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INTRODUCTION: Enameloplasty of maxillary canines is often needed for aesthetic substitution in patients with congenitally missing lateral incisors. The exact enamel thicknesses for the various canine surfaces are unknown because previous studies failed to employ accurate measurement tools to report and compare detailed enamel thicknesses for each surface at various crown heights. METHODS: Thirty-two extracted maxillary canines were collected and scanned in a microcomputed tomography scanner. The scans were imported into a custom-written MATLAB software (version 9.2; MathWorks, Natick, Mass) and the enamel thickness on the mesial, distal, labial, fossa, cingulum, and incisal edge of each tooth was computed, obtaining the mean value from slices at 0.1 mm intervals. The overall mean enamel thickness for each surface was also calculated, and these values were compared using paired t tests. Incisal wear stage and incisal enamel thickness that was measured were compared using Spearman rank correlation coefficient. RESULTS: The mean enamel thickness was significantly thinner at the gingival level when compared with the incisal for all surfaces that were analyzed (1-tailed, P <0.001). The mean enamel coverage at the mesial was significantly thinner than the distal when measured gingival to the widest mesiodistal area. The mean enamel coverage of the cingulum was particularly thin and therefore requires extreme care in reshaping it. Incisal edge enamel thickness was highly negatively correlated with the wear stage of the scoring system that was used (1-tailed, P <0.001). CONCLUSIONS: The enamel coverage of the maxillary canine varies depending on the tooth surface and the incisogingival measurement location.
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Diente Canino , Estética Dental , Esmalte Dental , Humanos , Maxilar , Odontometría , Microtomografía por Rayos XRESUMEN
Complexation of Pu(iv) with the actinide extractant CyMe4-BTPhen (2,9-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin-3-yl)-1,10-phenanthroline) was followed by vis-NIR spectroscopy in acetonitrile solution. The solid-state structure of the crystallized product suggests that Pu(iv) is reduced to Pu(iii) upon complexation. Analysis by DFT modeling is consistent with metal-based rather than ligand-based reduction.
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Water soluble anionic and cationic bis-triazine ligands are able to suppress (mask) the extraction of corrosion and fission products such as Ni(II) and Pd(II) that are found in PUREX raffinates. Thus it is possible to separate these elements from the minor actinide Am(III). Although some masking agents have previously been developed that retard the extraction of Pd(II), this is the first time a masking agent has been developed for Ni(II).
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It has been shown that modification of the phenanthroline backbone of CyMe4-BTPhen leads to subtle electronic modulation, permitting differential ligation of Am(III) and Cm(III) resulting in separation factors up to 7.
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We report the first examples of hydrophilic 6,6'-bis(1,2,4-triazin-3-yl)-2,2'-bipyridine (BTBP) and 2,9-bis(1,2,4-triazin-3-yl)-1,10-phenanthroline (BTPhen) ligands, and their applications as actinide(iii) selective aqueous complexing agents. The combination of a hydrophobic diamide ligand in the organic phase and a hydrophilic tetrasulfonated bis-triazine ligand in the aqueous phase is able to separate Am(iii) from Eu(iii) by selective Am(iii) complex formation across a range of nitric acid concentrations with very high selectivities, and without the use of buffers. In contrast, disulfonated bis-triazine ligands are unable to separate Am(iii) from Eu(iii) in this system. The greater ability of the tetrasulfonated ligands to retain Am(iii) selectively in the aqueous phase than the corresponding disulfonated ligands appears to be due to the higher aqueous solubilities of the complexes of the tetrasulfonated ligands with Am(iii). The selectivities for Am(iii) complexation observed with hydrophilic tetrasulfonated bis-triazine ligands are in many cases far higher than those found with the polyaminocarboxylate ligands previously used as actinide-selective complexing agents, and are comparable to those found with the parent hydrophobic bis-triazine ligands. Thus we demonstrate a feasible alternative method to separate actinides from lanthanides than the widely studied approach of selective actinide extraction with hydrophobic bis-1,2,4-triazine ligands such as CyMe4-BTBP and CyMe4-BTPhen.
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It has been shown that CyMe4-BTPhen-functionalized silica-coated maghemite (γ-Fe2O3) magnetic nanoparticles (MNPs) are capable of quantitative separation of Am(III) from Eu(III) from HNO3 solutions. These MNPs also show a small but significant selectivity for Am(III) over Cm(III) with a separation factor of around 2 in 4 M HNO3. The water molecule in the cavity of the BTPhen may also play an important part in the selectivity.
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Neocuproine has been covalently bound to silica-coated maghemite (γ-Fe2O3) magnetic nanoparticles (MNPs) by a phenyl ether linkage. The resulting MNPs are able to remove Cu(II) from 12 ppm aqueous solution with an extraction efficiency of up to 99% at pH 2.
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Effects of bromine substitution at the 5 and 5,6-positions of the 1,10-phenanthroline nucleus of BTPhen ligand on their extraction properties for Ln(III) and An(III) cations have been studied. Compared to C5-BTPhen, electronic modulation in BrC5-BTPhen and Br2C5-BTPhen enabled these ligands to be fine-tuned in order to enhance the separation selectivity of Am(III) from Eu(III).
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Neisseria meningitidis is a commensal of humans that can colonize the nasopharyngeal epithelium for weeks to months and occasionally invades to cause life-threatening septicemia and meningitis. Comparatively little is known about meningococcal gene expression during colonization beyond those first few hours. In this study, the transcriptome of adherent serogroup B N. meningitidis strain MC58 was determined at intervals during prolonged cocultivation with confluent monolayers of the human respiratory epithelial cell line 16HBE14. At different time points up to 21 days, 7 to 14% of the meningococcal genome was found to be differentially regulated. The transcriptome of adherent meningococci obtained after 4 h of coculture was markedly different from that obtained after prolonged cocultivation (24 h, 96 h, and 21 days). Genes persistently upregulated during prolonged cocultivation included three genes (hfq, misR/phoP, and lrp) encoding global regulatory proteins. Many genes encoding known adhesins involved in epithelial adherence were upregulated, including those of a novel locus (spanning NMB0342 to NMB0348 [NMB0342-NMB0348]) encoding epithelial cell-adhesive function. Sixteen genes (including porA, porB, rmpM, and fbpA) encoding proteins previously identified by their immunoreactivity to sera from individuals colonized long term with serogroup B meningococci were also upregulated during prolonged cocultivation, indicating that our system models growth conditions in vivo during the commensal state. Surface-expressed proteins downregulated in the nasopharynx (and thus less subject to selection pressure) but upregulated in the bloodstream (and thus vulnerable to antibody-mediated bactericidal activity) should be interesting candidate vaccine antigens, and in this study, three new proteins fulfilling these criteria have been identified: NMB0497, NMB0866, and NMB1882.
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Células Epiteliales/microbiología , Neisseria meningitidis/crecimiento & desarrollo , Neisseria meningitidis/genética , Transcriptoma , Adhesión Bacteriana , Línea Celular , Genes Bacterianos , Humanos , Estudios Longitudinales , Neisseria meningitidis/fisiología , Factores de Tiempo , Factores de Virulencia/biosíntesisRESUMEN
Two members of the tetradentate N-donor ligand families 6,6'-bis(1,2,4-triazin-3-yl)-2,2'-bipyridine (BTBP) and 2,9-bis(1,2,4-triazin-3-yl)-1,10-phenanthroline (BTPhen) currently being developed for separating actinides from lanthanides have been studied. It has been confirmed that CyMe4-BTPhen 2 has faster complexation kinetics than CyMe4-BTBP 1. The values for the HOMO-LUMO gap of 2 are comparable with those of CyMe4-BTBP 1 for which the HOMO-LUMO gap was previously calculated to be 2.13 eV. The displacement of BTBP from its bis-lanthanum(III) complex by BTPhen was observed by NMR, and constitutes the only direct evidence for the greater thermodynamic stability of the complexes of BTPhen. NMR competition experiments suggest the following order of bis-complex stability: 1:2 bis-BTPhen complex ≥ heteroleptic BTBP/BTPhen 1:2 bis-complex > 1:2 bis-BTBP complex. Kinetics studies on some bis-triazine N-donor ligands using the stopped-flow technique showed a clear relationship between the rates of metal ion complexation and the degree to which the ligand is preorganized for metal binding. The BTBPs must overcome a significant (ca. 12 kcal mol(-1)) energy barrier to rotation about the central biaryl C-C axis in order to achieve the cis-cis conformation that is required to form a complex, whereas the cis-cis conformation is fixed in the BTPhens. Complexation thermodynamics and kinetics studies in acetonitrile show subtle differences between the thermodynamic stabilities of the complexes formed, with similar stability constants being found for both ligands. The first crystal structure of a 1:1 complex of CyMe4-BTPhen 2 with Y(NO3)3 is also reported. The metal ion is 10-coordinate being bonded to the tetradentate ligand 2 and three bidentate nitrate ions. The tetradentate ligand is nearly planar with angles between consecutive rings of 16.4(2)°, 6.4(2)°, 9.7(2)°, respectively.
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The removal of the most long-lived radiotoxic elements from used nuclear fuel, minor actinides, is foreseen as an essential step toward increasing the public acceptance of nuclear energy as a key component of a low-carbon energy future. Once removed from the remaining used fuel, these elements can be used as fuel in their own right in fast reactors or converted into shorter-lived or stable elements by transmutation prior to geological disposal. The SANEX process is proposed to carry out this selective separation by solvent extraction. Recent efforts to develop reagents capable of separating the radioactive minor actinides from lanthanides as part of a future strategy for the management and reprocessing of used nuclear fuel are reviewed. The current strategies for the reprocessing of PUREX raffinate are summarized, and some guiding principles for the design of actinide-selective reagents are defined. The development and testing of different classes of solvent extraction reagent are then summarized, covering some of the earliest ligand designs right through to the current reagents of choice, bis(1,2,4-triazine) ligands. Finally, we summarize research aimed at developing a fundamental understanding of the underlying reasons for the excellent extraction capabilities and high actinide/lanthanide selectivities shown by this class of ligands and our recent efforts to immobilize these reagents onto solid phases.
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The quadridentate N-heterocyclic ligand 6-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin-3-yl)-2,2' : 6',2''-terpyridine (CyMe(4)-hemi-BTBP) has been synthesized and its interactions with Am(III), U(VI), Ln(III) and some transition metal cations have been evaluated by X-ray crystallographic analysis, Am(III)/Eu(III) solvent extraction experiments, UV absorption spectrophotometry, NMR studies and ESI-MS. Structures of 1:1 complexes with Eu(III), Ce(III) and the linear uranyl (UO(2)(2+)) ion were obtained by X-ray crystallographic analysis, and they showed similar coordination behavior to related BTBP complexes. In methanol, the stability constants of the Ln(III) complexes are slightly lower than those of the analogous quadridentate bis-triazine BTBP ligands, while the stability constant for the Yb(III) complex is higher. (1)H NMR titrations and ESI-MS with lanthanide nitrates showed that the ligand forms only 1:1 complexes with Eu(III), Ce(III) and Yb(III), while both 1:1 and 1:2 complexes were formed with La(III) and Y(III) in acetonitrile. A mixture of isomeric chiral 2:2 helical complexes was formed with Cu(I), with a slight preference (1.4:1) for a single directional isomer. In contrast, a 1:1 complex was observed with the larger Ag(I) ion. The ligand was unable to extract Am(III) or Eu(III) from nitric acid solutions into 1-octanol, except in the presence of a synergist at low acidity. The results show that the presence of two outer 1,2,4-triazine rings is required for the efficient extraction and separation of An(III) from Ln(III) by quadridentate N-donor ligands.
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An emergent clone of Haemophilus influenzae biogroup aegyptius (Hae) is responsible for outbreaks of Brazilian purpuric fever (BPF). First recorded in Brazil in 1984, the so-called BPF clone of Hae caused a fulminant disease that started with conjunctivitis but developed into septicemic shock; mortality rates were as high as 70%. To identify virulence determinants, we conducted a pan-genomic analysis. Sequencing of the genomes of the BPF clone strain F3031 and a noninvasive conjunctivitis strain, F3047, and comparison of these sequences with 5 other complete H. influenzae genomes showed that >77% of the F3031 genome is shared among all H. influenzae strains. Delineation of the Hae accessory genome enabled characterization of 163 predicted protein-coding genes; identified differences in established autotransporter adhesins; and revealed a suite of novel adhesins unique to Hae, including novel trimeric autotransporter adhesins and 4 new fimbrial operons. These novel adhesins might play a critical role in host-pathogen interactions.
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Infecciones por Haemophilus/microbiología , Haemophilus influenzae/genética , Haemophilus influenzae/patogenicidad , Adhesinas Bacterianas/genética , Orden Génico , Genoma Bacteriano , Haemophilus influenzae/clasificación , Interacciones Huésped-Patógeno , Humanos , Anotación de Secuencia Molecular , Datos de Secuencia Molecular , Operón , Filogenia , Homología de Secuencia , Virulencia , Factores de Virulencia/genéticaRESUMEN
BACKGROUND AND OBJECTIVES: Public concern about an unsubstantiated link between MMR vaccine and autism stemmed from a 1998 paper by Dr Andrew Wakefield and colleagues, and the substantial media coverage which that work attracted. Though the Wakefield paper is now discredited and an MMR-autism link has never been demonstrated empirically, this concern has manifested in over a decade of suboptimal MMR uptake. Few qualitative studies have explored parents' MMR decision-making since uptake began to improve in 2004. This study updates and adds methodological rigour to the evidence base. METHODS: 24 mothers planning to accept, postpone or decline the first MMR dose (MMR1) for their 11-36 month-old children, described their decision-making in semi-structured interviews. Mothers were recruited via General Practice, parents' groups/online forums, and chain referral. MMR1 status was obtained from General Practice records 6 months post-interview. Interview transcripts were coded and interpreted using a modified Grounded Theory approach. RESULTS: Five themes were identified: MMR vaccine and controversy; Social and personal consequences of MMR decision; Health professionals and policy; Severity and prevalence of measles, mumps and rubella infections; Information about MMR and alternatives. Results indicated that MMR1 acceptors were sympathetic toward Wakefield as a person, but universally rejected his study which sparked the controversy; parents opting for single vaccines expressed the sense that immune overload is not a consideration but that not all three components of MMR are warranted by disease severity; and MMR1 rejectors openly criticised other parents' MMR decisions and decision-making. CONCLUSIONS: This study corroborated some previous qualitative work but indicated that the shrinking group of parents now rejecting MMR comprises mainly those with more extreme and complex anti-immunisation views, whilst parents opting for single vaccines may use second-hand information about the controversy. In response, policymakers and practitioners should revise their expectations of today's MMR decision-makers, and their methods for supporting them.
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Toma de Decisiones , Conocimientos, Actitudes y Práctica en Salud , Vacuna contra el Sarampión-Parotiditis-Rubéola/administración & dosificación , Aceptación de la Atención de Salud , Vacunación/psicología , Adulto , Trastorno Autístico/epidemiología , Humanos , Madres/psicología , Reino UnidoRESUMEN
The synthesis, lanthanide complexation, and solvent extraction of actinide(III) and lanthanide(III) radiotracers from nitric acid solutions by a phenanthroline-derived quadridentate bis-triazine ligand are described. The ligand separates Am(III) and Cm(III) from the lanthanides with remarkably high efficiency, high selectivity, and fast extraction kinetics compared to its 2,2'-bipyridine counterpart. Structures of the 1:2 bis-complexes of the ligand with Eu(III) and Yb(III) were elucidated by X-ray crystallography and force field calculations, respectively. The Eu(III) bis-complex is the first 1:2 bis-complex of a quadridentate bis-triazine ligand to be characterized by crystallography. The faster rates of extraction were verified by kinetics measurements using the rotating membrane cell technique in several diluents. The improved kinetics of metal ion extraction are related to the higher surface activity of the ligand at the phase interface. The improvement in the ligand's properties on replacing the bipyridine unit with a phenanthroline unit far exceeds what was anticipated based on ligand design alone.
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BACKGROUND AND OBJECTIVE: Parents' attitudes toward MMR vaccine and measles, mumps and rubella infections relate to their child's MMR status, therefore improving these attitudes is central to improving current suboptimal MMR uptake. However, no study has yet combined evidence-based, comprehensive and psychometrically validated assessment of these attitudes with reliable objective MMR status data, in order to identify through multivariate analyses the strongest attitudinal predictors of MMR uptake for interventions to target. The present study fills this lacuna by developing and testing a robust evidence-based MMR attitudes measurement instrument. DESIGN: Cross-sectional self-administered postal/telephone questionnaire with objective behavioural outcome. SETTING AND PARTICIPANTS: 535 parents of children aged 5-18 in London and north-west England, UK (response rate 18.1%). Recruitment via Primary Care Trust records, age-stratified purposive sample with suboptimally immunised cases oversampled. MAIN OUTCOME MEASURES: Parents' responses to evidence-based measurement instrument comprising 20 attitude/previous behaviour items (collapsing to 5 scales) and 7 demographic items, and their children's PCT-recorded 5th birthday status for MMR dose 1 (on-time, late or none) and MMR dose 2 (on-time or none). RESULTS: The attitudes measurement instrument was psychometrically robust: content valid, and demonstrating good or acceptable internal consistency (Cronbach's alpha=0.55-0.75 for all scales), test-retest reliability (Pearson's correlation >0.60-0.80, p<0.01 to <0.001 for all scales and 11 individual items), concurrent/construct validity (t-tests for difference between MMR status groups p<0.05 for four scales and thirteen individual items), and predictive/criterion validity (OR=0.66, 95% confidence interval=0.48-0.92 to OR=1.97, 95% CI=1.18-3.31 for three scales and five individual items). Black and minority ethnicity (OR=1.94, 95% CI=1.15-3.30 to OR=4.15, 95% CI=2.40-7.19), positive MMR attitudes (OR=1.63, 95% CI=1.00-2.66 to OR=1.97, 95% CI=1.18-1.31), and positive social attitudes (OR=1.64, 95% CI=1.23-2.40 to OR=1.72, 95% CI=1.13-2.38) independently predicted uptake for both MMR doses. MMR status groups differed most strongly on preference for single measles, mumps and rubella vaccines (6-9% variance in status explained), previous MMR acceptance/rejection (5-9%), and wishing to protect others through vaccinating one's own child (6-8%). CONCLUSIONS: The measurement instrument is robust on multiple validity and reliability dimensions, and is appropriate for use in research and practice as a tool for designing and evaluating interventions. Parents appear to act in line with their attitudes toward MMR vaccine, though attitudes toward measles infection bore little relation to MMR uptake. This study indicates populations and attitudes to be prioritized in MMR uptake improvement interventions.
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Conocimientos, Actitudes y Práctica en Salud , Vacuna contra el Sarampión-Parotiditis-Rubéola/administración & dosificación , Padres/psicología , Aceptación de la Atención de Salud/estadística & datos numéricos , Encuestas y Cuestionarios , Vacunación/psicología , Adolescente , Adulto , Niño , Preescolar , Estudios Transversales , Demografía , Inglaterra , Medicina Basada en la Evidencia , Humanos , Londres , Sarampión/prevención & control , Análisis Multivariante , Paperas/prevención & control , Aceptación de la Atención de Salud/psicología , Reproducibilidad de los Resultados , Rubéola (Sarampión Alemán)/prevención & control , Vacunación/estadística & datos numéricos , Adulto JovenRESUMEN
Suboptimal childhood vaccination uptake results in disease outbreaks, and in developed countries is largely attributable to parental choice. To inform evidence-based interventions, we conducted a systematic review of factors underlying parental vaccination decisions. Thirty-one studies were reviewed. Outcomes and methods are disparate, which limits synthesis; however parents are consistently shown to act in line with their attitudes to combination childhood vaccinations. Vaccine-declining parents believe that vaccines are unsafe and ineffective and that the diseases they are given to prevent are mild and uncommon; they mistrust their health professionals, Government and officially-endorsed vaccine research but trust media and non-official information sources and resent perceived pressure to risk their own child's safety for public health benefit. Interventions should focus on detailed decision mechanisms including disease-related anticipated regret and perception of anecdotal information as statistically representative. Self-reported vaccine uptake, retrospective attitude assessment and unrepresentative samples limit the reliability of reviewed data - methodological improvements are required in this area.
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Conducta de Elección , Toma de Decisiones , Padres/psicología , Vacunación/psicología , Preescolar , Países Desarrollados , Conocimientos, Actitudes y Práctica en Salud , Humanos , Vacuna contra el Sarampión-Parotiditis-Rubéola/administración & dosificación , Vacunas Combinadas/administración & dosificaciónRESUMEN
The new ligand 6,6''-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin-3-yl)-2,2':6',2''-terpyridine (CyMe4-BTTP) has been synthesized in 4 steps from 2,2':6',2''-terpyridine. Detailed NMR and mass spectrometry studies indicate that the ligand forms 1:2 complexes with lanthanide(III) perchlorates where the aliphatic rings are conformationally constrained whereas 1:1 complexes are formed with lanthanide(III) nitrates where the rings are conformationally mobile. An optimized structure of the 1:2 solution complex with Yb(III) was obtained from the relative magnitude of the induced paramagnetic shifts. X-Ray crystallographic structures of the ligand and of its 1:1 complex with Y(III) were also obtained. The NMR and mass spectra of [Pd(CyMe4-BTTP)]n(2n+) are consistent with a dinuclear double helical structure (n = 2). In the absence of a phase-modifier, CyMe4-BTTP in n-octanol showed a maximum distribution coefficient of Am(III) of 0.039 (±20%) and a maximum separation factor of Am(III) over Eu(III) of 12.0 from nitric acid. The metal(III) cations are extracted as the 1:1 complex from nitric acid. The generally low distribution coefficients observed compared with the BTBPs arise because the 1:1 complex of CyMe4-BTTP is considerably less hydrophobic than the 1:2 complexes formed by the BTBPs. In M(BTTP)(3+) complexes, there is a competition between the nitrate ions and the ligand for the complexation of the metal.
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2009 H1N1 influenza A ("swine flu") vaccine has been offered to healthy UK children aged 6 months-5 years since December 2009, though around 50% of parents plan to reject the vaccine. This study examined whether such parents exhibit omission bias (preference for errors arising from inaction over errors arising from action). One-hundred and forty-two parents completed an online questionnaire in which they rated (a) probability of occurrence, (b) symptoms and (c) duration of a hypothetical disease and a hypothetical vaccine adverse event (VAE). Almost all attributes were rated significantly less favourably when relating to VAE than to disease (p<0.01 for 17 of 22 outcomes), despite the attributes being objectively identical. These data suggest that any vaccine is at a disadvantage in many parents' consciousness in comparison with the infection itself, and that minor safety concerns could have disproportionately detrimental effects on vaccine uptake. Behavioural science offers strategies to ameliorate the impact of this bias and these should be explored further.