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1.
Surg Endosc ; 2019 Nov 19.
Artigo em Inglês | MEDLINE | ID: mdl-31745632

RESUMO

BACKGROUND: 3D vascular anatomy roadmaps are currently being implemented for surgical planning and navigation. Quality of the reconstruction is critical. The aim of this article is to compare anatomical completeness of models produced by manual and semi-automatic segmentation. METHODS: CT-datasets from patients included in an ongoing trial, underwent 3D vascular reconstruction applying two different segmentation methods. This produced manually-segmented models (MSMs) and semi-automatically segmented models (SAMs) which underwent a paired comparison. Datasets were delivered for reconstruction in 4 batches of 6, of which only batch 4 contained patients with abnormal anatomy. Model completeness was assessed quantitatively using alignment and distance error indexes and qualitatively with systematic inspection. MSMs were the gold standard. Assessed vessels were those of interest to the surgeon performing D3-right colectomy. RESULTS: 24 CT-datasets (13 females, age 44-77) were used in a paired comparative analysis of 48 3D-models. Quantitatively, SAMs showed structural improvement from Batch 1 to 3. Batch 4, with abnormal vessels, showed the highest error-index values. Qualitatively, 91.7% of SAMs did not contain all mesenteric branches relevant to the surgeon. In SAMs, 1 (12.5%) right colic artery-RCA scored as a complete vessel. 3 (37.5%) RCAs scored as incomplete and 4 (50%) RCAs were absent. 6 (25%) of 24 middle colic arteries-MCA scored as complete vessels. 11 (45.8%) scored as incomplete while 7 (29.2%) MCAs were absent. 13 (54.2%) of 24 ileocolic arteries-ICA were complete vessels. 11 (45.8%) scored as incomplete. None (0%) were absent. Additionally, it was observed that 10 (41.7%) of SAMs contained all their jejunal arteries, when compared to MSMs. Calibers of "complete" vessels were significantly higher than in "missing" vessels (MCA p < 0.001, RCA p = 0.016, ICA p < 0.001, JAs p < 0.001). CONCLUSION: Despite acceptable results from quantitative analysis, qualitative comparison indicates that semi-automatically generated 3D-models of the central mesenteric vasculature could cause considerable confusion at surgery.

2.
Surg Endosc ; 33(2): 567-575, 2019 02.
Artigo em Inglês | MEDLINE | ID: mdl-30014328

RESUMO

BACKGROUND: Three-dimensional (3D) printing technology has recently been well approved as an emerging technology in various fields of medical education and practice; e.g., there are numerous studies evaluating 3D printouts of solid organs. Complex surgery such as extended mesenterectomy imposes a need to analyze also the accuracy of 3D printouts of more mobile and complex structures like the diversity of vascular arborization within the central mesentery. The objective of this study was to evaluate the linear dimensional anatomy landmark differences of the superior mesenteric artery and vein between (1) 3D virtual models, (2) 3D printouts, and (3) peroperative measurements. METHODS: The study included 22 patients from the ongoing prospective multicenter trial "Safe Radical D3 Right Hemicolectomy for Cancer through Preoperative Biphasic MDCT Angiography," with preoperative CT and peroperative measurements. The patients were operated in Norway between January 2016 and 2017. Their CT datasets underwent 3D volume rendering and segmentation, and the virtual 3D model produced was then exported for stereolithography 3D printing. RESULTS: Four parameters were measured: distance between the origins of the ileocolic and the middle colic artery, distance between the termination of the gastrocolic trunk and the ileocolic vein, and the calibers of the middle colic and ileocolic arteries. The inter-arterial distance has proven a strong correlation between all the three modalities implied (Pearson's coefficient 0.968, 0.956, 0.779, respectively), while inter-venous distances showed a weak correlation between peroperative measurements and both virtual and physical models. CONCLUSION: This study showed acceptable dimensional inter-arterial correlations between 3D printed models, 3D virtual models and authentic soft tissue anatomy of the central mesenteric vessels, and weaker inter-venous correlations between all the models, reflecting the highly variable nature of veins in situ.


Assuntos
Colectomia/métodos , Neoplasias do Colo/cirurgia , Artéria Mesentérica Superior/anatomia & histologia , Impressão Tridimensional , Adulto , Idoso , Idoso de 80 Anos ou mais , Pontos de Referência Anatômicos , Angiografia/métodos , Feminino , Humanos , Imageamento Tridimensional , Masculino , Artéria Mesentérica Superior/diagnóstico por imagem , Artéria Mesentérica Superior/cirurgia , Mesentério/diagnóstico por imagem , Mesentério/cirurgia , Pessoa de Meia-Idade , Tomografia Computadorizada Multidetectores , Sistema Porta/anatomia & histologia , Sistema Porta/diagnóstico por imagem , Estudos Prospectivos
3.
Dalton Trans ; 47(25): 8489-8490, 2018 06 25.
Artigo em Inglês | MEDLINE | ID: mdl-29901048

RESUMO

Correction for 'Magnetic properties of the seven-coordinated nanoporous framework material Co(bpy)1.5(NO3)2 (bpy = 4,4'-bipyridine)' by Elena Bartolomé et al., Dalton Trans., 2012, 41, 10382-10389.

4.
Chemistry ; 24(2): 388-399, 2018 Jan 09.
Artigo em Inglês | MEDLINE | ID: mdl-28858419

RESUMO

The characterization of the crystal structure, phase transitions, magnetic structure and dielectric properties has been carried out on [CH3 NH3 ][Co(COOH)3 ] (1) perovskite-like metal-organic compound through variable-temperature single-crystal and powder neutron and X-ray diffraction and relative permittivity measurements. The paraelectric to antiferroelectric-like phase transition observed at around 90 K is triggered by a structural phase transition; the structural studies show a change from Pnma space group at RT (1A) to P21 /n space group at low temperature (1B). This phase transition involves the occurrence of small distortions in the framework and counterions. Neutron diffraction studies have shown a magnetic order showing spontaneous magnetization below 15 K, due to the occurrence of a non-collinear antiferromagnetic structure with a weak ferromagnetic component, mainly due to the single-ion anisotropy of the CoII ions.

5.
Dalton Trans ; 46(3): 720-732, 2017 Jan 17.
Artigo em Inglês | MEDLINE | ID: mdl-27990520

RESUMO

In this paper we present the characterization of a complex with the formula [Mn2Ca2(hmp)6(H2O)4(CH3CN)2](ClO4)4 (1), where hmp-H = 2-(hydroxymethyl)pyridine. Compound 1 crystallizes in the monoclinic space group C2/c with the cation lying on an inversion centre. Static magnetic susceptibility, magnetization and heat capacity measurements reflect a unique Mn(iii) valence state, and single-ion ligand field parameters with remarkable large rhombic distortion (D/kB = -6.4 K, E/kB = -2.1 K), in good agreement with the high-field electron paramagnetic resonance experiments. At low temperature Mn2Ca2 cluster behaves as a system of ferromagnetically coupled (J/kB = 1.1 K) Mn dimers with a ST = 4 and mT = ±4 ground state doublet. Frequency dependent ac susceptibility measurements reveal the slow magnetic relaxation characteristic of a single molecule magnet (SMM) below T = 4 K. At zero magnetic field, an Orbach-type spin relaxation process (τ ∼ 10-5 s) with an activation energy Ea = 5.6 K is observed, enabled by the large E/D rhombicity of the Mn(iii) ions. Upon the application of a magnetic field, a second, very slow process (τ ∼ 0.2 s) is observed, attributed to a direct relaxation mechanism with enhanced relaxation time owing to the phonon bottleneck effect.

6.
Chemistry ; 21(34): 12171-80, 2015 Aug 17.
Artigo em Inglês | MEDLINE | ID: mdl-26178233

RESUMO

Compounds [Fe3 Ln(tea)2 (dpm)6 ] (Fe3 Ln; Ln= Tb-Yb, H3 tea=triethanolamine, Hdpm=dipivaloylmethane) were synthesized as lanthanide(III)-centered variants of tetrairon(III) single-molecule magnets (Fe4 ) and isolated in crystalline form. Compounds with Ln=Tb-Tm are isomorphous and show crystallographic threefold symmetry. The coordination environment of the rare earth, given by two tea(3-) ligands, can be described as a bicapped distorted trigonal prism with D3 symmetry. Magnetic measurements showed the presence of weak ferromagnetic Fe⋅⋅⋅Ln interactions for derivatives with Tb, Dy, Ho, and Er, and of weak antiferromagnetic or negligible coupling in complexes with Tm and Yb. Alternating current susceptibility measurements showed simple paramagnetic behavior down to 1.8 K and for frequencies reaching 10000 Hz, despite the easy-axis magnetic anisotropy found in Fe3 Dy, Fe3 Er, and Fe3 Tm by single-crystal angle-resolved magnetometry. Relativistic quantum chemistry calculations were performed on Fe3 Ln (Ln=Tb-Tm): the ground J multiplet of Ln(3+) ion is split by the crystal field to give a ground singlet state for Tb and Tm, and a doublet for Dy, Ho, and Er with a large admixture of mJ states. Gyromagnetic factors result in no predominance of gz component along the threefold axis, with comparable gx and gy values in all compounds. It follows that the environment provided by the tea(3-) ligands, though uniaxial, is unsuitable to promote slow magnetic relaxation in Fe3 Ln species.

7.
Beilstein J Nanotechnol ; 5: 2267-74, 2014.
Artigo em Inglês | MEDLINE | ID: mdl-25551055

RESUMO

Single-crystal angular-resolved magnetometry and wavefunction-based calculations have been used to reconsider the magnetic properties of a recently reported Dy(III)-based single-molecule magnet, namely [Dy(hfac)3(L(1))] with hfac(-) = 1,1,1,5,5,5-hexafluoroacetylacetonate and L(1) = 2-(4,5-bis(propylthio)-1,3-dithiol-2-ylidene)-6-(pyridin-2-yl)-5H-[1,3]dithiolo[4',5':4,5]benzo[1,2-d]imidazole. The magnetic susceptibility and magnetization at low temperature are found to be strongly influenced by supramolecular interactions. Moreover, taking into account the hydrogen-bond networks in the calculations allows to explain the orientation of the magnetic axes. This strongly suggests that hydrogen bonds play an important role in the modulation of the electrostatic environment around the Dy(III) center that governs the nature of its magnetic ground-state and the orientation of its anisotropy axes. We thus show here that SMM properties that rely on supramolecular organization may not be transferable into single-molecule devices.

8.
Dalton Trans ; 42(28): 10153-71, 2013 Jul 28.
Artigo em Inglês | MEDLINE | ID: mdl-23719687

RESUMO

The synthesis and magnetostructural properties of a new low-dimensional magnetic system based on α-furoate ligands, {[Dy(α-C4H3OCOO)(µ-(α-C4H3OCOO))2(H2O)3]}n, abbreviated {Dy(α-fur)3}n, are reported. X-ray diffraction experiments results evidence the presence of two different Dy coordination environment types differing only in the position of one of the furoate ligands. The crystallographic structure is formed by polymeric chains along the c-axis, each composed of just one Dy type, coupled within the bc-plane with chains of the same Dy type. These planes, each of them containing only one Dy type, are randomly stacked along the a-axis. The magnetic behaviour was studied by magnetization, static and dynamic susceptibility, heat capacity measurements and ab initio simulations. The directions of the easy axes of magnetization, gyromagnetic values and energy level structures of the two Dy types were obtained from ab initio calculations. {Dy(α-fur)3}n exhibits slow magnetic relaxation dynamics below 10 K. The two Dy types with different coordination environments behave as single-ion magnets, with different thermal activation energies of 80.5(6) K and 32.4(5) K, until they reach, upon cooling, a quantum tunneling (QT) regime. Magnetic diluted samples, substituting Dy by Y, {Y(x)Dy(1-x)(α-fur)3}n, were prepared to study the effect of intercluster interactions. Decreasing the Dy interaction by dilution by 90-95% leaves the activation energy unchanged, but shifts the transition to the QT regime to lower temperatures. At T = 2.4 K the tunneling time constant has been shown to decrease weakly with the field in the x = 0 case, and more strongly for x = 0.9. As the external field increases, quantum tunneling is quenched and a new slow relaxation appears that is identified at high fields as caused by a direct relaxation process. As the temperature is decreased, interchain AF coupling becomes effective and gives rise to the occurrence of an antiferromagnetic 3D order transition at T(N) = 0.66 K. From all the evidence, it is concluded that within each bc-plane Dy ions arrange in chains along the c-direction, having weak uncompensated ferromagnetic spin-canted intrachain coupling and antiferromagnetic interchain coupling.

9.
Dalton Trans ; 42(19): 6728-31, 2013 May 21.
Artigo em Inglês | MEDLINE | ID: mdl-23584715

RESUMO

Two Dy(III) ions can be water bridged to form a textbook example of ferromagnetic short-bridged Dy-dimers where strong Ising anisotropy can be evidenced by single-crystal rotating magnetometry. The dimers present both single ion and single molecule magnet behaviour. Magnetic dilution evidences the influence of the ferromagnetic coupling on magnetic relaxation and especially quantum tunnelling.

10.
Angew Chem Int Ed Engl ; 52(1): 350-4, 2013 Jan 02.
Artigo em Inglês | MEDLINE | ID: mdl-23208792

RESUMO

Spotting trends: Upon going from Tb(III) to Yb(III) centers in the complexes of the DOTA(4-) ligand, a reorientation of the easy axis of magnetization from perpendicular to parallel to the Ln-O bond of the apical water molecule is experimentally observed and theoretically predicted (SMM=single-molecule magnet). Only ions with an odd number of electrons show slow relaxation of the magnetization.

11.
Dalton Trans ; 41(44): 13556-67, 2012 Nov 28.
Artigo em Inglês | MEDLINE | ID: mdl-22936346

RESUMO

Due to their usual large magnetic moments and large magnetic anisotropy lanthanide ions are investigated for the search of Single Molecule Magnets with high blocking temperature. However, the low symmetry crystal environment, the complexity of the electronic states or the non-collinearity of the magnetic anisotropy easy-axes in polynuclear systems make the rationalization of the magnetic behaviour of lanthanide based molecular systems difficult. In this perspective article we expose a methodology in which the use of additional characterization techniques, like single crystal magnetic measurements or luminescence experiments, complemented by relativistic ab initio calculations and a suitable choice of spin Hamiltonian models, can be of great help in order to overcome such difficulties, representing an essential step for the rational design of lanthanide based Single Molecule Magnets with enhanced physical properties.

12.
Dalton Trans ; 41(34): 10382-9, 2012 Sep 14.
Artigo em Inglês | MEDLINE | ID: mdl-22810276

RESUMO

The magnetic properties of the porous metal-organic complex Co(bpy)(1.5)(NO(3))(2) (bpy = 4,4'-bipyridine), investigated by SQUID magnetometry, EPR and heat capacity measurements, are reported. The tongue-and-groove structure of this complex is formed by the assembly of T-shaped building blocks, where each Co is bound to three bpy ligands. Co(II) is hepta-coordinated by three N atoms from the bpy units, and four O atoms from two nitrate groups. Experimental results showed a large crystal field effect induced anisotropy with a zero field splitting of Δ = 198 K between the ground and excited Kramers doublets, a factor of two larger than previously reported values in Co(II) hepta-coordinated complexes. EPR revealed orthorhombic crystal field anisotropy, with gyromagnetic principal values of g(1)* = 6.1, g(2)* = 4.2 and g(3)* = 2.2, in an S* = 1/2 effective spin on the ground state Kramers doublet. Ab initio simulations allowed us to assign the anisotropy easy axis of magnetization to the binary symmetry axis of the molecule, aligned with the Co-N apical direction of the T-block.

13.
Eur J Endocrinol ; 166(5): 839-45, 2012 May.
Artigo em Inglês | MEDLINE | ID: mdl-22307573

RESUMO

OBJECTIVE: Type 2 deiodinase gene (DIO2) polymorphisms have been associated with changes in pituitary-thyroid axis homeostasis. The -258A/G (SNP rs12885300) polymorphism has been associated with increased enzymatic activity, but data are conflicting. To characterize the effects of -258A/G polymorphism on intrathyroidal thyroxine (T(4)) to triiodothyronine (T(3)) conversion and thyroid hormone (TH) secretion pattern, we studied the effects of acute, TRH-mediated, TSH stimulation of the thyroid gland. DESIGN: Retrospective analysis. METHODS: The TH secretion in response to 500  µg i.v. TRH injection was studied in 45 healthy volunteers. RESULTS: Twenty-six subjects (16 females and ten males, 32.8 ± 10.4 years) were homozygous for the ancestral (-258A/A) allele and 19 (11 females and eight males, 31.1 ± 10.9 years) were carriers of the (-258G/x) variant. While no differences in the peak TSH and T(3) levels were observed, carriers of the -258G/x allele showed a blunted rise in free T(4) (FT(4); P<0.01). The -258G/x92Thr/Thr haplotype, compared with the other groups, had lower TSH values at 60  min (P<0.03). No differences were observed between genotypes in baseline TH levels. CONCLUSIONS: The -258G/x DIO2 polymorphism variant is associated with a decreased rate of acute TSH-stimulated FT(4) secretion with a normal T(3) release from the thyroid gland consistent with a shift in the reaction equilibrium toward the product. These data indicate that the -258G DIO2 polymorphism causes changes in the pattern of hormone secretion. These findings are a proof of concept that common polymorphisms in DIO2 can subtly affect the circulating levels of TH and might modulate the TH homeostasis.


Assuntos
Iodeto Peroxidase/genética , Polimorfismo de Nucleotídeo Único/genética , Hormônio Liberador de Tireotropina/sangue , Tireotropina/biossíntese , Nucleotídeos de Adenina/genética , Adulto , Estudos de Coortes , Feminino , Nucleotídeos de Guanina/genética , Homeostase/genética , Humanos , Iodeto Peroxidase/fisiologia , Masculino , Estudos Prospectivos , Estudos Retrospectivos , Tireotropina/metabolismo , Hormônio Liberador de Tireotropina/metabolismo , Adulto Jovem
15.
Thyroid ; 20(12): 1407-12, 2010 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-21054208

RESUMO

BACKGROUND: The common Thr92Ala D2 polymorphism has been associated with changes in pituitary-thyroid axis homeostasis, but published results are conflicting. To investigate the effects of the Thr92Ala polymorphism on intrathyroidal thyroxine (T4) to triiodothyronine (T3) conversion, we designed prospective pharmacogenomic intervention aimed to detect differences in T3 levels after thyrotropin (TSH)-releasing hormone (TRH)-mediated TSH stimulation of the thyroid gland. METHODS: Eighty-three healthy volunteers were screened and genotyped for the Thr92Ala polymorphism. Fifteen volunteers of each genotype (Thr/Thr, Thr/Ala, and Ala/Ala) underwent a 500 mcg intravenous TRH stimulation test with serial measurements of serum total T3 (TT3), free T4, and TSH over 180 minutes. RESULTS: No differences in baseline thyroid hormone levels were seen among the study groups. Compared to the Thr/Thr group, the Ala/Ala group showed a significantly lower TRH-stimulated increase in serum TT3 at 60 minutes (12.07 ± 2.67 vs. 21.07 ± 2.86 ng/dL, p = 0.029). Thr/Ala subjects showed an intermediate response. Compared to Thr/Thr subjects, the Ala/Ala group showed a blunted rate of rise in serum TT3 as measured by mean time to 50% maximum delta serum TT3 (88.42 ± 6.84 vs. 69.56 ± 6.06 minutes, p = 0.028). Subjects attained similar maximal (180 minutes) TRH-stimulated TT3 levels. TRH-stimulated TSH and free T4 levels were not significantly different among the three genotype groups. CONCLUSIONS: The commonly occurring Thr92Ala D2 variant is associated with a decreased rate of acute TSH-stimulated T3 release from the thyroid consistent with a decrease in intrathyroidal deiodination. These data provide a proof of concept that the Thr92Ala polymorphism is associated with subtle changes in thyroid hormone homeostasis.


Assuntos
Iodeto Peroxidase/genética , Hormônio Liberador de Tireotropina , Tri-Iodotironina/metabolismo , Adulto , Estudos de Coortes , Humanos , Pessoa de Meia-Idade , Farmacogenética , Polimorfismo Genético , Estudos Prospectivos , Tiroxina/sangue , Tri-Iodotironina/sangue
17.
Chem Commun (Camb) ; (44): 6765-7, 2009 Nov 28.
Artigo em Inglês | MEDLINE | ID: mdl-19885472

RESUMO

A simple trinuclear dysprosium complex shows complex slow relaxation of the magnetisation.

18.
J Am Chem Soc ; 131(15): 5573-9, 2009 Apr 22.
Artigo em Inglês | MEDLINE | ID: mdl-20560638

RESUMO

A mixed theoretical and experimental approach was used to determine the local magnetic anisotropy of the dysprosium(III) ion in a low-symmetry environment. The susceptibility tensor of the monomeric species having the formula [Dy(hfac)(3)(NIT-C(6)H(4)-OEt)(2)], which contains nitronyl nitroxide (NIT-R) radicals, was determined at various temperatures through angle-resolved magnetometry. These results are in agreement with ab initio calculations performed using the complete active space self-consistent field (CASSCF) method, validating the predictive power of this theoretical approach for complex systems containing rare-earth ions, even in low-symmetry environments. Susceptibility measurements performed with the applied field along the easy axis eventually permitted a detailed analysis of the temperature and field dependence of the magnetization, providing evidence that the Dy ion transmits an antiferromagnetic interaction between radicals but that the Dy-radical interaction is ferromagnetic.

19.
Phys Rev Lett ; 100(24): 247205, 2008 Jun 20.
Artigo em Inglês | MEDLINE | ID: mdl-18643625

RESUMO

Single crystal magnetic studies combined with a theoretical analysis show that cancellation of the magnetic moments in the trinuclear Dy3+ cluster [Dy{3}(mu{3}-OH)2L3Cl(H2O){5}]Cl{3}, resulting in a nonmagnetic ground doublet, originates from the noncollinearity of the single-ion easy axes of magnetization of the Dy3+ ions that lie in the plane of the triangle at 120 degrees one from each other. This gives rise to a peculiar chiral nature of the ground nonmagnetic doublet and to slow relaxation of the magnetization with abrupt accelerations at the crossings of the discrete energy levels.

20.
J Phys Chem A ; 112(25): 5742-8, 2008 Jun 26.
Artigo em Inglês | MEDLINE | ID: mdl-18512895

RESUMO

A periodic density functional theory method using the B3LYP hybrid exchange-correlation potential is applied to the Prussian blue analogue RbMn[Fe(CN)6] to evaluate the suitability of the method for studying, and predicting, the photomagnetic behavior of Prussian blue analogues and related materials. The method allows correct description of the equilibrium structures of the different electronic configurations with regard to the cell parameters and bond distances. In agreement with the experimental data, the calculations have shown that the low-temperature phase (LT; Fe(2+)(t(6)2g, S = 0)-CN-Mn(3+)(t(3)2g e(1)g, S = 2)) is the stable phase at low temperature instead of the high-temperature phase (HT; Fe(3+)(t(5)2g, S = 1/2)-CN-Mn(2+)(t(3)2g e(2)g, S = 5/2)). Additionally, the method gives an estimation for the enthalpy difference (HT <--> LT) with a value of 143 J mol(-1) K(-1). The comparison of our calculations with experimental data from the literature and from our calorimetric and X-ray photoelectron spectroscopy measurements on the Rb0.97Mn[Fe(CN)6]0.98 x 1.03 H2O compound is analyzed, and in general, a satisfactory agreement is obtained. The method also predicts the metastable nature of the electronic configuration of the high-temperature phase, a necessary condition to photoinduce that phase at low temperatures. It gives a photoactivation energy of 2.36 eV, which is in agreement with photoinduced demagnetization produced by a green laser.

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