RESUMO
We report optical absorption and luminescence measurements in pure and trivalent neodymium (Nd3+) doped LaVO4 crystals up to 25 GPa. Nd3+ luminescence has been employed as a tool to follow the structural changes in the crystal. We also present band-structure and crystal-field calculations that provide the theoretical framework to accurately explain the observed experimental results. In particular, both optical absorption and luminescence measurements evidence that a phase transition takes place close to 12 GPa. They also provide information on the pressure dependence of the band-gap as well as the emission lines under compression. We found drastic changes in the optical properties of LaVO4 when the phase transition to a BaWO4-II structure occurs, which can be related to changes in the coordination number of vanadium ions and in the local sites of Nd3+. Reported results are analyzed in comparison with those of previous X-ray diffraction and Raman experiments, as well as with the features of related compounds. For the first time, a consistent picture is reported explaining the behavior of the optical and electronic properties of LaVO4 at high-pressures.
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The thermal sensing capability of the Tm3+-doped yttrium orthoaluminate nanoperovskite in the infrared range, synthetized by a sol-gel method, was studied. The temperature dependence of the infrared upconverted emission bands located at around 705 nm (3F2,3â3H6) and 800 nm (3H4â3H6) of YAP: Tm3+ nanoperovskite under excitation at 1210 nm was analyzed from RT up to 425 K. Calibration of the optical sensor has been made using the fluorescence intensity ratio technique, showing a high sensitivity in the near-infrared compared to other trivalent rare-earth based optical sensors working in the same range. In addition, a second calibration procedure of the YAP: Tm3+ optical sensor was performed by using the FIR technique on the emission band associated to the 3H4â3H6 transition in the physiological temperature range (293-333 K), showing a very high relative sensitivity compared with other rare-earth based optical temperature sensors working in the physiological range. Moreover, the main advantage compared with other optical sensors is that the excitation source and the upconverted emissions do not overlap, since they lie in different biological windows, thus allowing its potential use as an optical temperature probe in the near-infrared range for biological applications.
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A structural transformation from the zircon-type structure to an amorphous phase has been found in YVO4:Eu(3+) nanoboxes at high pressures above 12.7 GPa by means of x-ray diffraction measurements. However, the pair distribution function of the high-pressure phase shows that the local structure of the amorphous phase is similar to the scheelite-type YVO4. These results are confirmed both by Raman spectroscopy and Eu(3+) photoluminescence which detect the phase transition to a scheelite-type structure at 10.1 and 9.1 GPa, respectively. The irreversibility of the phase transition is observed with the three techniques after a maximum pressure in the upstroke of around 20 GPa. The existence of two (5)D0-->(7)F0 photoluminescence peaks confirms the existence of two local environments for Eu(3+), at least for the low-pressure phase. One environment is the expected for substituting Y(3+) and the other is likely a disordered environment possibly found at the surface of the nanoboxes.
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An ab initio study of the structural, elastic and vibrational properties of the lutetium gallium garnet (Lu3Ga5O12) under pressure has been performed in the framework of the density functional theory, up to 95 GPa. Pressure dependence of the elastic constants and the mechanical stability are analyzed, showing that the garnet structure is mechanically unstable above 87 GPa. Lattice-dynamics calculations in bulk at different pressures have been performed and compared with Raman scattering measurements of the nanocrystalline Tm(3+)-doped Lu3Ga5O12 up to 60 GPa. The theoretical frequencies and pressure coefficients of the Raman active modes for bulk Lu3Ga5O12 are in good agreement with the experimental data measured for the nano-crystals. The contributions of the different atoms to the vibrational modes have been analyzed based on the calculated total and partial phonon density of states. The vibrational modes have been discussed in relation to the internal and external modes of the GaO4 tetrahedron and the GaO6 octahedron. The calculated infrared modes and their pressure dependence are also reported. Our results show that with this nano-garnet size the sample has essentially bulk properties.
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Hypersensitivity to pressure and temperature is observed in the near-infrared emission lines of the Nd(3+) ion in a Cr(3+),Nd(3+):Gd(3)Sc(2)Ga(3)O(12) crystal, associated to the R(1,2)((4)F(3/2))âZ(5)((4)I(9/2)) and R(1,2)((4)F(3/2))âZ(1)((4)I(9/2)) transitions. The former emissions show large linear pressure coefficients of -11.3 cm(-1)/GPa and -8.8 cm(-1)/GPa, while the latter show high thermal sensitivity in the low temperature range. Thus this garnet crystal can be considered a potential optical pressure and/or temperature sensor in high pressure and temperature experiments up to 12 GPa and below room temperature, used in diamond anvil cells and excited with different UV and visible commercial laser due to the multiple Cr(3+) and Nd(3+) absorption bands.
Assuntos
Gadolínio/química , Medições Luminescentes/instrumentação , Fotometria/instrumentação , Transdutores de Pressão , Cristalização , Desenho de Equipamento , Análise de Falha de EquipamentoRESUMO
Lu3Ga5O12 nano-garnet powders doped with Ho(3+)/Yb(3+) ions have been prepared using a citrate sol-gel technique. The structural and morphological properties have been investigated by X-ray diffraction, scanning electron microscopy and Fourier transform infrared spectroscopy. The materials are found to exist in single phase of cubic garnet structure with an average particle size of around 45 nm. The Ho(3+)/Yb(3+)-doped Lu3Ga5O12 nano-garnet powders give rise to an intense green and weak red emission of Ho3+ ions under 457.5 nm direct excitation. Moreover, when the Yb3+ ions are excited at 950 nm a very bright green luminescence of the Ho3+ ions is observed by the naked eyes even for such low laser power as 10 mW and the intensity of the red emission have been increased compared to that found under direct excitation of the Ho3+ ions. The power dependency and dynamics of the infrared-to-visible upconverted luminescence confirm the existence of different two-photon energy transfer processes. All these results have been compared with those obtained for other garnets doped with similar lanthanide ions which suggest that the Lu3Ga5O12 nano-garnets are potential materials for light emitting devices.
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Cristalização/métodos , Luminescência , Medições Luminescentes , Lutécio/química , Nanoestruturas/química , Nanoestruturas/ultraestrutura , Substâncias Macromoleculares/química , Teste de Materiais , Conformação Molecular , Tamanho da Partícula , Propriedades de SuperfícieRESUMO
BACKGROUND: Patients who experience a pelvic cancer recurrence in or near a region that received initial radiotherapy, typically have few options for treatment. Organs at risk (OAR) have often reached their dose constraint limits leaving minimal dose remaining for standard re-irradiation (reRT). However, photon based stereotactic ablative radiotherapy (SABR) has been utilised for reRT with promising initial results although meeting OAR constraints can be challenging. Proton beam therapy (PBT) could offer an advantage. MATERIALS AND METHODS: SABR plans used for treatment for ten pelvic reRT patients were dosimetrically compared to PBT plans retrospectively planned using the same CT and contour data. PBT plans were created to match the CTV dose coverage of SABR treatment plans with V100% ≥95%. An 'as low as reasonably achievable' approach was taken to OAR tolerances with consideration of OAR dose from the initial radiation (using equivalent dose in 2 Gy fractions). RESULTS: Dosimetric comparison of relevant OAR statistics showed a decrease in OAR dose using PBT over SABR in all patients, with equivalent target coverage. The largest statistically significant reduction was seen for the colon D0.5 cm3 with a median reduction from 13.1 Gy to 5.9 Gy. There were statistically significant dose reductions in the median dose to small bowel, sacral plexus and cauda equina. CONCLUSION: PBT has the potential for significant dose reductions for OARs in the pelvic reRT setting compared to SABR. However, it remains unclear if the magnitude of these OAR dose reductions will translate into clinical benefit.
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The concentration and pressure dependent luminescence properties of the Tb(3+) ions in a lithium fluoroborate glasses have been studied by analyzing the deexcitation processes of the (5)D(4) level at ambient conditions as well as a function of pressure up to 35 GPa at room temperature. The luminescence spectra of Tb(3+) ions have been measured as a function of pressure and observed a continuous redshift as well as a progressive increase in the magnitude of the crystal-field splittings for the (5)D(4)-->(7)F(3,4,5) transitions. Monitoring the (5)D(4)-->(7)F(5) transition, the luminescence decay curves have been measured and analyzed in order to understand the dynamics of the deexcitation of the Tb(3+) ions in these glasses. At ambient conditions a nonexponential behavior has been found for doping concentrations as low as 0.1 mol % of Tb(4)O(7), although no cross-relaxation channels exist to explain this behavior. The modelization of the energy transfer processes surprisingly shows that the nonexponential character of the decay curves of the (5)D(4) level with concentration or with pressure has to be ascribed to energy transfer to traps without migration of energy between Tb(3+) ions. For all the experimental situations the nonexponential character of the decay curves is well described by the generalized Yokota-Tanimoto model with a dipole-dipole interaction between the Tb(3+) ions and the nearby luminescence quenching traps. The luminescence properties observed with releasing pressure are slightly different to those obtained while increasing pressure suggesting a local structural hysteresis in the lithium fluoroborate glass matrix giving rise to the generation of a new distribution of environments for the Tb(3+) ions.
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AIMS: To review delivery of definitive chemoradiation (dCRT) for patients with oesophageal cancer within a large regional cancer centre. To assess toxicity, tolerability and outcomes and compare with published data. MATERIALS AND METHODS: A retrospective review of patients undergoing dCRT between November 2009 and November 2014 was carried out. Data were collected regarding treatment completion, radiotherapy plans, toxicity, failure and death. Kaplan-Meier survival curves with a Log-rank test for significance were used for survival analysis. RESULTS: In total, 179 patients were analysed. The median age at diagnosis was 70 years. Forty-four (24.6%) patients had T1 or T2 tumours, 113 (63.1%) T3 and 18 (10.1%) T4; 117 (65.4%) patients were node positive on initial staging. One hundred and forty patients were treated before 2012 with CRT and two adjuvant cycles of cisplatin and capecitabine. Of these, only 50% completed both adjuvant cycles of chemotherapy. Thirty-nine patients were treated after 2012 with neoadjuvant cisplatin and capecitabine followed by CRT. Of these, 92% completed all planned chemotherapy. Ninety-five per cent of patients completed radiotherapy without interruption, but only 46% completed concurrent capecitabine. The mean planning target volume (PTV) length was 13 cm (range 6.9-22.2 cm) and 27 (15%) patients had a PTV length greater than 16 cm. After a median follow-up of 19.6 months (range 3.0-71.9), 83 patients (46%) had relapsed, with 43 (24%) patients having isolated locoregional recurrence. The median overall survival was 26 months (95% confidence interval 20.2-31.8) with a 5 year overall survival rate of 19.7% (95% confidence interval 10.4-31.2). CONCLUSIONS: Our series shows comparable survival rates with published data despite an unselected population. The transition to neoadjuvant chemotherapy before CRT has improved tolerability and increased rates of completion of treatment. The locoregional failure rate remains significant and strategies for improving this, such as changing the chemotherapy back bone and radiation dose escalation, are eagerly awaited within the SCOPE-2 study.
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Protocolos de Quimioterapia Combinada Antineoplásica/uso terapêutico , Quimiorradioterapia , Neoplasias Esofágicas/patologia , Neoplasias Esofágicas/terapia , Recidiva Local de Neoplasia , Idoso , Idoso de 80 Anos ou mais , Protocolos de Quimioterapia Combinada Antineoplásica/efeitos adversos , Institutos de Câncer , Capecitabina/administração & dosagem , Quimiorradioterapia/efeitos adversos , Quimioterapia Adjuvante , Cisplatino/administração & dosagem , Feminino , Fluoruracila/administração & dosagem , Humanos , Estimativa de Kaplan-Meier , Masculino , Pessoa de Meia-Idade , Terapia Neoadjuvante , Recidiva Local de Neoplasia/patologia , Estadiamento de Neoplasias , Estudos Retrospectivos , Taxa de SobrevidaRESUMO
OBJECTIVE: There has been a dramatic increase in the interest and practice of laparoscopic urology, with nephrectomy having become the commonest laparoscopic urological procedure. Compared with open nephrectomy, it results in reduced morbidity and shorter convalescence times while maintaining oncological safety. However, while these results predominately stem from institutions with well developed laparoscopic programmes, little is known about the results in centres that have newly adopted this technique. The introduction of a laparoscopic urological service at the Royal Hallamshire Hospital provided an opportunity to study these factors. METHODS: Since the appointment in October 2000 of a urological surgeon (N Oakley) to develop the laparoscopic service, there have been over 200 laparoscopic procedures including 121 nephrectomies performed at this centre. Full details were collected for each of these cases, and in addition, compared with retrospective data for 50 open nephrectomies performed during the same time period. RESULTS: With increased operator experience the median operative duration, complication, transfusion, and conversion rates significantly improved. While a learning curve was evident, the overall operative complication (9%) and conversion rates (6%) were low, in addition to patient morbidity (16.5%) and mortality (0%) rates, showing that this learning curve had no deleterious effects upon patient care. The median hospital stay was four days, which reduced to three with experience and was significantly shorter than for open nephrectomy at this institution (p = 0.001). CONCLUSIONS: The development of a successful laparoscopic programme can be achieved with a comparatively short learning curve and without detriment to the patient provided the necessary steps are observed.
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Carcinoma de Células Renais/cirurgia , Carcinoma de Células de Transição/cirurgia , Competência Clínica/normas , Neoplasias Renais/cirurgia , Laparoscopia/normas , Nefrectomia/normas , Feminino , Humanos , Complicações Intraoperatórias/etiologia , Laparoscopia/estatística & dados numéricos , Tempo de Internação , Masculino , Pessoa de Meia-Idade , Nefrectomia/métodos , Nefrectomia/estatística & dados numéricos , Complicações Pós-Operatórias/etiologia , Resultado do Tratamento , Carga de TrabalhoRESUMO
The magnetic properties of two similar Er(3+) complexes have been investigated. [Er(tpm)3(bipy)] (Htpm = 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione and bipy = 2,2'-bipyridine) displays thermally activated slow relaxation of magnetisation under a zero direct-current (DC) field. Under an applied HDC field of 1000 G, [Er(tpm)3(bipy)] exhibits two thermally activated processes with energy barriers of 9 and 40 K, while [Er(tfa)3(bipy)] (Htfa = 4,4,4-trifluoro-1-(2-furyl)-1,3-butanedione) shows only one activated process with a barrier of 15 K. Both compounds are luminescent in the solid state, emitting in the near IR region.
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The compression process in the α-phase of europium trimolybdate was revised employing several experimental techniques. X-ray diffraction (using synchrotron and laboratory radiation sources), Raman scattering and photoluminescence experiments were performed up to a maximum pressure of 21 GPa. In addition, the crystal structure and Raman mode frequencies have been studied by means of first-principles density functional based methods. Results suggest that the compression process of α-Eu2(MoO4)3 can be described by three stages. Below 8 GPa, the α-phase suffers an isotropic contraction of the crystal structure. Between 8 and 12 GPa, the compound undergoes an anisotropic compression due to distortion and rotation of the MoO4 tetrahedra. At pressures above 12 GPa, the amorphization process starts without any previous occurrence of a crystalline-crystalline phase transition in the whole range of pressure. This behavior clearly differs from the process of compression and amorphization in trimolybdates with [Formula: see text]-phase and tritungstates with α-phase.
RESUMO
Using a fluorinated 1,1,1-trifluoro-2,4-pentanedione (Htfac) ligand and either 2,2'-bipyridine (bipy), bathophenanthroline (bath) or 5-nitro-1,10-phenanthroline (5NO2phen) as an ancillary ligand, three new ternary erbium(iii) octacoordinated complexes have been synthesized. The single crystal structures of the new complexes (namely [Er(tfac)3(bipy)], [Er(tfac)3(bath)] and [Er(tfac)3(5NO2phen)]) have been determined and their properties have been investigated by Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy and thermodynamic analysis. After ligand-mediated excitation of these complexes in the UV, they all show the characteristic near-infrared (NIR) luminescence of the corresponding Er(3+) ion at 1532 nm. The same emission in the C-band transmission window can also be obtained from the solution-processed organic light-emitting diodes (OLEDs) with structure: glass/ITO/PEDOT:PSS/[Er(tfac)3(N,N-donor)]/Ca/Al. In spite of the fact that the photoluminescence intensity of [Er(tfac)3(5NO2phen)] is stronger than those of [Er(tfac)3(bipy)] and [Er(tfac)3(bath)], the best electroluminescence results correspond to the OLED based on the [Er(tfac)3(bath)] complex, as a consequence of the superior electron transport capabilities of bathophenanthroline.
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We describe the results of x-ray absorption experiments carried out to deduce structural and chemical information in Eu(3+) doped, transparent, oxyfluoride glass and nanostructured glass-ceramic samples. The spectra were measured at the Pb and Eu-L(III) edges. The Eu environment in the glass samples is observed to be similar to that of EuF(3). Complementary x-ray diffraction experiments show that thermal annealing creates ß-PbF(2) type nanocrystals. X-ray absorption indicates that Eu ions act as seeds in the nanocrystal formation. There is evidence of interstitial fluorine atoms around Eu ions as well as Eu dimers. X-ray absorption at the Pb-L(III) edge shows that after the thermal treatment most lead atoms form a PbO amorphous phase and that only 10% of the lead atoms remain available to form ß-PbF(2) type nanocrystals. Both x-ray diffraction and absorption point to a high Eu content in the nanocrystals. Our study suggests new approaches to the oxyfluoride glass-ceramic synthesis in order to further improve their properties.
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Cerâmica/química , Cristalização/métodos , Európio/química , Vidro/química , Nanoestruturas/química , Nanoestruturas/ultraestrutura , Espectroscopia por Absorção de Raios X/métodos , Teste de Materiais , Conformação Molecular , Tamanho da Partícula , Transição de FaseAssuntos
Transplante de Medula Óssea , Doadores de Tecidos , Adulto , Medula Óssea , Pré-Escolar , Feminino , Humanos , Lactente , Masculino , Gravidez , Encaminhamento e Consulta , Resultado do TratamentoAssuntos
Hospitalização , Testes de Inteligência , Transtornos Psicóticos/psicologia , Vocabulário , Logro , Adolescente , Feminino , Humanos , Masculino , PsicometriaRESUMO
A study was carried out of 73 patients of the Clinic of Orthodontics of the Faculty of Stomatology of Havana, treated with the Poussin technique and discharged. 31 of them had Class I Syndrome, 30 Class II Syndrome and 12 Class III Syndrome. The initial and final models of each patient were subjected to the Eisman method. In this way, the changes occurred after finishing the treatment were determined individually. When analyzing the results it was observed that at the onset of the treatment 91.8% ranked in groups III, IV and V (with moderate, severe and very severe affections), while at the end all the patients were in groups I and II (no affections and mild affections).