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1.
Clin Oral Investig ; 27(8): 4553-4566, 2023 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-37300738

RESUMO

OBJECTIVES: This study aimed to histologically evaluate the healing at 8 weeks after coronally advanced flap (CAF) with either a superficial (SCTG) or deep palatal connective tissue graft (DCTG), or a collagen matrix (CM) to cover recession defects at teeth and implants. MATERIAL AND METHODS: One mandibular side of 6 miniature pigs received each 3 titanium implants 12 weeks after extraction. Eight weeks later, recession defects were created around implants and contralateral premolars and 4 weeks later randomly subjected to CAF + SCTG, CAF + DCTG, or CAF + CM. After 8 weeks, block biopsies were histologically analyzed. RESULTS: For the primary outcome, i.e., keratinization of the epithelium, all teeth and implants exhibited a keratinized epithelium with no histological differences among them also not in terms of statistically significant differences in length (SCTG 0.86 ± 0.92 mm, DCTG 1.13 ± 0.62 mm, and Cm, 1.44 ± 0.76 mm). Pocket formation was histologically seen at all teeth, around most implants with SCTG and DCTG, however not in the CM implant group. The connective tissue grafts showed hardly signs of degradation, whereas the CM was partly degraded and integrated in connective tissue. The mean gain in gingival height was similar in all experimental groups (SCTG 3.89 ± 0.80 mm, DCTG 4.01 ± 1.40 mm, CM 4.21 ± 0.64 mm). Statistically significant differences were found in the height of the junctional epithelium between the control teeth and the connective tissue groups (p = 0.009 and 0.044). CONCLUSIONS: In this animal model, the use of either a superficial or deep connective tissue graft or a collagen membrane did not seem to have any impact on the epithelial keratinization around both teeth and implants. All procedures (CAF + SCTG/DCTG/CM) resulted in a long JE that was even longer at implants. CLINICAL RELEVANCE: Deep/superficial palatal connective tissue graft yielded similar keratinization around teeth/implants. Given the absence of pocket formation and inflammatory processes at implants when using a CM, CAF + CM might bear potential clinical benefits.


Assuntos
Retração Gengival , Animais , Suínos , Porco Miniatura , Retração Gengival/cirurgia , Colágeno , Tecido Conjuntivo/transplante , Gengiva/transplante , Resultado do Tratamento , Raiz Dentária/patologia
2.
Periodontol 2000 ; 88(1): 64-72, 2022 02.
Artigo em Inglês | MEDLINE | ID: mdl-35103317

RESUMO

Clinical considerations and treatment criteria in implant placement are constantly evolving. Prosthetically driven implant surgery has become the standard of care to improve short and long-term functional and esthetic outcomes. Therefore, implant position and angulation are planned according to the available bone, anatomical structures, and the requirements of the future prosthetic superstructure. In parallel with these developments, significant progress has been made in data imaging and different software technologies to allow the integration of data within a digital file format. Digitalization in implant surgery enables optimal planning of implant position, as well as the ability to transfer this planning to the surgical field-a process defined as "computer-supported implant planning and guided surgery." The aims of the present review are as follows: (a) to critically appraise the indications and potential "added value" of guided implant surgery, elaborating the main differences between dynamic and static guidance; and (b) to discuss the most important clinical considerations relevant for the different steps of the workflow that might influence the surgical outcome and to offer recommendations on how to avoid or reduce process errors in order to optimize treatment outcomes.


Assuntos
Implantes Dentários , Cirurgia Assistida por Computador , Desenho Assistido por Computador , Implantação Dentária Endóssea/métodos , Humanos , Cirurgia Assistida por Computador/métodos , Resultado do Tratamento , Fluxo de Trabalho
3.
Orv Hetil ; 159(11): 415-422, 2018 Mar.
Artigo em Húngaro | MEDLINE | ID: mdl-29526126

RESUMO

The aim of the present review is to provide an up-to-date picture of what we know about the connection between odontogenic foci and non-oral diseases. After a brief historical summary, we give an overview on how the odontogenic focus causes disease in distant areas of the body in general, and then we start the discussion of the particular conditions, such as cardiovascular diseases, pneumonia, diabetes mellitus, metabolic syndrome, rheumatoid arthritis and adverse pregnancy outcomes. The review is centered around the two main odontogenic foci: periodontitis and periapical periodontitis, the latter being a widely recognized but rarely discussed oral focus. Finally, we offer a few considerations that the practicing dentist may find useful when dealing with odontogenic foci. Orv Hetil. 2018; 159(11): 415-422.


Assuntos
Infecções/etiologia , Doenças Periodontais/complicações , Artrite Reumatoide/etiologia , Doenças Cardiovasculares/etiologia , Diabetes Mellitus/etiologia , Suscetibilidade a Doenças , Feminino , Humanos , Masculino , Síndrome Metabólica/etiologia , Pneumonia Bacteriana/etiologia , Gravidez , Complicações Infecciosas na Gravidez/etiologia , Fatores de Risco
4.
Artigo em Inglês | MEDLINE | ID: mdl-38727247

RESUMO

Background: Non-perforated Polytetrafluoroethylene (PTFE) membranes are effectively utilized in guided bone regeneration (GBR) but may hinder cell migration due to limited interaction with the periosteum. This study compared bone regeneration using occlusive or perforated membranes combined with acellular collagen sponge (ACS) and recombinant human bone morphogenic protein-2 (rhBMP-2) in a canine mandibular model. Material and Methods: Male beagle dogs (n=3) received two mandibular defects each to compare ACS/rhBMP-2 with experimental (perforated group) and control (non-perforated group) membranes (n=3 defects/group). Tissue healing was assessed histomorphologically, histomorphometrically and through volumetric reconstruction using microcomputed tomography. Results: The perforated group showed increased bone formation and reduced soft tissue formation compared to the non-perforated group. For the primary outcome, histomorphometric analysis revealed significantly greater total regenerated bone in the perforated group (67.08 ± 6.86%) relative to the nonperforated group (25.18 ± 22.44%) (p = 0.036). Perforated membranes had less soft tissue infiltration (32.91 ± 6.86%) compared to non-perforated membranes (74.82 ± 22.44%) (p = 0.036). Conclusion: The increased permeability of membranes in the perforated group potentially enabled periosteal precursor cells greater accessibility to rhBMP-2. The availability may have accelerated their differentiation into mature bone-forming cells, contributing to the stimulation of new bone production, relative to the non-perforated group.

5.
Inorg Chem ; 52(3): 1559-69, 2013 Feb 04.
Artigo em Inglês | MEDLINE | ID: mdl-23320898

RESUMO

Six dichloroiron(III) complexes of 1,3-bis(2'-arylimino)isoindoline (BAIH) with various N-donor aryl groups have been characterized by spectroscopy (infrared, UV-vis), electrochemistry (cyclic voltammetry), microanalysis, and in two cases X-ray crystallography. The structurally characterized Fe(III)Cl(2)(L(n)) complexes (n = 3, L(3) = 1,3-bis(2'-thiazolylimino)isoindoline and n = 5, L(5) = 1,3-bis(4-methyl-2'-piridylimino)isoindoline) are five-coordinate, trigonal bipyramidal with the isoindoline ligands occupying the two axial and one equatorial positions meridionally. These compounds served as precursors for catechol dioxygenase models that were formed in solution upon addition of 3,5-di-tert-butylcatechol (H(2)DBC) and excess triethylamine. These adducts react with dioxygen in N,N-dimethylformamide, and the analysis of the products by chromatography and mass spectrometry showed high intradiol over extradiol selectivity (the intradiol/extradiol product ratios varied between 46.5 and 6.5). Kinetic measurements were performed by following the change in the intensity of the catecholate to iron ligand-to-metal charge transfer (LMCT) band, the energy of which is influenced by the isoindolinate-ligand (827-960 nm). In combination with electrochemical investigations the kinetic studies revealed an inverse trend between reaction rates and oxidation potentials associated with the coordinated DBC(2-). On the basis of these results, a substrate activation mechanism is suggested for this system in which the geometry of the peroxide-bridged intermediate may be of key importance in regioselectivity.


Assuntos
Catecol 1,2-Dioxigenase/química , Compostos Férricos/química , Catecol 1,2-Dioxigenase/metabolismo , Cristalografia por Raios X , Compostos Férricos/síntese química , Isoindóis/química , Ligantes , Modelos Moleculares , Estrutura Molecular
6.
Diagnostics (Basel) ; 12(1)2022 Jan 17.
Artigo em Inglês | MEDLINE | ID: mdl-35054390

RESUMO

The aim of this study was to assess the reliability of the artificial intelligence (AI) automatic evaluation of panoramic radiographs (PRs). Thirty PRs, covering at least six teeth with the possibility of assessing the marginal and apical periodontium, were uploaded to the Diagnocat (LLC Diagnocat, Moscow, Russia) account, and the radiologic report of each was generated as the basis of automatic evaluation. The same PRs were manually evaluated by three independent evaluators with 12, 15, and 28 years of experience in dentistry, respectively. The data were collected in such a way as to allow statistical analysis with SPSS Statistics software (IBM, Armonk, NY, USA). A total of 90 reports were created for 30 PRs. The AI protocol showed very high specificity (above 0.9) in all assessments compared to ground truth except from periodontal bone loss. Statistical analysis showed a high interclass correlation coefficient (ICC > 0.75) for all interevaluator assessments, proving the good credibility of the ground truth and the reproducibility of the reports. Unacceptable reliability was obtained for caries assessment (ICC = 0.681) and periapical lesions assessment (ICC = 0.619). The tested AI system can be helpful as an initial evaluation of screening PRs, giving appropriate credibility reports and suggesting additional diagnostic methods for more accurate evaluation if needed.

7.
Org Biomol Chem ; 9(19): 6559-65, 2011 Oct 07.
Artigo em Inglês | MEDLINE | ID: mdl-21808806

RESUMO

The palladium-catalyzed Suzuki-Miyaura cross-coupling reactions of halo derivatives of 4H-pyrido[1,2-a]pyrimidin-4-one with (het)arylboronic acids allow easy access to (het)aryl and vinyl derivatives of this bicycle in good to excellent yields, even from chloro derivatives. The sequence of reactivity of the halogen in the different positions of the ring system was also investigated. 6-Phenyl-4H-pyrido[1,2-a]pyrimidin-4-one could be prepared by thermal cyclization of isopropylidene (6-phenylpyrid-2-ylamino)methylenemalonate, together with a small amount of 7-phenyl-1,4-dihydro-1,8-naphthyridin-4-one.


Assuntos
Pirimidinonas/síntese química , Catálise , Cristalografia por Raios X , Modelos Moleculares , Estrutura Molecular , Paládio/química , Pirimidinonas/química , Teoria Quântica , Estereoisomerismo
8.
Magn Reson Chem ; 49(12): 801-11, 2011 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-22102509

RESUMO

In this paper, we report on the use and limitations of the popular double-quantum recoupling sequence back-to-back in studies of (31)P-(31)P spatial proximities in Pd-phosphine complexes at medium field (9.38 T) under the conditions of fast MAS. The effects of internuclear distances in different spin systems and the impact of isotropic chemical shift and chemical shift anisotropy (CSA) offsets on the detectibility of SQ-DQ correlations were of particular interest to us. Selected model compounds with these requirements in mind were synthesized. By optimization of the excitation times of SQ-DQ correlations up to 4.6 Å could be obtained even in four-spin systems; however, certain long-range correlations may be weak or missing. Although under fast MAS, CSA values up to 270 ppm are well tolerated, in multi-spin systems in cases of isotropic chemical shift offsets larger than 50 ppm, the DQ coherences cannot be properly excited.

9.
Artigo em Inglês | MEDLINE | ID: mdl-33805172

RESUMO

Facial soft tissue esthetics is a priority in orthodontic treatment, and emerging of the digital technologies can offer new methods to help the orthodontist toward an esthetic outcome. This prospective study aimed to assess the soft tissue changes of the face after six months of retention following Rapid Maxillary Expansion (RME). The sample consisted of 25 patients (13 females, 12 males, mean age: 11.6 years) who presented with unilateral or bilateral posterior crossbite requiring RME, which was performed with a Hyrax expander. 3D facial images were obtained before treatment (T0) and at the end of a six-month retention period after the treatment (T1) using a structured-light 3D handheld scanner. Linear and angular measurements were performed and 3D deviation analyses were done for six morphological regions of the face. Significant changes in various areas of the nasal and the upper lip regions were observed. Based on the results of the study and within the limitations of the study, RME with a Hyrax expander results in significant morphological changes of the face after a six-month retention period.


Assuntos
Má Oclusão , Técnica de Expansão Palatina , Criança , Face/diagnóstico por imagem , Feminino , Humanos , Masculino , Má Oclusão/diagnóstico por imagem , Má Oclusão/terapia , Nariz , Estudos Prospectivos
10.
Artigo em Inglês | MEDLINE | ID: mdl-34444300

RESUMO

The objective of this study was to explore dental students' facial profile preferences in a large sample of students. Nine hundred and nineteen dental students of four dental schools were involved. As part of a larger study on dentofacial esthetics, six photo series consisting of one unaltered and four altered variants of the same female profile were distributed among the students. The altered features were ones that are esthetically significant according to the literature. The students had to indicate the photo in each series that they preferred. The data were analyzed in a regression model in which preference in the given photo series was the dependent variable and gender, grade of studies, and dental school were the factors. Eight hundred and sixty-one students (93.7%) responded. Gender and dental school were not associated with the observed preferences, but the grade of studies was associated for three of the modified parameters: chin prominence, the sagittal position of the maxillary dental arch, and the simultaneous modification of the prominence of the chin and the nose. This study has confirmed several earlier observations, and new observations have also been made. We have demonstrated that the anteroposterior position of the maxillary incisors may be an important determinant of profile esthetics, even if this position does not influence the situation of the soft tissues and if the forehead cannot be used as a reference. We have also shown that the harmony between the nose and the chin overrides the importance of their individual dimensions.


Assuntos
Estética Dentária , Estudantes de Odontologia , Queixo , Estudos Transversais , Face , Feminino , Humanos
11.
Chemistry ; 15(40): 10620-33, 2009 Oct 12.
Artigo em Inglês | MEDLINE | ID: mdl-19746472

RESUMO

The coordination properties of N,N'-bis[4-(4-pyridyl)phenyl]acenaphthenequinonediimine (L(1)) and N,N'-bis[4-(2-pyridyl)phenyl]acenaphthenequinonediimine (L(2)) were investigated in self-assembly with palladium diphosphane complexes [Pd(P;P)(H(2)O)(2)](OTf)(2) (OTf = triflate) by using various analytical techniques, including multinuclear ((1)H, (15)N, and (31)P) NMR spectroscopy and mass spectrometry (P;P = dppp, dppf, dppe; dppp = bis(diphenylphosphanyl)propane, dppf = bis(diphenylphosphanyl)ferrocene, and dppe = bis(diphenylphosphanyl)ethane). Beside the expected trimeric and tetrameric species, the interaction of an equimolar mixture of [Pd(dppp)](2+) ions and L(1) also generates pentameric aggregates. Due to the E/Z isomerism of L(1), a dimeric product was also observed. In all of these species, which correspond to the general formula [Pd(dppp)L(1)](n)(OTf)(2n) (n = 2-5), the L(1) ligand is coordinated to the Pd center only through the terminal pyridyl groups. Introduction of a second equivalent of the [Pd(dppp)](2+) tecton results in coordination to the internal, sterically more encumbered chelating site and induces enhancement of the higher nuclearity components. The presence of higher-order aggregates (n = 5, 6), which were unexpected for the interaction of cis-protected palladium corners with linear ditopic bridging ligands, has been demonstrated both by mass-spectrometric and DOSY NMR spectroscopic analysis. The sequential coordination of the [Pd(dppp)](2+) ion is attributed to the dissimilar steric properties of the two coordination sites. In the self-assembled species formed in a 1:1:1 mixture of [Pd(dppp)](2+)/[Pd(dppe)](2+)/L(1), the sterically more demanding [Pd(dppp)](2+) tectons are attached selectively to the pyridyl groups, whereas the more hindered imino nitrogen atoms coordinate the less bulky dppe complexes, thus resulting in a sterically directed, size-selective sorting of the metal tectons. The propensity of the new ligands to incorporate hydrogen-bonded solvent molecules at the chelating site was confirmed by X-ray diffraction studies.

12.
Chem Commun (Camb) ; (24): 3630-2, 2009 Jun 28.
Artigo em Inglês | MEDLINE | ID: mdl-19521631

RESUMO

Mononuclear iron(iii) flavonolate was synthesized as synthetic enzyme-substrate complex, and its direct and carboxylate-enhanced dioxygenation as biomimetic functional models with relevance to flavonol 2,4-dioxygenase are briefly described.


Assuntos
Materiais Biomiméticos/síntese química , Ácidos Carboxílicos/química , Dioxigenases/química , Ferro/química , Materiais Biomiméticos/química , Dioxigenases/metabolismo , Cinética , Modelos Moleculares , Estrutura Molecular , Espectrofotometria
13.
J Inorg Biochem ; 102(4): 773-80, 2008 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-18222003

RESUMO

The mononuclear [Mn(6'Me(2)indH)(H(2)O)(2)(CH(3)CN)](ClO(4))(2) (6'Me(2)indH: 1,3-bis(6'-methyl-2'-pyridylimino)isoindoline) complex has been prepared and characterized by various techniques such as elemental analysis, IR, UV-visible and ESR spectroscopy. The title compound was suitable as catalyst for the catalytic oxidation of 3,5-di-tert-butylcatechol (3,5-DTBCH(2)) to 3,5-di-tert-butyl-1,2-benzoquinone (3,5-DTBQ) (catecholase activity), and o-aminophenol (OAPH) to 2-aminophenoxazine-3-one (APX) (phenoxazinone synthase activity) with dioxygen at ambient condition in good yields. Kinetic measurements revealed first-order dependence on the catalyst and dioxygen concentration and saturation type behavior with respect to the corresponding substrate. It was also found that the added triethylamine in both systems accelerates the reaction.


Assuntos
Catecol Oxidase/metabolismo , Isoindóis/farmacologia , Manganês/química , Oxirredutases/metabolismo , Espectroscopia de Ressonância de Spin Eletrônica , Isoindóis/química , Cinética , Modelos Moleculares , Espectrofotometria Infravermelho , Espectrofotometria Ultravioleta
14.
Chem Commun (Camb) ; (8): 1004-5, 2004 Apr 21.
Artigo em Inglês | MEDLINE | ID: mdl-15069516

RESUMO

The reaction of 1H-2-phenyl-3-hydroxy-4-oxoquinoline (PhquinH(2); 1) with metallic copper leads to Cu(II)(PhquinH)(2) while in the presence of PPh(3) to Cu(I)(2)Cu(II)(Phquin)(2)(PPh(3))(4). In the presence of tmeda and O(2) ring cleavage occurs to give Cu(II)(tmeda)(PhquinH)(N-baa). Both reactions represent a mild N-H activation and an oxidative C-C bond scission.

15.
J Inorg Biochem ; 91(1): 190-8, 2002 Jul 25.
Artigo em Inglês | MEDLINE | ID: mdl-12121775

RESUMO

The preparation and characterization of dinuclear [M(II)(dbcat)(idpa)](2) (M[double bond]Zn (1), Cu (3); dbcat[double bond]3,5-di-tert-butylcatecholate; idpa[double bond]3,3'-iminobis(N,N-dimethylpropylamine)) complexes are described. Crystallographic characterization of the complex [Cu(II)(dbcat)(idpa)](2) has shown that the co-ordination geometry around copper(II) ions is distorted square pyramidal (triclinic, P-1, a=10.576(1) A, b=11.927(1) A, c=12.621(1) A, alpha=77.89(1) degrees, beta=88.65(1) degrees, gamma=70.21(1) degrees, V=1462.7(2) A(3), Z=2, R=0.0387). Both 1 and 3 were suitable catalysts for the catalytic oxidation of dbcatH(2) to dtbq (dtbq=3,5-di-tert-butyl-1,2-benzoquinone) with dioxygen at ambient conditions in good yields. However, on the basis of kinetic studies the copper- and zinc-catalyzed reactions showed different mechanisms. In the first case valence tautomerism [Cu(II)(dbcat)(idpa)]<==>[Cu(I)(dbsq)(idpa)] precedes the reaction with O(2), while with the zinc complex metal-bound catecholate reacts directly with O(2) with the formation of free superoxide anion.


Assuntos
Catecóis/química , Cobre/química , Oxirredutases/química , Zinco/química , Catecóis/metabolismo , Cristalografia por Raios X , Espectroscopia de Ressonância de Spin Eletrônica , Estrutura Molecular , Oxirredução , Oxirredutases/metabolismo , Soluções
16.
Angew Chem Int Ed Engl ; 38(10): 1442-1446, 1999 May 17.
Artigo em Inglês | MEDLINE | ID: mdl-29711589

RESUMO

The crystalline, spinless π dimer (1.+ ⋅PF6 )2 was obtained by the oxidation of bipyrrole 1 with ferrocenium hexafluorophosphate. The diamagnetic species generated electrochemically in solution was identified as the σ dimer by NMR spectroscopy.

18.
J Am Chem Soc ; 128(26): 8392-3, 2006 Jul 05.
Artigo em Inglês | MEDLINE | ID: mdl-16802792

RESUMO

Charge flipping (CF) is an amazingly simple structure solution method that uses single-crystal X-ray diffraction data. It is truly ab initio, no preliminary information on atom types, chemical composition, or space group symmetry is required. The algorithm is iterative and alternates between real and reciprocal spaces. Its simplest version only changes (flips) the sign of the electron density below a threshold, while in reciprocal space, it prescribes the moduli of observed structure factors. In this communication, we apply the algorithm in practice. The selected example presents a whole range of difficulties: it is large, contains only light atoms, is noncentrosymmetric, and shows a particularly awkward pseudosymmetry. To solve it with any of the traditional methods requires many hours of computer time, followed by a day of expert's handwork to find missing and to remove spurious atoms. In contrast, the CF algorithm provides the complete structure in a few seconds and without human intervention. It is also remarkable that the success rate is 100%, that is, any starting point in the high-dimensional phase space leads to the solution. The treatment of translational pseudosymmetry is obviously a favorable case. Similar resistant structures with pseudosymmetries or ambiguous space groups are the practical applications where the CF method could well complement standard software procedures.

19.
Inorg Chem ; 45(18): 7480-7, 2006 Sep 04.
Artigo em Inglês | MEDLINE | ID: mdl-16933952

RESUMO

The 6-coordinate dioximatomanganese(II) complex [Mn(HL)(CH3OH)]+ (2, where H2L is [HON=C(CH3)C(CH3)=NCH2CH2]2NH), formed by instant solvolysis of [Mn2(HL)2](BPh4)2 (1) in methanol, accelerates the triethylamine (TEA)-catalyzed oxidation of 3,5-di-tert-butylcatechol (H2dtbc) by O2 to the corresponding o-benzoquinone. Significantly, 2 alone has no catalytic effect. The observed rate increase can be explained by the interaction of 2 with the hydroperoxo intermediate HdtbcO2- formed from Hdtbc- and O2 in the TEA-catalyzed oxidation. The kinetics of the TEA-catalyzed and Mn-enhanced reaction has been studied by gas-volumetric monitoring of the amount of O2 consumed. The initial rate of O2 uptake (V(in)) shows a first-order dependence on the concentration of 2 and O2 and saturation kinetics with respect to both H2dtbc and TEA. The observed kinetic behavior is consistent with parallel TEA-catalyzed and Mn-enhanced oxidation paths. The 3,5-di-tert-butylsemiquinone anion radical is an intermediate detectable by electron spin resonance (ESR) spectroscopy. The dimeric catalyst precursor has been characterized by X-ray diffraction and electrospray ionization mass spectrometry and the monomeric catalyst by ESR spectroscopy.


Assuntos
Catecóis/química , Manganês/química , Compostos Organometálicos/química , Oxigênio/química , Benzoquinonas/síntese química , Benzoquinonas/química , Biomimética , Catálise , Cristalografia por Raios X , Cinética , Ligantes , Modelos Moleculares , Estrutura Molecular , Oxirredução
20.
Inorg Chem ; 44(18): 6415-24, 2005 Sep 05.
Artigo em Inglês | MEDLINE | ID: mdl-16124822

RESUMO

Electrospray ionization (ESI) quadrupole ion trap mass spectrometry (QIT-MS) and collisionally activated dissociation (CAD) were used to evaluate the rare-earth binding properties of two hydrophobic carbamoylmethylphosphine oxide (CMPO) ligands, the normal bidentate variety, (t-BuC6H4)2P(O)CH2C(O)N(i-Bu)2 (A), a new potentially tridentate extractant, (t-BuC6H4)2P(O)CH[CH2C(O)N(i-Bu)2]C(O)N(i-Bu)2 (B), and tributyl phosphate. The mass spectral results obtained from analysis of 1% HNO3/methanol solution containing the ligands and dissolved lanthanide salts reveal that the favorable stoichiometries of the ligand/metal/nitrate complexes are 2:1:2 for the bidentate ligand A, 1:1:2 for the tridentate ligand B, and 3:1:2 for the monodentate tributyl phosphate. These observed stoichiometries correlate with the number of available binding sites on each ligand as well as with potential steric effects. Energy-variable collisionally activated dissociation experiments showed that for the 2:1:2 complexes involving ligand A or B, as the ionic radius of the bound metal decreased, the removal of nitric acid required less energy and resulted in less extensive spontaneous solvent coordination. This experimental trend suggests that, as the ionic radius of the lanthanide ion decreases, a pair of the carbamoylmethylphosphine ligands is able to more completely solvate the bound metal ion thereby weakening the nitrate-metal interaction.

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