Phase stability and dense polymorph of the BaCa(CO3)2 barytocalcite carbonate.

The double carbonate BaCa(CO3)2 holds potential as host compound for carbon in the Earth's crust and mantle. Here, we report the crystal structure determination of a high-pressure BaCa(CO3)2 phase characterized by single-crystal X-ray diffraction. This phase, named post-barytocalcite, was obtained at 5.7 GPa and can be described by a monoclinic Pm space group. The barytocalcite to post-baritocalcite phase transition involves a significant discontinuous 1.4% decrease of the unit-cell volume, and the increase of the coordination number of 1/4 and 1/2 of the Ba and Ca atoms, respectively. High-pressure powder X-ray diffraction measurements at room- and high-temperatures using synchrotron radiation and DFT calculations yield the thermal expansion of barytocalcite and, together with single-crystal data, the compressibility and anisotropy of both the low- and high-pressure phases. The calculated enthalpy differences between different BaCa(CO3)2 polymorphs confirm that barytocalcite is the thermodynamically stable phase at ambient conditions and that it undergoes the phase transition to the experimentally observed post-barytocalcite phase. The double carbonate is significantly less stable than a mixture of the CaCO3 and BaCO3 end-members above 10 GPa. The experimental observation of the high-pressure phase up to 15 GPa and 300 ºC suggests that the decomposition into its single carbonate components is kinetically hindered.

Gold(i) sulfide: unusual bonding and an unexpected computational challenge in a simple solid.

We report the experimental high-pressure crystal structure and equation of state of gold(i) sulfide (Au2S) determined using diamond-anvil cell synchrotron X-ray diffraction. Our data shows that Au2S has a simple cubic structure with six atoms in the unit cell (four Au in linear, and two S in tetrahedral, coordination), no internal degrees of freedom, and relatively low bulk modulus. Despite its structural simplicity, Au2S displays very unusual chemical bonding. The very similar and relatively high electronegativities of Au and S rule out any significant metallic or ionic character. Using a simple valence bond (Lewis) model, we argue that the Au2S crystal possesses two different types of covalent bonds: dative and shared. These bonds are distributed in such a way that each Au atom engages in one bond of each kind. The multiple arrangements in space of dative and shared bonds are degenerate, and the multiplicity of configurations imparts the system with multireference character, which is highly unusual for an extended solid. The other striking feature of this system is that common computational (DFT) methods fail quite spectacularly to describe it, with 20% and 400% errors in the equilibrium volume and bulk modulus, respectively. We explain this by the poor treatment of static correlation in common density-functional approximations. The fact that the solid is structurally very simple, yet presents unique chemical bonding and is unmodelable using current DFT methods, makes it an interesting case study and a computational challenge.

High-pressure/high-temperature phase diagram of zinc.

The phase diagram of zinc (Zn) has been explored up to 140 GPa and 6000 K, by combining optical observations, x-ray diffraction, and ab initio calculations. In the pressure range covered by this study, Zn is found to retain a hexagonal close-packed (hcp) crystal symmetry up to the melting temperature. The known decrease of the axial ratio (c/a) of the hcp phase of Zn under compression is observed in x-ray diffraction experiments from 300 K up to the melting temperature. The pressure at which c/a reaches [Formula: see text] (≈10 GPa) is slightly affected by temperature. When this axial ratio is reached, we observed that single crystals of Zn, formed at high temperature, break into multiple poly-crystals. In addition, a noticeable change in the pressure dependence of c/a takes place at the same pressure. Both phenomena could be caused by an isomorphic second-order phase transition induced by pressure in Zn. The reported melt curve extends previous results from 24 to 135 GPa. The pressure dependence obtained for the melting temperature is accurately described up to 135 GPa by using a Simon-Glatzel equation: [Formula: see text], where P is the pressure in GPa. The determined melt curve agrees with previous low-pressure studies and with shock-wave experiments, with a melting temperature of 5060(30) K at 135 GPa. Finally, a thermal equation of state is reported, which at room-temperature agrees with the literature.

High-pressure structural and vibrational properties of monazite-type BiPO4, LaPO4, CePO4, and PrPO4.

Monazite-type BiPO4, LaPO4, CePO4, and PrPO4 have been studied under high pressure by ab initio simulations and Raman spectroscopy measurements in the pressure range of stability of the monazite structure. A good agreement between experimental and theoretical Raman-active mode frequencies and pressure coefficients has been found which has allowed us to discuss the nature of the Raman-active modes. Besides, calculations have provided us with information on how the crystal structure is modified by pressure. This information has allowed us to determine the equation of state and the isothermal compressibility tensor of the four studied compounds. In addition, the information obtained on the polyhedral compressibility has been used to explain the anisotropic axial compressibility and the bulk compressibility of monazite phosphates. Finally, we have carried out a systematic discussion on the high-pressure behavior of the four studied phosphates in comparison to results of previous studies.

The plastic crystalline A15 phase of dimethylaminoalane, [N(CH3)2-AlH2]3.

A plastic crystalline phase of dimethylaminoalane has been discovered at T > 332 K. The phase transitions solid - plastic phase - liquid are fully reversible. The plastic crystalline phase exhibits a cubic unit cell, space group Pm3[combining macron]n, in which the dimethylaminoalane molecules rotate and adopt a structural arrangement reminiscent of the A15 phase.

Pressure-induced amorphization of YVO4:Eu³âº nanoboxes.

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.

Design and validation of an augmented reality system for laparoscopic surgery in a real environment.

PURPOSE: This work presents the protocol carried out in the development and validation of an augmented reality system which was installed in an operating theatre to help surgeons with trocar placement during laparoscopic surgery. The purpose of this validation is to demonstrate the improvements that this system can provide to the field of medicine, particularly surgery. METHOD: Two experiments that were noninvasive for both the patient and the surgeon were designed. In one of these experiments the augmented reality system was used, the other one was the control experiment, and the system was not used. The type of operation selected for all cases was a cholecystectomy due to the low degree of complexity and complications before, during, and after the surgery. The technique used in the placement of trocars was the French technique, but the results can be extrapolated to any other technique and operation. RESULTS AND CONCLUSION: Four clinicians and ninety-six measurements obtained of twenty-four patients (randomly assigned in each experiment) were involved in these experiments. The final results show an improvement in accuracy and variability of 33% and 63%, respectively, in comparison to traditional methods, demonstrating that the use of an augmented reality system offers advantages for trocar placement in laparoscopic surgery.

Anomalous high-pressure Jahn-Teller behavior in CuWO4.

High-pressure optical-absorption measurements performed in CuWO(4) up to 20 GPa provide experimental evidence of the persistence of the Jahn-Teller (JT) distortion in the whole pressure range both in the low-pressure triclinic and in the high-pressure monoclinic phase. The electron-lattice couplings associated with the e(g)(E⊗e) and t(2g)(T⊗e) orbitals of Cu(2+) in CuWO(4) are obtained from correlations between the JT distortion of the CuO(6) octahedron and the associated structure of Cu(2+) d-electronic levels. This distortion and its associated JT energy (E(JT)) decrease upon compression in both phases. However, both the distortion and associated E(JT) increase sharply at the phase-transition pressure (P(PT)=9.9 GPa), and we estimate that the JT distortion persists for a wide pressure range not being suppressed up to 37 GPa. These results shed light on the transition mechanism of multiferroic CuWO(4), suggesting that the pressure-induced structural phase transition is a way to minimize the distortive effects associated with the toughness of the JT distortion.

[Interobserver agreement in the visual and semi-quantitative analysis of the 123I-FP-CIT SPECT images in the diagnosis of Parkinsonian syndrome]. / Concordancia interobservador en el análisis visual y semicuantitativo de las imágenes SPECT (123)I-FP-CIT en el diagnóstico del síndrome parkinsoniano.

AIMS: Using (123)I-FP-CIT SPECT images makes it possible to identify presynaptic deterioration of the dopaminergic pathway by studying the dopamine transporter (DAT). A correct analysis of the SPECT images contributes to an adequate interpretation and diagnosis of movement disorders. Aims: 1. To compare visual and semiquantitative analysis of (123)I-FP-CIT SPECT images in patients with movement disorders. 2. To evaluate interobserver agreement in visual and semiquantitative analysis. 3. To obtain a cut-off in the semiquantitative analysis to discriminate primary Parkinsonism Syndrome (PS) from non-primary PS. METHODS: A (123)I-FP-CIT SPECT was performed in 32 patients with movement disorders suggestive of primary PS. Visual and semiquantitative images analyses were performed independently by two nuclear medicine physicians. Visual analysis was based on the visual interpretation. Semiquantitative analysis was calculated as specific uptake (caudate, putamen and striatum) versus non-specific uptake (occipital). Sensitivity, specificity, PPV, and NPV were calculated. Data were compared using ANOVA test followed by Bonferroni post-hoc test. Interobserver agreement of the visual and semiquantitative analysis was assessed by intraclass correlation coefficient and Kappa statistics, respectively. ROC curve was generated with semiquantitative data. RESULTS: Visual analysis showed 86% sensitivity and 100-88% specificity for the differential diagnosis of primary PS from non-primary PS. Semiquantitative analysis showed a gradual hypo-uptake proportional to the disease severity obtained in the visual analysis. Semiquantitative analysis did not provide any additional information to the visual analysis. Intraclass correlation coefficient and Kappa statistics showed 0.92 and 0.80 values, respectively. The Cut-off value to differentiate primary PS from non-primary PS was 1.9 on the putamen index.

Randomised study of single dose (8 Gy vs. 6 Gy) of analgesic radiotherapy plus zoledronic acid in patients with bone metastases.

OBJECTIVE: To assess the effectiveness of a single dose of radio therapy (8 Gy vs. 6 Gy) plus zoledronic acid in cancer patients with bone metastases in treating pain; quality of life, time to onset of skeletal events and functional status. MATERIAL AND METHODS: A total of 139 patients from 22 Spanish hospitals were randomly assigned to: Group A, administered a single dose of 8 Gy+zoledronic acid (4 mg iv, in 15-min infusions), and Group B, administered a single dose of 6 Gy+zoledronic acid (4 mg iv, in 15-min infusions). The main variable was pain, which was assessed with the Visual Analogue Pain Scale (VAS) in supine, seated and standing positions. RESULTS: There was a total of 118 patients for intention to treat (n=67 in Group A and n=51 in Group B). The most frequent primary neoplasms were the lung (29.66%), prostate (22.03%) and breast (21.19%). Sixty patients were analysed per protocol, n=34 in group A and n=26 in group B. Improvements were observed in the VAS scores for pain in all three positions. The mean time to onset of the event was greater (p=0.0211) in Group A than in Group B (122 vs. 81.62 days). Functional status improved in Group A, and quality of life improved in both groups. CONCLUSION: The two groups achieved similar levels of pain control in supine, seated and standing positions. Quality of life also improved in both groups. However, the higher dose (8 Gy dose) in combination with zoledronic acid is associated with a longer period without skeletal events.

[Dementia with Lewy bodies and Alzheimer's disease: differential diagnosis by cardiac sympathetic innervation MIBG imaging]. / Demencia con cuerpos de Lewy y enfermedad de Alzheimer: diagnóstico diferencial mediante estudio de la inervación simpática cardíaca con MIBG.

UNLABELLED: Dementia with Lewy bodies (DLB) is the second most common cause of degenerative dementia after Alzheimer's disease (AD). At present, pre-mortem diagnosis of DLB can only be made clinically using the International Consensus Criteria. However, an accurate differential diagnosis between these diseases could improve the therapeutic handling of patients with DLB, due to their supersensitivity to neuroleptic treatment and the difficult treatment of their psychotic symptoms. OBJECTIVE: To assess the utility of cardiac MIBG imaging as diagnostic study for DLB, to help in the differential diagnosis with AD. MATERIAL AND METHODS: Cardiac MIBG imaging was performed in 11 patients with clinical criteria of probable DLB (7 males, mean age 77 years [range 62-89 years], mean MMSE 17 [range 11-28], and in 9 patients with clinical criteria of probable AD (3 males, mean age 79 years [range 61-87 years], mean MMSE 17 [range 4-25]). Planar anterior images of the thorax were acquired at 15 minutes. (early study) and 4 hours (late study) after tracer injection. Myocardial MIBG activity was quantified by means of a heart-to-mediastinum ratio (HMR). A HMR > 1.8 was considered normal. RESULTS: Respect AD patients, patients with DLB showed decreased HMR in the early study (1.34 +/- 0.27 [range 1.03-1.98] vs. 1.84 +/- 0.22 [range 1.53-2.15], p<0.001) and in the late study (1.22 +/- 0.23 [range 0.95-1.75] vs. 1.73 +/- 0.08 [range 1.59-1.89], p<0.0001). CONCLUSIONS: Cardiac MIBG imaging could be a useful tool for differential diagnosis between DLB and AD.

Accuracy of simplified sampling procedures for estimating milk composition in dairy ewes.

Simplified designs of milk-composition recording, based on information from a single monthly milking, adjusted or not for interval between milkings and for milk yield, were simulated and evaluated for 2553 ewe-test-day records belonging to 155 lactations of Churra dairy ewes. Accuracy of simplified methods was evaluated by comparing estimated trait values (fat, protein, casein and total solid yields) with those observed both in a reference plan, where the two daily milkings were recorded at weekly intervals (A1), and in the official A4 milk recording (monthly records of the two daily milkings). Trait yields per lactation were estimated and adjusted to the only milking period (days in milk 30-120). Estimates of milk component traits were less precise when monthly designs, including the A4 design, were compared with a weekly sampling of both a.m. and p.m. milkings, with fat yield being the most difficult trait to estimate. All options with one daily milking every month were more accurate when the corresponding plan was based on, or began with, the a.m. milking. Adjustment for the preceding interval between milkings or milk yield did not improve sampling accuracy. The design alternating a.m. and p.m. milkings every month, without adjustment, is suggested for recoding milk component traits in dairy ewes.

[Reasons for consultation between primary care and the second level]. / Motivos de interconsulta entre atención primaria y el segundo nivel.

OBJECTIVE: To identify the reasons causing most referrals from primary care to specialist clinics in our health area. In addition, we analysed the quality of compliance in the inter-clinic forms. DESIGN: Descriptive and observational study. SETTING: Primary care in the Toledo Health Area. POPULATION: Inter-clinic forms (ICF) issued by doctors in 17 primary care teams (PCTs) during 2 weeks in November 2002. Measurements. Age and sex of patient, PCT, type of referral (first time, check-up), referral path (normal, preferential), specialty, reason for referral, ICF quality. MAIN RESULTS: 1610 ICFs from 125 doctors were analysed. 64.6% belonged to women. Average age was 43.5 (95% confidence interval [CI], 42.4-44.6). 74.6% (95% CI, 72.2-76.5) were new consultations. 12.9% (95% CI, 11.3-14.7) were preferential referrals. Specialties with most referrals were: Gynaecology (20.2%), traumatology (17.4%), and Ophthalmology (14.9%). The early diagnosis of gynaecological cancer (13.01%; 95% CI, 11.4-14.8), reduction in visual sharpness (6.95%; 95% CI, 5.8-8.3) and benign skin tumours (4.18%; 95% CI, 3.3-5.3) were the 3 reasons for most referrals. ICF quality was thought good in 13.1% of cases, acceptable in 82.8%, and poor in 4.1%. CONCLUSIONS: A high number of referrals were due to reasons that could be resolved at the primary care level. Most inter-clinical referrals were to medical-surgical specialists. Inter-clinical forms are still open to considerable improvement.

DMSA study performed during febrile urinary tract infection: a predictor of patient outcome?

Technetium-99m dimercaptosuccinic acid (DMSA) study has been advocated as a method for the assessment of renal sequelae after acute febrile urinary tract infection (UTI). However, it is not known whether DMSA scintigraphy performed during acute UTI has any prognostic value for outcome assessment. The objective of this study was to evaluate the usefulness of DMSA scintigraphy performed during UTI as a predictor of patient outcome, to identify children at risk of events [vesico-ureteral reflux (VUR) or recurrent UTI] that may lead to the development of progressive renal damage. One hundred and fifty-two children (including 78 girls) with a mean age of 20 months (range 1 month to 12 years) with first febrile UTI were evaluated by DMSA scintigraphy during acute UTI. After acute UTI, children were explored by voiding cysto-urethrography. Children who presented an abnormal DMSA study, or a normal DMSA study but VUR or recurrent UTI, underwent a DMSA control study 6 months after UTI. Children with VUR were followed up by direct radionuclide cystography. DMSA scintigraphy performed during acute UTI was normal in 112 children (74%). In 95 of these children, follow-up DMSA scintigraphy was not performed owing to a good clinical outcome. In the remaining 17 children, follow-up scintigraphy was normal. Forty children (26%) presented abnormal DMSA study during acute UTI. Twenty-five of them presented a normal follow-up DMSA, and 15 presented cortical lesions. Children with abnormal DMSA had a higher frequency of VUR than children with normal DMSA (48% vs 12%). It is concluded that children with normal DMSA during acute UTI have a low risk of renal damage. Children with normal follow-up DMSA and low-grade VUR have more frequent spontaneous resolution of VUR.