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1.
Contemp Clin Dent ; 13(2): 118-124, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-35846577

RESUMO

Context: Recurrent caries are the leading cause of composite resin failure. Aims: The purpose of this pilot study was to test the efficacy of a novel copper iodide (CuI) containing dental adhesive in an in vitro caries model. Subjects and Methods: Streptococcus mutans and Lactobacillus acidophilus were grown individually on the complex medium for 48 h at 37°C. The pH of the mixed medium was 7.0 initially and tested every 24 h. 40 extracted teeth were prepared with standardized cavity preparations and coated with control or experimental CuI adhesives and imaged using a micro-computed tomography (microCT). Four study groups were evaluated: (1) control (2) 0.5 µg/ml CuI (3) 1.0 µg/ml CuI, 4) 5.0 µg/ml CuI. After incubation, the teeth were re-imaged using the microCT. Utilizing AnalyzePro software the three-dimensional data sets were overlaid and demineralization was measured and statistics were run. Statistics: Stratified ANOVA models were run to determine if there were differences between the control and experimental adhesive groups. Similarly, pH and bacterial concentrations were evaluated to ensure the viability of polymicrobial specimen. Results and Conclusions: Significant differences were found between the control group and the 1.0 and 5.0 CuI adhesive groups. No differences in pH were noted between the groups. Overlaid changes in demineralization were recorded as volume loss. CuI adhesives with 5 mg/ml or higher have the potential to limit tooth demineralization after bacterial penetration of a dental restoration in an in vitro caries model. Further testing is needed.

2.
Energy Fuels ; 33(7): 6088-6097, 2019 Jul 18.
Artigo em Inglês | MEDLINE | ID: mdl-31354183

RESUMO

Determination of the molecular structures of petroporphyrins has been crucial to understand the diagenetic pathways and maturation of petroleum. However, these studies have been hampered by their structural complexity and the challenges associated with their isolation. In comparison to the skeletal macrocyclic structures, much less is known about the substitutions, which are more sensitive to the maturation and diagenesis pathways. While these isolated vanadyl petroporphyrins largely consist of etioporphyrin and deoxophylloerythroetioporphyrin as expected, surprisingly, we find evidence that one or a few ß hydrogens are present in petroporphyrins of low carbon numbers using a combination of ultraviolet-visible spectroscopy, Fourier transform ion cyclotron resonance mass spectrometry, and non-contact atomic force microscopy. Petroporphyrins with ß hydrogens were not anticipated on the basis of their biological precursors. The data support dealkylation under catagenesis but not transalkylation or random alkylation of the ß and meso positions, despite the fact that more complex porphyrin structures are formed.

3.
J Esthet Restor Dent ; 31(4): 369-377, 2019 07.
Artigo em Inglês | MEDLINE | ID: mdl-31058428

RESUMO

OBJECTIVES: An impression accuracy study using a cadaver maxilla was performed using both prepared and intact teeth as well as palatal tissue. MATERIALS AND METHODS: Three crown preparations were performed on a cadaver maxilla. Seven different digital impression systems along with polyvinylsiloxane impressions were used to create digital models of the maxilla. Three-dimensional (3D) files of the experimental models were compared to a master model. The 3D files were overlaid and analyzed using a comparison software to create color coded figures that were measured for deviations between the master and experimental models. RESULTS: For scanning tooth structure, only the Planscan was significantly less accurate than the rest of impression techniques. No significant differences in accuracy were found between models created using digital impressions and those created from traditional vinyl polysiloxane impressions with cross arch deviations ranging from 18 to 39 µm for each. CONCLUSIONS: Impressions taken using all digital impression systems, save for the Planscan, were able to accurately replicate the tissues of a complete arch human maxilla. CLINICAL SIGNIFICANCE: Studies examining accuracy of digital impression systems have generally been performed on materials other than dental tissues. Optically, materials such as plastic and metal have properties different from enamel and dentin. This study evaluates accuracy of digital impression systems on human dentin, enamel, and soft tissues.


Assuntos
Técnica de Moldagem Odontológica , Maxila , Desenho Assistido por Computador , Arco Dental , Materiais para Moldagem Odontológica , Humanos , Imageamento Tridimensional , Modelos Dentários
4.
J Esthet Restor Dent ; 30(2): 113-118, 2018 03.
Artigo em Inglês | MEDLINE | ID: mdl-29476599

RESUMO

OBJECTIVE: Clinicians have been slow to adopt digital impression technologies due possibly to perceived technique sensitivities involved in data acquisition. This research has two aims: determine whether scan pattern and sequence affects the accuracy of the three-dimensional (3D) model created from this digital impression and to compare the 5 imaging systems with regards to their scanning accuracy for sextant impressions. MATERIALS AND METHODS: Six digital intraoral impression systems were used to scan a typodont sextant with optical properties similar to natural teeth. The impressions were taken using five different scan patterns and the resulting digital models were overlayed on a master digital model to determine the accuracy of each scanner performing each scan pattern. Furthermore, regardless of scan pattern, each digital impression system was evaluated for accuracy to the other systems in this same manner. RESULTS: No differences of significance were noted in the accuracy of 3D models created using six distinct scan patterns with one exception involving the CEREC Omnicam. Planmeca Planscan was determined to be the truest scanner while 3Shape Trios was determined to be the most precise for sextant impression making. CONCLUSIONS: Scan pattern does not significantly affect the accuracy of the resulting digital model for sextant scanning. CLINICAL SIGNIFICANCE: Companies who make digital impression systems often recommend a scan pattern specific for their system. However, every clinical scanning scenario is different and may require a different approach. Knowing how important scan pattern is with regards to accuracy would be helpful for guiding a growing number of practitioners who are utilizing this technology.


Assuntos
Técnica de Moldagem Odontológica , Modelos Dentários , Desenho Assistido por Computador , Arco Dental , Imageamento Tridimensional
5.
J Oral Implantol ; 44(1): 15-26, 2018 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-29064779

RESUMO

Existing root-analog dental implant systems have no standardized protocols regarding retentive design, surface manipulation, or prosthetic attachment design relative to the site's unique anatomy. Historically, existing systems made those design choices arbitrarily. For this report, strategies were developed that deliberately reference the adjacent anatomy, implant and restorable path of draw, and bone density for implant and retentive design. For proof of concept, dentate arches from human cadavers were scanned using cone-beam computed tomography and then digitally modeled. Teeth of interest were virtually extracted and manipulated via computer-aided design to generate root-analog implants from zirconium. We created a stepwise protocol for analyzing and developing the implant sites, implant design and retention, and prosthetic emergence and connection all from the pre-op cone-beam data. Root-analog implants were placed at the time of extraction and examined radiographically and mechanically concerning ideal fit and stability. This study provides proof of concept that retentive root-analog implants can be produced from cone-beam data while improving fit, retention, safety, esthetics, and restorability when compared to the existing protocols. These advancements may provide the critical steps necessary for clinical relevance and success of immediately placed root-analog implants. Additional studies are necessary to validate the model prior to clinical trial.


Assuntos
Desenho Assistido por Computador , Tomografia Computadorizada de Feixe Cônico , Implantes Dentários , Planejamento de Prótese Dentária , Raiz Dentária/diagnóstico por imagem , Densidade Óssea , Cadáver , Retenção em Prótese Dentária , Humanos , Carga Imediata em Implante Dentário , Projetos Piloto , Estudo de Prova de Conceito , Propriedades de Superfície , Extração Dentária
6.
Clin Oral Investig ; 21(1): 369-379, 2017 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-27020910

RESUMO

OBJECTIVES: This study investigated the antibacterial properties and micro-hardness of polyacrylic acid (PAA)-coated copper iodide (CuI) nanoparticles incorporated into glass ionomer-based materials, and the effect of PAA-CuI on collagen degradation. MATERIALS AND METHODS: PAA-CuI nanoparticles were incorporated into glass ionomer (GI), Ionofil Molar AC, and resin-modified glass ionomer (RMGI), Vitrebond, at 0.263 wt%. The antibacterial properties against Streptococcus mutans (n = 6/group) and surface micro-hardness (n = 5/group) were evaluated. Twenty dentin beams were completely demineralized in 10 wt% phosphoric acid and equally divided in two groups (n = 10/group) for incubation in simulated body fluid (SBF) or SBF containing 1 mg/ml PAA-CuI. The amount of dry mass loss and hydroxyproline (HYP) released were quantified. Kruskal-Wallis, Student's t test, two-way ANOVA, and Mann-Whitney were used to analyze the antibacterial, micro-hardness, dry mass, and HYP release data, respectively (p < 0.05). RESULTS: Addition of PAA-CuI nanoparticles into the glass ionomer matrix yielded significant reduction (99.999 %) in the concentration of bacteria relative to the control groups. While micro-hardness values of PAA-CuI-doped GI were no different from its control, PAA-CuI-doped RMGI demonstrated significantly higher values than its control. A significant decrease in dry mass weight was shown only for the control beams (10.53 %, p = 0.04). Significantly less HYP was released from beams incubated in PAA-CuI relative to the control beams (p < 0.001). CONCLUSIONS: PAA-CuI nanoparticles are an effective additive to glass ionomer-based materials as they greatly enhance their antibacterial properties and reduce collagen degradation without an adverse effect on their mechanical properties. CLINICAL RELEVANCE: The use of copper-doped glass ionomer-based materials under composite restorations may contribute to an increased longevity of adhesive restorations, because of their enhanced antibacterial properties and reduced collagen degradation.


Assuntos
Resinas Acrílicas/farmacologia , Antibacterianos/farmacologia , Colágeno/efeitos dos fármacos , Cobre/farmacologia , Cimentos de Ionômeros de Vidro/farmacologia , Iodetos/farmacologia , Streptococcus mutans/efeitos dos fármacos , Adolescente , Dentina/efeitos dos fármacos , Dureza , Humanos , Técnicas In Vitro , Teste de Materiais , Microscopia Eletrônica , Dente Molar , Nanopartículas , Tamanho da Partícula , Propriedades de Superfície , Adulto Jovem
7.
J Esthet Restor Dent ; 27(4): 194-202, 2015.
Artigo em Inglês | MEDLINE | ID: mdl-26177118

RESUMO

PURPOSE: This study evaluated the marginal gap of crowns fabricated using two new chairside computer-aided design/computer-aided manufacturing systems on preparations completed by clinicians with varying levels of expertise to identify whether common preparation errors affect marginal fit. The null hypothesis is that there is no difference in the mean marginal gaps of restorations of varying qualities and no difference in the mean marginal gap size between restorations fabricated using the PlanScan (D4D, Richardson, TX, USA) and the CEREC Omnicam (Sirona, Bensheim, Germany). MATERIAL AND METHODS: The fit of 80 lithium disilicate crowns fabricated with the E4D PlanScan or CEREC Omnicam systems on preparations of varying quality were examined for marginal fit by using the replica technique. These same preparations were then visually examined against common criteria for anterior all-ceramic restorations and placed in one of four categories: excellent, good, fair, and poor. Linear mixed modeling was used to evaluate associations between marginal gap, tooth preparation rating, and fabrication machine. RESULTS: The fit was not significantly different between both systems across all qualities of preparation. The average fit was 104 µm for poor-quality preparations, 87.6 µm for fair preparations, 67.2 µm for good preparations, and 36.6 µm for excellent preparations. CONCLUSION: The null hypothesis is rejected. It can be concluded that preparation quality has a significant impact on marginal gap regardless of which system is used. However, no significant difference was found when comparing the systems to each other. CLINICAL SIGNIFICANCE: Within the limitations of this in vitro study, it can be concluded that crown preparation quality has a significant effect on marginal gap of the restoration when the clinician uses either CEREC Omnicam or E4D PlansScan.


Assuntos
Desenho Assistido por Computador , Coroas , Planejamento de Prótese Dentária/métodos , Humanos
8.
J Dent Educ ; 79(6): 697-704, 2015 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-26034035

RESUMO

Traditionally, evaluating student work in preclinical courses has relied on the judgment of experienced clinicians utilizing visual inspection. However, research has shown significant disagreement between different evaluators (interrater reliability) and between results from the same evaluator at different times (intrarater reliability). This study evaluated a new experimental software (E4D Compare) to compare 66 student-produced tooth wax-ups at one U.S. dental school to an ideal standard after both had been digitally scanned. Using 3D surface-mapping technology, a numerical evaluation was generated by calculating the surface area of the student's work that was within a set range of the ideal. The aims of the study were to compare the reliability of faculty and software grades and to determine the ideal tolerance value for the software. The investigators hypothesized that the software would provide more consistent feedback than visual grading and that a tolerance value could be determined that closely correlated with the faculty grade. The results showed that a tolerance level of 450 µm provided 96% agreement of grades compared with only 53% agreement for faculty. The results suggest that this software could be used by faculty members as a mechanism to evaluate student work and for students to use as a self-assessment tool.


Assuntos
Dentística Operatória/educação , Educação em Odontologia , Avaliação Educacional/métodos , Tecnologia Educacional , Programas de Autoavaliação , Software , Desenho Assistido por Computador , Docentes de Odontologia , Retroalimentação , Humanos , Imageamento Tridimensional/métodos , Modelos Dentários , Variações Dependentes do Observador , Reprodutibilidade dos Testes , Estudantes de Odontologia , Propriedades de Superfície , Dente/anatomia & histologia
9.
J Dent ; 43(5): 546-55, 2015 May.
Artigo em Inglês | MEDLINE | ID: mdl-25731156

RESUMO

OBJECTIVES: This study aimed to investigate incorporation of polyacrylic acid (PAA) coated copper iodide (CuI) nanoparticles into dental adhesives, and to evaluate for the first time, their antibacterial properties, bond strength and cytotoxicity. METHODS: PAA-CuI nanoparticles were synthesized and incorporated into commercially available adhesives Optibond XTR (1.0mg/ml) and XP Bond (0.5 and 1.0mg/ml). The antibacterial properties of experimental and control specimens were evaluated (n=8), after ageing for 18h or 1 year, against Streptococcus mutans (1×10(8)cells/ml). Bond strength to human dentine of the control and experimental adhesives was evaluated by shear bond strength (n=10). For cytotoxicity evaluation, HGF cells were cultured with gingival fibroblast media and exposed to control and experimental adhesive blends (n=3). An MTT cell viability assay was used to assess cell metabolic function. A one-way analysis of variance followed by Tukey's test was used for data analysis. RESULTS: Significantly greater antibacterial properties were demonstrated for PAA-CuI containing adhesives after ageing for 18h or 1 year relative to all control groups. A reduction in Streptococcus mutans viable cell count of 99.99%, 99.99% and 79.65% was shown for XP Bond - 0.5mg/ml, XP Bond - 1.0mg/ml and Optibond XTR - 1.0mg/ml PAA-CuI after ageing for 18h, and 99.99% for both XP Bond - 0.5mg/ml and XP Bond - 1.0mg/ml PAA-CuI after ageing for 1 year. No significant variations in shear bond strength or cytotoxicity were detected between the experimental resins and their corresponding controls. CONCLUSIONS: PAA-CuI nanoparticles are an effective additive to adhesive blends as it renders them antibacterial without adversely affecting their bond strength or cytotoxicity. CLINICAL SIGNIFICANCE: The incorporation of PAA-coated copper iodide particles into adhesive resins renders the adhesive antibacterial to S. mutans for at least 1 year in vitro. This may prevent or delay bacterial invasion and the consequent development of caries lesions if the adhesive interface becomes defective.


Assuntos
Resinas Acrílicas/química , Antibacterianos/administração & dosagem , Cobre/administração & dosagem , Cimentos Dentários/química , Iodetos/administração & dosagem , Resinas Acrílicas/administração & dosagem , Antibacterianos/química , Biofilmes/efeitos dos fármacos , Linhagem Celular , Cobre/química , Colagem Dentária , Análise do Estresse Dentário , Humanos , Iodetos/química , Dente Molar , Nanopartículas/administração & dosagem , Nanopartículas/química , Streptococcus mutans/efeitos dos fármacos , Streptococcus mutans/fisiologia
10.
J Dent Educ ; 78(10): 1424-31, 2014 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-25281676

RESUMO

The aim of this study was to evaluate dental students' opinions regarding the utilization of a new grading software program for student self-assessment and a faculty-grading tool in a preclinical course. Using surface mapping technology, this program, called E4D Compare, yields a digital model of a student's preparation that is color-coded to show deficient areas. The program has now been used for two years at the James B. Edwards College of Dental Medicine at the Medical University of South Carolina, and the students previously assessed with E4D Compare have now entered into the dental clinics. For this study, students were asked to complete an anonymous survey for the investigators to evaluate students' attitudes and opinions on the effectiveness of this software in their preclinical courses to determine if this type of feedback helped them develop clinical skills. The survey also sought to collect students' opinions on the traditional objective criteria-based grading system. The survey was distributed to all members of the Classes of 2014 and 2015; it yielded a 59 percent response rate for the two classes, with a total of eighty-one students responding. Overall, the majority of students preferred the E4D Compare grading system over traditional hand-grading methods. The grading system provided instant, objective, and visual feedback that allowed students to easily see where their deficiencies were and encouraged them to work towards an ideal final product.


Assuntos
Atitude , Desenho Assistido por Computador , Avaliação Educacional/métodos , Tecnologia Educacional/métodos , Software , Estudantes de Odontologia/psicologia , Coroas , Facetas Dentárias , Educação em Odontologia , Docentes de Odontologia , Retroalimentação Sensorial , Humanos , Imageamento Tridimensional/métodos , Prostodontia/educação , Autoavaliação (Psicologia) , Tecnologia Odontológica/educação , Preparo Prostodôntico do Dente/métodos
11.
J Dent Educ ; 77(2): 168-75, 2013 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-23382526

RESUMO

The traditional method of evaluating student tooth preparations in preclinical courses has relied on the judgment of experienced clinicians primarily utilizing visual inspection. At times, certain aids such as reduction matrices or reduction instruments of known dimension are used to assist the evaluator in determining the grade. Despite the skill and experience of the evaluator, there is still a significant element of uncertainty and inconsistency in these methods. Students may perceive this inconsistency as a form of subjective, arbitrary, and empirical evaluation, which often results in students' focusing more on the grade than the actual learning or developing skills necessary to accomplish the preparation properly. Perceptions of favoritism, discrimination, and unfairness (whether verbalized or not) may interfere with the learning process. This study reports the use of a new experimental scanning and evaluation software program (E4D Compare) that can consistently and reliably scan a student's tooth preparation and compare it to a known (faculty-determined) standardized preparation. An actual numerical evaluation is generated by the E4D Compare software, thereby making subjective judgments by the faculty unnecessary. In this study, the computer-generated result was found to be more precise than the hand-graded method.


Assuntos
Educação em Odontologia , Avaliação Educacional/normas , Software , Preparo do Dente/normas , Coroas , Método Duplo-Cego , Tecnologia Educacional/métodos , Docentes de Odontologia , Humanos , Processamento de Imagem Assistida por Computador/métodos , Prostodontia/educação , Interface Usuário-Computador
12.
J Prosthet Dent ; 108(5): 310-5, 2012 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-23107239

RESUMO

STATEMENT OF PROBLEM: Confusion exists as to what constitutes an ideal ceramic crown preparation and whether certain deviations from the ideal can affect the marginal fit of the milled restoration. PURPOSE: This study evaluated the marginal gap of E4D crowns fabricated on preparations completed by clinicians with varying levels of expertise to identify whether common errors affect marginal fit. MATERIAL AND METHODS: The fit of 75 crowns fabricated with the E4D system on preparations of varying quality were examined for marginal fit by using the replica technique. These same preparations were then visually examined for common criteria for ceramic restorations and placed in one of 3 categories: excellent, fair, or poor. These visual examinations sought the presence of common preparation errors, particularly those involving the finish line. The average marginal gap values and standard deviations were calculated for each category, and the Kruskal-Wallis test was used to determine significance. RESULTS: The results showed a statistically significant correlation between the marginal fit of a CAD/CAM fabricated crown and the quality of the preparation. The mean marginal gap of the crowns fabricated on ideal preparations was 38.5 µm, those considered fair had a mean marginal gap of 58.3 µm, while those categorized as poor averaged 90.1 µm. The fit differences among all 3 groups were statistically significant (P<.05). CONCLUSIONS: Within the limitations of this in vitro study, it can be concluded that preparation quality has a significant impact on marginal gap on crowns fabricated with a CAD/CAM system.


Assuntos
Desenho Assistido por Computador , Coroas , Adaptação Marginal Dentária , Porcelana Dentária , Planejamento de Prótese Dentária , Preparo Prostodôntico do Dente/métodos , Humanos , Técnicas de Réplica , Estatísticas não Paramétricas
13.
Anal Chem ; 84(10): 4544-51, 2012 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-22524203

RESUMO

Collision-induced dissociation Fourier Transform ion cyclotron resonance mass spectrometry (CID-FTICR MS) was developed to determine structural building blocks in heavy petroleum systems. Model compounds with both single core and multicore configurations were synthesized to study the fragmentation pattern and response factors in the CID reactions. Dealkylation is found to be the most prevalent reaction pathway in the CID. Single core molecules exhibit primarily molecular weight reduction with no change in the total unsaturation of the molecule (or Z-number as in chemical formula C(c)H(2c+Z)N(n)S(s)O(o)VNi). On the other hand, molecules containing more than one aromatic core will decompose into the constituting single cores and consequently exhibit both molecular weight reduction and change in Z-numbers. Biaryl linkage, C(1) linkage, and aromatic sulfide linkage cannot be broken down by CID with lab collision energy up to 50 eV while C(2)+ alkyl linkages can be easily broken. Naphthenic ring-openings were observed in CID, leading to formation of olefinic structures. Heavy petroleum systems, such as vacuum resid (VR) fractions, were characterized by the CID technology. Both single-core and multicore structures were found in VR. The latter is more prevalent in higher aromatic ring classes.

14.
Anal Chem ; 82(1): 413-9, 2010 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-19994859

RESUMO

We report here the first high resolution mass spectrometric evidence of nickel porphyrins in petroleum. A petroleum asphaltene sample is fractionated by a silica-gel cyclograph. Nickel content is enriched by approximately 3 fold in one of the cyclograph fractions. The fraction is subsequently analyzed by atmospheric pressure photoionization (APPI) Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) with an average mass resolving power of over 500 K (M/DeltaM(fwhm)). Similar to vanadyl porphyrins, monocylcoalkano-type (presumed to be deocophylerythro-etioporphyrin DPEP) Ni porphyrins are found to be the most abundant family followed by etio, bicycloalkano-type, and rhodo-monocylcoalkano-type Ni porphyrins. A Z number ranging from -28 to -44 and a carbon number ranging from 26 to 41 were observed. A significant amount of nickel and vanadyl geoporphyrins are in more condensed tetrapyrrolic cores than just chlorophyll-derived DPEP- and etioporphyrins. Ni has a higher etio/DPEP ratio and rhodo-etio/rhodo-DPEP ratio than does VO.

15.
Rapid Commun Mass Spectrom ; 22(14): 2153-60, 2008 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-18536070

RESUMO

Vanadyl (VO) porphyrins and sulfur-containing vanadyl (VOS) porphyrins of a wide carbon number range (C(26) to C(52)) and Z-number range (-28 to -54) were detected and identified in a petroleum asphaltene by atmospheric pressure photonionization (APPI) and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). APPI provides soft ionization of asphaltene molecules (including VO and VOS porphyrins), generating primarily molecular ions (M(+.)). The ultra-high mass resolving power (m/Delta m(FWHM) approximately 500 K) of FTICR-MS enabled resolution and positive identification of elemental formulae for the entire family of VO and VOS porphyrins in a complicated asphaltene matrix. Deocophylerythro-etioporphyrin (DPEP) is found to be the most prevalent structure, followed by etioporphyrins (etio)- and rhodo (benzo)-DPEP. The characteristic Z-distribution of VO porphyrins suggests benzene and naphthene increment in the growth of porphyrin ring structures. Bimodal carbon number distributions of VO porphyrins suggest possible different origins of low and high molecular weight species. To our knowledge, the observation of VOS porphyrins in a petroleum product has not previously been reported. The work is also the first direct identification of the entire vanadyl porphyrin family by ultra-high resolution mass spectrometry without chromatographic separation or demetallation.

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