Novel polyoxometalate-templated, 3-D supramolecular networks based on lanthanide dimers: Synthesis, structure, and fluorescent properties of [Ln(2)(DNBA)(4)(DMF)(8)][Mo6O19] (DNBA=3,5-dinitrobenzoate)

The spherical Lindquist type polyoxometalate, Mo6O192-, has been used as a noncoordinating anionic template for the construction of novel three-dimensional lanthanide-aromatic monocarboxylate dimer supramolecular networks [Ln(2)(DNBA)(4)(DMF)(8)][Mo6O19] (Ln = La 1, Ce 2, and Eu 3, DNBA = 3,5-dinitrobenzoate, DMF = dimethylformamide). The title compounds are characterized by elemental analyses, IR, and single-crystal X-ray diffractions. X-ray diffraction experiments reveal that two Ln(III) ions are bridged by four 3,5-dinitrobenzoate anions as asymmetrically bridging ligands, leading to dimeric cores, [Ln(2)(DNBA)(4)(DMF)(8)](2+); [Ln(2)(DNBA)(4)(DMF)(8)](2+) groups are joined together by pi-pi stacking interactions between the aromatic groups to form a two-dimensional grid-like network; the 2-D supramolecular layers are further extended into 3-D supramolecular networks with 1-D box-like channels by hydrogen-bonding interactions, in which hexamolybdate polyanions reside. The compounds represent the first examples of 3-D carboxylate-bridged lanthanide dimer supramolecular "host" networks formed by pi-pi stacking and hydrogen-bonding interactions encapsulating noncoordinating "guest" polyoxoanion species. The fluorescent activity of compound 3 is reported.

Restauração directa de classes II em pré-molares com compósitos

Tese de Doutoramento apresentada à Universidade Fernando Pessoa como parte dos requisitos para obtenção do grau de Doutor em em Biotecnologia e Saúde, Epidemiologia e Saúde Pública.

Midlatitude daytime D region ionosphere variations measured from radio atmospherics

We measured the midlatitude daytime ionospheric D region electron density profile height variations in July and August 2005 near Duke University by using radio atmospherics (or sferics for short), which are the high-power, broadband very low frequency (VLF) signals launched by lightning discharges. As expected, the measured daytime D region electron density profile heights showed temporal variations quantitatively correlated with solar zenith angle changes. In the midlatitude geographical regions near Duke University, the observed quiet time heights decreased from ∼80 km near sunrise to ∼71 km near noon when the solar zenith angle was minimum. The measured height quantitative dependence on the solar zenith angle was slightly different from the low-latitude measurement given in a previous work. We also observed unexpected spatial variations not linked to the solar zenith angle on some days, with 15% of days exhibiting regional differences larger than 0.5 km. In these 2 months, 14 days had sudden height drops caused by solar flare X-rays, with a minimum height of 63.4 km observed. The induced height change during a solar flare event was approximately proportional to the logarithm of the X-ray flux. In the long waveband (wavelength, 1-8 Å), an increase in flux by a factor of 10 resulted in 6.3 km decrease of the height at the flux peak time, nearly a perfect agreement with the previous measurement. During the rising and decaying phases of the solar flare, the height changes correlated more consistently with the short, rather than the long, wavelength X-ray flux changes. © 2010 by the American Geophysical Union.

Fractures in myelomeningocele.

BACKGROUND: In patients with myelomeningocele (MMC), a high number of fractures occur in the paralyzed extremities, affecting mobility and independence. The aims of this retrospective cross-sectional study are to determine the frequency of fractures in our patient cohort and to identify trends and risk factors relevant for such fractures. MATERIALS AND METHODS: Between March 1988 and June 2005, 862 patients with MMC were treated at our hospital. The medical records, surgery reports, and X-rays from these patients were evaluated. RESULTS: During the study period, 11% of the patients (n = 92) suffered one or more fractures. Risk analysis showed that patients with MMC and thoracic-level paralysis had a sixfold higher risk of fracture compared with those with sacral-level paralysis. Femoral-neck z-scores measured by dual-energy X-ray absorptiometry (DEXA) differed significantly according to the level of neurological impairment, with lower z-scores in children with a higher level of lesion. Furthermore, the rate of epiphyseal separation increased noticeably after cast immobilization. Mainly patients who could walk relatively well were affected. CONCLUSIONS: Patients with thoracic-level paralysis represent a group with high fracture risk. According to these results, fracture and epiphyseal injury in patients with MMC should be treated by plaster immobilization. The duration of immobilization should be kept to a minimum (<4 weeks) because of increased risk of secondary fractures. Alternatively, patients with refractures can be treated by surgery, when nonoperative treatment has failed.

The effect of prenatal or early postnatal irradiation on the production of anti-arsonate antibodies and Cross-reactive idiotypes

Preliminary studies on the long-term effects of prenatal and early postnatal irradiation on the immune response to arsonate were performed using A/J mice. Pregnant mice were irradiated (0·5 Gy, X-rays) or sham-irradiated on a single occasion during gestation (between day 5 and 18 post-conception). Alternatively, newborn mice received the same treatment between day 2 and 7 after birth. Mice were immunized with keyhole limpet haemocyanin-arsonate (KLH-Ars) in adjuvant from 2 months after birth. The levels of specific antibodies to arsonate (anti-Ars) were measured by radioimmunoassay. In addition, the Ars-related cross-reactive idiotype (CRIA) was measured by the haemagglutination technique. In the primary response the titre of anti-Ars was reduced in animals that had been irradiated between day 12 and 15 of gestation. In the second response, in contrast, they had increased levels of anti-Ars. After immunization with KLH-Ars, high levels of CRIA were observed in all groups. However, in mice irradiated 18-20 days after conception the level of CRIA was often much higher than the level of anti-Ars, indicating that a large proportion of the CRIA-positive molecules were not specific for Ars. Thus, in this particular case, some specificity of the immune response was lost after irradiation. The expression of recurrent idiotypes may be a sensitive indicator of immunological perturbations after irradiation. © 1988 Informa UK Ltd All rights reserved: reproduction in whole or part not permitted.

Dielectronic recombination in highly charged He-like ions

We have determined resonant strengths of the KLn (2 less than or equal to n less than or equal to 5) resonances for helium-like Ti ions and (3 less than or equal to n less than or equal to 5) resonances for helium-like Fe ions. The results were obtained using the Tokyo electron beam ion trap. Characteristic X-rays from both dielectronic recombination and radiative recombination were detected as the electron beam energy was scanned through the resonances. (C) 2003 Elsevier Science B.V. All rights reserved.

Dielectronic recombination in He-like titanium ions

Dielectronic recombination (DR) has been studied in highly charged He-like Ti ions using an electron beam ion trap. X-rays emitted from radiative recombination (RR) and DR were observed as the electron beam energy was scanned through the resonances. Differential DR resonant strengths were determined by normalizing the DR x-ray intensity to the RR intensity using theoretical RR cross sections. KLn (2 less than or equal to n less than or equal to 5) resonant strengths were determined for He-like Ti ions. The differential resonant strengths were calibrated without reference to any theoretical DR calculations while the electron energy scale was derived with reference to the well-known energy for ionization of the He-like and H-like ions from the ground state. Calibration in this way facilitates a more exacting comparison between theory and experiment than has been reported previously. To facilitate this comparison, total and differential theoretical resonance strengths were calculated. These calculations were found to be in good agreement with the measured results.

Dielectronic recombination of hydrogen-like ions

Decay dynamics of dielectronic recombination (DR) processes of H-like titanium ions was investigated with an electron beam ion trap. In the DR of H-like ions a K-shell vacancy is available even after the decay of the doubly excited state produced by the recombination. Therefore secondary X-ray emission is possible. An observed X-ray spectrum of DR obtained in the present experiment was well reproduced theoretically by taking into account the secondary X-rays. (c) 2005 Elsevier B.V. All rights reserved.

Two-electron QED contributions to the ground-state binding energy in He-like Kr34+ ions

The two-electron QED contributions to the ground-state binding energy of Kr34+ ions have been determined in two independent experiments performed with electron beam ion traps (EBIT) in Heidelberg (HD) and Tokyo (BT, Belfast-Tokyo collaboration). X rays arising from radiative recombination (RR) of free electrons to the ground state of initially bare Kr36+ and hydrogenlike Kr35+ ions were observed as a function of the interacting electron energy. The K edge absorption by thin Eu and W foils provided fixed photon energy references used to measure the difference in binding energy Delta E-2e between the H- and He-like Kr ions (Kr35+ and Kr34+, respectively). The two values agree well, yielding a final result of Delta E-2e=641.8 +/- 1.7 eV, confirming recent results of rigorous QED calculations. This accuracy is just of the order required to access screened radiative QED contributions.

Lifestyle limitations of children and young people with severe cerebral palsy: a population study protocol

Aim.  This paper is a presentation of a study protocol to establish the prevalence of orthopaedic problems (hip dislocation, pelvic obliquity, spinal deformity and contractures) and their impact on pain, function, participation and health in a population of children and young people with severe cerebral palsy.

Background.  Cerebral palsy is the commonest cause of motor impairment in childhood and is associated with life-long disability. An estimated 30% of people with cerebral palsy have severe forms and are non-ambulant. Although the underlying neurological damage is not amenable to correction, many health services are dedicated to providing therapeutic and adaptive support to help people with the condition reach their potential.

Method.  A cross-sectional survey of children and young people, aged 4–25 years with severe, non-ambulant cerebral palsy as defined using the Gross Motor Function Classification System (Levels IV and V). Study participants will be identified from a pre-existing, geographically defined case register and recruited via a healthcare professional known to them. Two assessments will be undertaken: one involving parents/carers at home and using questionnaires; the other involving the child/young person ideally in one of three settings and including X-rays if clinically indicated.

Discussion.  This study will contribute to our knowledge of the history and epidemiology of orthopaedic problems in children and young people with cerebral palsy and how these problems accumulate and impact on participation, health and well-being. The study will also identify unmet need and make recommendations for good practice in relation to the orthopaedic care and management for people with severe cerebral palsy

Radiation-induced bystander and adaptive responses in cell and tissue models.

The use of microbeam approaches has been a major advance in probing the relevance of bystander and adaptive responses in cell and tissue models. Our own studies at the Gray Cancer Institute have used both a charged particle microbeam, producing protons and helium ions and a soft X-ray microprobe, delivering focused carbon-K, aluminium-K and titanium-K soft X-rays. Using these techniques we have been able to build up a comprehensive picture of the underlying differences between bystander responses and direct effects in cell and tissue-like models. What is now clear is that bystander dose-response relationships, the underlying mechanisms of action and the targets involved are not the same as those observed for direct irradiation of DNA in the nucleus. Our recent studies have shown bystander responses even when radiation is deposited away from the nucleus in cytoplasmic targets. Also the interaction between bystander and adaptive responses may be a complex one related to dose, number of cells targeted and time interval.

Radiotherapy in the presence of contrast agents: a general figure of merit and its application to gold nanoparticles

Delivering sufficient dose to tumours while sparing surrounding tissue is one of the primary challenges of radiotherapy, and in common practice this is typically achieved by using highly penetrating MV photon beams and spatially shaping dose. However, there has been a recent increase in interest in the possibility of using contrast agents with high atomic number to enhance the dose deposited in tumours when used in conjunction with kV x-rays, which see a significant increase in absorption due to the heavy element's high-photoelectric cross-section at such energies. Unfortunately, the introduction of such contrast agents significantly complicates the comparison of different source types for treatment efficacy, as the dose deposited now depends very strongly on the exact composition of the spectrum, making traditional metrics such as beam quality less valuable. To address this, a 'figure of merit' is proposed, which yields a value which enables the direct comparison of different source types for tumours at different depths inside a patient. This figure of merit is evaluated for a 15 MV LINAC source and two 150 kVp sources (both of which make use of a tungsten target, one with conventional aluminium filtration, while the other uses a more aggressive thorium filter) through analytical methods as well as numerical models, considering tissue treated with a realistic concentration and uptake ratio of gold nanoparticle contrast agents (10 mg ml(-1) concentration in 'tumour' volume, 10: 1 uptake ratio). Finally, a test case of human neck phantom is considered with a similar contrast agent to compare the abstract figure to a more realistic treatment situation. Good agreement was found both between the different approaches to calculate the figure of merit, and between the figure of merit and the effectiveness in a more realistic patient scenario. Together, these observations suggest that there is the potential for contrast-enhanced kilovoltage radiation to be a useful therapeutic tool for a number of classes of tumour on dosimetric considerations alone, and they point to the need for further research in this area.

Polarization studies of radiative electron capture into highly-charged uranium ions

Recent advances in the development of 2D microstrip detectors open up new possibilities for hard x-ray spectroscopy, in particular for polarization studies. These detectors make ideal Compton polarimeters, which enable us to study precisely the polarization of hard x-rays. Here, we present recent results from measurements of Radiative Electron Capture into the K-shell of highly-charged uranium ions. The experiments were performed with a novel 2D Si(Li) Compton polarimeter at the Experimental Storage Ring at GSI. Stored and cooled beams of U91+ and U92+ ions, with kinetic energies of 43 MeV/u and 96 MeV/u respectively, were crossed with a hydrogen gasjet. The preliminary data analysis shows x-rays from the K-REC process, emitted perpendicularly to the ion beam, to be strongly linearly polarized.

Application to argon ions of a new technique to measure the two-electron contribution to the ground state energy of helium-like ions

We have measured the two-electron contribution of the ground state energy of helium-like argon ions using an electron beam ion trap (EBIT). A two-dimensional map was measured showing the intensity of x-rays from the trap passing through a krypton-filled absorption cell. The independent axes of this map were electron beam energy and x-ray energy. From this map, we deduced the two-electron contribution of the ground state of helium-like argon. This experimentally determined Value (312.4 +/- 9.5 eV) was found to be in good agreement with our calculated values (about 303.35 eV) and previous calculations of the same quantity. Based on these measurements, we have shown that a ten-day absorption spectroscopy run with a super-EBIT should be sufficient to provide a new benchmark value for the two-electron contribution to the ground state of helium-like krypton. Such a measurement would then constitute a test of quantum electrodynamics to second order.

Attosecond phase locking of harmonics emitted from laser-produced plasmas

Laser-driven coherent extreme-ultraviolet (XUV) sources provide pulses lasting a few hundred attoseconds(1,2), enabling real-time access to dynamic changes of the electronic structure of matter(3,4), the fastest processes outside the atomic nucleus. These pulses, however, are typically rather weak. Exploiting the ultrahigh brilliance of accelerator-based XUV sources(5) and the unique time structure of their laser-based counterparts would open intriguing opportunities in ultrafast X-ray and high-field science, extending powerful nonlinear optical and pump-probe techniques towards X-ray frequencies, and paving the way towards unequalled radiation intensities. Relativistic laser-plasma interactions have been identified as a promising approach to achieve this goal(6-13). Recent experiments confirmed that relativistically driven overdense plasmas are able to convert infrared laser light into harmonic XUV radiation with unparalleled efficiency, and demonstrated the scalability of the generation technique towards hard X-rays(14-19). Here we show that the phases of the XUV harmonics emanating from the interaction processes are synchronized, and therefore enable attosecond temporal bunching. Along with the previous findings concerning energy conversion and recent advances in high-power laser technology, our experiment demonstrates the feasibility of confining unprecedented amounts of light energy to within less than one femtosecond.