furthermore, three components were observed for the Soret band (at ~425, 455 and 488 nm). Raman spectra of the isolated solids excited at 457.9 nm, 488.0 nm and 514.5 nm suggest the occurrence of porphyrin protonation, nonplanar distortion and rotation of the meso substituent. Based on the vibrational data, an acidity scale was proposed for the clays: vermiculite < Laponite < SWy-2 < Syn-1. The relative contribution of the protonated spectra is larger at 457.9 nm than at 488.0 nm, suggesting that the peak at 455 nm corresponds to the protonated species. In Laponite, the relative intensity of the meso substituent band at ~1635 cm-1 indicates that the dihedral angle formed between the porphyrin and the methyl-pyridyl rings decreased in the non-protonated porphyrin as a consequence of intercalation. Raman data are thus consistent with the presence of at least two porphyrin species in resonance at 457.9 nm: the protonated and a more planar non-protonated porphyrin. At 488.0 nm the number of enhanced modes increases suggesting a decrease in the porphyrin symmetry. This allows assignment of the absorption band centered at 488 nm to a non-planar porphyrin conformation.

Morphological and Mineral Analysis of Dental Enamel After Erosive Challenge in Gastric Juice and Orange Juice

This study evaluated and compared in vitro the morphology and mineral composition of dental enamel after erosive challenge in gastric juice and orange juice. Human enamel specimens were submitted to erosive challenge using gastric juice (from endoscopy exam) (n = 10), and orange juice (commercially‐available) (n = 10), as follows: 5 min in 3 mL of demineralization solution, rinse with distilled water, and store in artificial saliva for 3 h. This cycle was repeated four times a day for 14 days. Calcium (Ca) loss after acid exposure was determined by atomic emission spectroscopy. The presence of carbonate (CO) and phosphate (PO) in the specimens was evaluated before and after the erosive challenge by FT‐Raman spectroscopy. Data were tested using t‐tests (P < 0.05). Morphology of enamel was observed in scanning electron microscopy (SEM). The mean loss of Ca was: 12.74 ± 3.33 mg/L Ca (gastric juice) and 7.07 ± 1.44 mg/L Ca (orange juice). The analysis by atomic emission spectroscopy showed statistically significant difference between erosive potential of juices (P = 0.0003). FT‐Raman spectroscopy found no statistically significant difference in the ratio CO/PO after the erosive challenge. The CO/PO ratios values before and after the challenge were: 0.16/0.17 (gastric juice) (P = 0.37) and 0.18/0.14 (orange juice) (P = 0.16). Qualitative analysis by SEM showed intense alterations of enamel surface. The gastric juice caused more changes in morphology and mineral composition of dental enamel than orange juice. The atomic emission spectroscopy showed to be more suitable to analyze small mineral loss after erosive challenge than FT‐Raman. Microsc. Res. Tech., 2011.

Properties and structural features of iron doped BABAL glasses

The chemical durability, density and structure of the BABAL glasses with batch compositions (100-x)(0.30BaO·0.50B2O3·0.20Al2O3)·xFe 2O3 (1 < x < 10 mol%), were investigated using Mossbauer spectroscopy, electron paramagnetic resonance (EPR), X-ray diffraction, Raman and differential thermal analysis (DTA). The chemical durability for the glass of composition 27BaO·45B2O3·18Al 2O3·10Fe2O3 (mol%) at 90 °C in distilled water was 700 times lower than that of iron phosphate glass 40Fe2O3·60P2O 5 (mol%). The Mossbauer spectra indicate the presence of iron (II) and iron (III) in tetrahedral or octahedral coordination. The results obtained from the gef = 4.3 EPR line are typical of the occurrence of iron (III) occupying substitutional sites and the line gef = 2.0 is related to the association of two or more Fe ions found in the interstices (or holes occupied by the glass modifier cations) of the glass network. The paths of X-ray diffraction are typical for glasses based in borate glasses. The Raman spectra showed that the boroxol ring disappears with the increase of iron content, concomitant with the appearance of BO4 and tetraborate structural units. At these conditions, an increase of dissolution rate and clustering of iron ions is observed.

Modelos para dispersão Raman em polímeros conjugados

Raman dispersion refers to the dependence of the position of Raman bands on the energy of the exciting radiation. In this work, the three main models currently used to explain this phenomenon (Conjugated Length Model, Amplitude Mode Model and Effective Conjugation Coordinate Model) are discussed. Raman dispersion is a consequence of p electron delocalization, but each model describes in a different way how p electron delocalization affects the position of Raman bands. Here the features, qualities and problems of the three models are highlighted.