Defect-Induced Water Bilayer Growth on Anatase TiO2(101).

Preparing an anatase TiO2(101) surface with a high density of oxygen vacancies and associated reduced Ti species in the near-surface region results in drastic changes in the water adsorption chemistry compared to adsorption on a highly stoichiometric surface. Using synchrotron radiation excited photoelectron spectroscopy, we observe a change in the water growth mode, from layer-by-layer growth on the highly stoichiometric surface to bilayer growth on the reduced surface. Furthermore, we have been able to observe Ti3+ enrichment at the surface upon water adsorption. The Ti3+ enrichment occurs concomitant with effective water dissociation into hydroxyls with a very high thermal stability. The water bilayer on the reduced surface is thermally more stable than that on the stoichiometric surface, and it is more efficient in promoting further water dissociation upon heating. The results thus show how the presence of subsurface defects can alter the wetting mechanism of an oxide surface.

Oxidation and Reduction of TiOx Thin Films on Pd(111) and Pd(100).

Thin films of TiOx on Pd(100) and Pd(111) have been investigated with respect to their properties after oxidation and reduction cycles. High-resolution photoemission spectroscopy (HRPES) and low energy electron diffraction (LEED) have been applied to characterize the thin film oxidation states and structure before and after oxidation and reduction under ultrahigh vacuum conditions. Fully oxidized TiO2 films were formed on both surfaces. These structures display Moiré patterns in LEED, in one dimension for Pd(100) and in two dimensions for Pd(111), and they have previously not been reported for TiO2/Pd. The oxidation process causes strong reduction in the interaction between the oxide thin film and the Pd substrate, most significantly for Pd(111). Reversible oxidation/reduction cycling of TiOx thin films on Pd(111) and Pd(100) was possible.

Photochemistry of Carboxylate on TiO2(110) Studied with Synchrotron Radiation Photoelectron Spectroscopy.

We present a dedicated synchrotron radiation photoelectron spectroscopy (SR-PES) study of a photochemical reaction on the surface of rutile TiO2(110). The photoreaction kinetics of carboxylate species (trimethyl acetate, TMA) upon irradiation by UV and soft X-rays were monitored, and we show that it is possible to control the reaction rates from UV light and soft X-rays independently. We directly observe Ti4+ → Ti3+ conversion upon irradiation, attributed to electron trapping at Ti sites close to surface OH groups formed by deprotonation of the parent molecule, trimethylacetic acid (TMAA). TMA photolysis on two surface preparations with different oxygen vacancy densities shows that the vacancy-related charge quenches the amount of charge that can be trapped at hydroxyls upon irradiation. During the initial stages of reaction the correlation between the amount of photodepleted TMA and the amount of charge trapped in the Ti 3d band gap state is nearly 1:1. A first-order kinetics analysis reveals that the reaction rate decreases with decreasing TMA coverage. There is also a coverage-dependent difference in the electronic structure of TMA moieties, primarily involving the carboxyl anchor group. These changes are consistent with a decreased hole affinity of the adsorbed TMA and hence a decreased reaction rate. This discovery adds to the previously presented picture of a reactivity that is inversely proportional to the number of surface hydroxyls, suggesting that the balance between the amounts of TMA, OH, and trapped charge needs to be considered.

A solid target system with remote handling of irradiated targets for PET cyclotrons.

A solid target system was developed for a PET cyclotron. The system is compatible with many different target materials in the form of foils and electroplated/sputtered targets which makes it useful for production of a wide variety of different PET radionuclides. The target material is manually loaded into the system. Remote handling of irradiated target material is managed with a pneumatic piston and a vacuum technique which allows the targets to be dropped into a shielded transport container. To test the target performance, proton irradiations (12.8 MeV, 45 µA) of monoisotopic yttrium foils (0.64 mm, direct water cooling) were performed to produce 89Zr. The yields were 2200±200 MBq (1 h, n=13) and 6300±65 MBq (3 h, n=3).

Heterogeneous reaction between Li and anatase TiO2 nanoparticles under ultra-high vacuum.

We demonstrate heterogeneous chemistry between Li and anatase TiO2 nanoparticles under UHV. The reduction of TiO2 upon formation of lithium oxide proceeds via two different schemes: one that reduces Ti(4+) to Ti(3+) and one that reduces Ti(4+) directly to Ti(2+). The second scheme sets in only after a critical degree of reduction (i.e. Li amount) has been reached (Li/Ti = 0.28) and is associated with restructuring of the film. Two films with different morphologies were compared and the results demonstrate that the reaction between Li and larger TiO2 structures (30-50 nm) is kinetically restricted while such effects were significantly less prominent for small particles (10 nm).

A niobium water target for routine production of [¹8F]Fluoride with a MC 17 cyclotron.

A [(18)F]Fluoride water target was constructed for a Scanditronix MC 17 cyclotron, without a beam line, with a typical wide beam of ∼30 × 5 mm(2). Niobium was used as target chamber material. One hour irradiation with 45µA protons yields about 110 GBq [(18)F]Fluoride. The saturation yield is 8.0 ± 0.6 GBq/µA (EOB). The FDG yield is 60 ± 5% (EOS) with a TracerLab MX (G.E. Healthcare). More than 100 GBq FDG is routinely produced after a 2h irradiation.

High resolution photoemission and x-ray absorption spectroscopy of a lepidocrocite-like TiO2 nanosheet on Pt(110) (1 × 2).

The electronic structure of TiO(2) nanosheets on the Pt(110)-(1 × 2) surface has been investigated by using high resolution photoemission spectroscopy and x-ray absorption spectroscopy (XAS). The Ti 2p XAS spectra of the deposited TiO(2) films have been theoretically evaluated and, from the comparison with the experimental data, the assignment to a lepidocrocite-like structure is confirmed. Coexistence of TiO(2) islands with PtO(2) stripes for incomplete nanosheets is confirmed by high resolution photoemission data. The location of the valence and conduction band edges of the nanosheet has been experimentally determined allowing us to describe in details subtle electronic effects due to the interface with the substrate. The locations of the valence band maximum and the leading peak in the O 1s XAS spectrum indicate a band gap similar to anatase but with the Fermi level closer to mid-gap than found for bulk, n-type TiO(2).

Interface electronic states and molecular structure of a triarylamine based hole conductor on rutile TiO2(110).

The molecular and electronic surface structure of a triarylamine based hole-conductor (HC) molecule evaporated onto rutile TiO2(110) single crystal is investigated by means of synchrotron light based photoelectron spectroscopy and x-ray absorption spectroscopy in combination with calculations based on density functional theory. Different amounts of the HC molecule was evaporated spanning the monolayer to multilayer region. The molecular surface structure is investigated and the results indicate that no specific covalent chemical bonding is formed and that the plane formed by the different nitrogens in the HC molecules has a rather small angle versus the TiO2 substrate surface plane. Some molecular ordering also persists in the multilayer region. The experimental core level spectra, valence level spectra, and the N 1s x-ray absorption spectroscopy spectra are well modeled by calculations on an individual molecule. Interestingly, the formation of the TiO2HC interface results in significant binding energy shifts in core levels and valence levels shifting all peaks of a the HC material to the same extent. Smaller shifts were also observed in the substrate core level peaks. The shift is discussed in terms of nanoscale energy level bending and final state hole screening. With respect to electronic applications, specifically in a solid state dye-sensitized solar cell, it is argued that the observed energy level alignment at the TiO2HC interface can act as a hole trap.

Regional cerebral metabolic rate (positron emission tomography) during inhalation of nitrous oxide 50% in humans.

BACKGROUND: Recent studies in man have shown that cerebral blood flow increases during inhalation of nitrous oxide (N2O), a finding which is believed to be a result of an increased cerebral metabolic rate (CMR). However, this has not previously been evaluated in man. METHODS: Regional CMR(glu) (rCMR(glu)) was measured three dimensionally with positron emission tomography (PET) after injection of 2-(18F)fluoro-2-deoxy-D-glucose in 10 spontaneously breathing men (mean age 31 yr) inhaling either N2O 50% in O2 30% or O2 30% in N2. RESULTS: Global CMR(glu) in young men was 27 (3) micromol 100 g(-1) min(-1) [mean (SD)]. Inhalation of N2O 50% did not change global CMR(glu) [30 (5) micromol 100 g(-1) min(-1)] significantly, but it changed the distribution of the metabolism in the brain (P<0.0001 analysis of variance). Compared with inhalation of O2 30% in N2, N2O 50% inhalation increased the metabolism in the basal ganglia [14 (17)%, P<0.05] and thalamus [22 (23) %, P<0.05]. There was a prolonged metabolic effect of N2O inhalation seen on a succeeding PET scan with oxygen-enriched air (P<0.0001) performed 1 h after the N2O administration. CONCLUSIONS: Inhalation of N2O 50% did not change global CMR(glu), but the metabolism increased in central brain structures, an effect that was still present 1 h after discontinuation of N2O.

Electronic structure of a vapor-deposited metal-free phthalocyanine thin film.

The electronic structure of a vapor-sublimated thin film of metal-free phthalocyanine (H2Pc) is studied experimentally and theoretically. An atom-specific picture of the occupied and unoccupied electronic states is obtained using x-ray-absorption spectroscopy (XAS), core- and valence-level x-ray photoelectron spectroscopy (XPS), and density-functional theory (DFT) calculations. The DFT calculations allow for an identification of the contributions from individual nitrogen atoms to the experimental N1s XAS and valence XPS spectra. This comprehensive study of metal-free phthalocyanine is relevant for the application of such molecules in molecular electronics and provides a solid foundation for identifying modifications in the electronic structure induced by various substituent groups.

Interfacial properties of the nanostructured dye-sensitized solid heterojunction TiO(2)/RuL(2)(NCS)(2)/CuI.

The interfaces of the nanostructured dye-sensitized solid heterojunction TiO(2)/Ru-dye/CuI have been studied using photoelectron spectroscopy of core and valence levels, x-ray absorption spectroscopy and atomic force microscopy. A nanostructured anatase TiO(2) film sensitized with RuL(2)(NCS)(2) [cis-bis(4,4(')-dicarboxy-2,2(')-bipyridine)-bis(isothio-cyanato)-ruthenium(II)] was prepared in a controlled way using a novel combined in-situ and ex-situ (Ar atmosphere) method. Onto this film CuI was deposited in-situ. The formation of the dye-CuI interface and the changes brought upon the dye-TiO(2) interface could be monitored in a stepwise fashion. A direct interaction between the dye NCS groups and the CuI is evident in the core level photoelectron spectra. Concerning the energy matching of the valence electronic levels, the photoelectron spectra indicate that the dye HOMO overlaps in energy with the Cu 3d-I 5p hydrid states. The CuI grow in the form of particles, which at the initial stages displace the dye molecules causing dye-TiO(2) bond breaking. Consequently, the very efficient charge injection channel provided by the dye-TiO(2) carboxylic bonding is directly affected for a substantial part of the dye molecules. This may be of importance for the functional properties of such a heterojunction.

Photoneutron yields from tungsten in the energy range of the giant dipole resonance.

Photoneutron production on the nuclei of high-Z components of medical accelerator heads can lead to a significant secondary dose during a course of bremsstrahlung radiotherapy. However, a quantitative evaluation of secondary neutron dose requires improved data on the photoreaction yields. These have been measured as a function of photon energy, neutron energy and neutron angle for natW, using tagged photons at the MAX-Lab photonuclear facility in Sweden. This work presents neutron yields for natW(gamma, n) and compares these with the predictions of the Monte Carlo code MCNP-GN, developed specifically to simulate photoneutron production at medical accelerators.

Compton scattering from the deuteron and extracted neutron polarizabilities.

Differential cross sections for Compton scattering from the deuteron were measured at MAX-Lab for incident photon energies of 55 and 66 MeV at nominal laboratory angles of 45 degrees, 125 degrees, and 135 degrees. Tagged photons were scattered from liquid deuterium and detected in three NaI spectrometers. By comparing the data with theoretical calculations in the framework of a one-boson-exchange potential model, the sum and the difference of the isospin-averaged nucleon polarizabilities, alpha(N)+beta(N)=17.4+/-3.7 and alpha(N)-beta(N)=6.4+/-2.4 (in units of 10(-4) fm(3)), have been determined. By combining the latter with the global-averaged value for alpha(p)-beta(p) and using the predictions of the Baldin sum rule for the sum of the nucleon polarizabilities, we have obtained values for the neutron electric and magnetic polarizabilities of alpha(n)=8.8+/-2.4(total)+/-3.0(model) and beta(n)=6.5-/+2.4(total)-/+3.0(model), respectively.

Reduced postnatal cerebral glucose metabolism measured by PET after asphyxia in near term fetal lambs.

The effects of fetal asphyxia on cerebral function and development, involve the transition from fetal to neonatal life. Changes in cerebral glucose metabolism may be an early postnatal indicator of fetal asphyxia. The objective is to develop an experimental lamb model involving the transition from fetal to neonatal life and to examine the effect of fetal asphyxia with cerebral hypoxic ischemia on early postnatal cerebral glucose metabolism. Fetal asphyxia was induced by total umbilical cord occlusion in eight near-term fetal lambs (134-138 days) with the ewe under isoflurane-opiate anesthesia. The mean occlusion time until cardiac arrest was 14.5 (4.2) min (SD). Lambs were immediately delivered and standardized resuscitation was instituted after 2 min asystole. At 4 hr postnatal age, [18-F]Fluoro-2-deoxy-glucose (18-FDG) was injected intravenously in eight asphyxiated lambs and in eight controls. Cerebral glucose metabolism was examined by positron emission tomography (PET). As a result the mean arterial blood pressure, acid-base values, blood glucose and serum lactate at 4 hr postnatal age did not differ significantly between lambs subjected to umbilical cord occlusion and controls. EEG was abnormal in all lambs subjected to cord occlusion and normal in the controls at 4 hr postnatal age. Global cerebral metabolic rate (CMRgl) as determined by PET was significantly lower in lambs subjected to cord occlusion mean/median (SD) 22.2/19.6 (8.4) micromol/min/100 g) than in controls mean/median (SD) 37.8/35.9 (6.1); P < 0.01). Global CMRgl is significantly reduced in newborn lambs 4 hr after fetal asphyxia induced by umbilical cord occlusion. A reduction in CMRgl is an early indicator of global hypoxic cerebral ischemia.

Cerebral glucose metabolism measured by positron emission tomography in term newborn infants with hypoxic ischemic encephalopathy.

Total and regional cerebral glucose metabolism (CMRgl) was measured by positron emission tomography with 2-((18)F) fluoro-2-deoxy-D-glucose ((18)FDG) in 20 term infants with hypoxic ischemic encephalopathy (HIE) after perinatal asphyxia. All infants had signs of perinatal distress, and 15 were severely acidotic at birth. Six infants developed mild HIE, twelve moderate HIE, and two severe HIE during their first days of life. The positron emission tomographic scans were performed at 4-24 d of age (median, 11 d). One hour before scanning, 2-3.7 MBq/kg (54-100 microCi/kg) (18)FDG was injected i.v. No sedation was used. Quantification of CMRgl was based on a new method employing the glucose metabolism of the erythrocytes, requiring only one blood sample. In all infants, the most metabolically active brain areas were the deep subcortical parts, thalamus, basal ganglia, and sensorimotor cortex. Frontal, temporal, and parietal cortex were less metabolically active in all infants. Total CMRgl was inversely correlated with the severity of HIE (p < 0.01). Six infants with mild HIE had a mean (range) CMRgl of 55.5 (37.7-100.8) micromol.min(-1).100 g(-1), 11 with moderate HIE had 26.6 (13.0-65.1) micromol.min(-1).100 g(-1), and two with severe HIE had 10.4 and 15.0 micromol.min(-1).100 g(-1), respectively. Five of six infants who developed cerebral palsy had a mean (range) CMRgl of 18.1 (10.2-31.4) micromol.min(-1).100 g(-1) compared with 41.5 (13.0-100.8) micromol.min(-1).100 g(-1) in the infants with no neurologic sequela at 2 y. We conclude that CMRgl measured during the subacute period after perinatal asphyxia in term infants is highly correlated with the severity of HIE and short-term outcome.

Glucose utilisation in the lungs of septic rats.

Sequestration and degranulation of leucocytes in the pulmonary microcirculation is considered to be a key event in the development of acute respiratory distress syndrome in patients with sepsis. Glucose serves as the main source of energy in activated leucocytes. The aim of this study was to assess whether glucose utilisation in the lungs can be used as an indicator of pulmonary leucocyte accumulation in an experimental model of sepsis of intra-abdominal origin. Sepsis was induced in rats by abdominal implantation of a gelatine capsule containing bacteria and rat colonic contents. Empty gelatine capsules were implanted in control animals. Animals were studied 6 and 12 h after sepsis induction. Glucose utilisation was measured as the tissue uptake of fluorine-18-fluorodeoxyglucose ((18)FDG) 1 h after intravenous injection of the tracer. Micro-autoradiography was also performed after injection of tritiated deoxyglucose. We found increased uptake of (18)FDG in the lungs of septic animals. The uptake also increased with time after sepsis induction. (18)FDG uptake in circulating leucocytes was increased in septic animals compared with controls, and micro-autoradiography showed intense accumulation of deoxyglucose in leucocytes in the lungs of septic animals. We conclude that glucose utilisation is increased in the lungs of septic rats. Measurements of pulmonary glucose utilisation as an index of leucocyte metabolic activity may open new possibilities for studies of the pathophysiology of sepsis and for evaluation of therapeutic interventions.

An alternative method to normalize clinical FDG studies.

UNLABELLED: An alternative method of determining the integrated input function, necessary in the quantitative [18F]fluorodeoxyglucose (FDG) autoradiographic model, has been developed. Using erythrocytes as reference tissue, researchers require only one blood sample after injection of FDG to obtain the integrated input function. METHODS: The amount of FDG-6-PO4 in the erythrocytes is proportional to their exposure to FDG, that is, the integrated input function. Free FDG is removed by washing the erythrocytes twice. Inter- and intraindividual differences of the metabolic rate of erythrocytes are corrected for by an in vitro incubation with a known amount of FDG. RESULTS: Validation of the proposed method was done by correlating the integrated input function, based on the glucose metabolism of the erythrocytes, to the integrated input function obtained by multiple venous blood samples. The new method provides the integrated input function with an accuracy better than +/-8%. CONCLUSION: By using erythrocytes as a reference tissue, researchers can determine the integrated input function in the quantitative FDG autoradiographic model with an accuracy sufficient for clinical PET studies. The simplicity of the method also makes it suitable for FDG studies on small children. With two samples, the method can also be used for a simplified graphical Patlak analysis.

Early prediction of treatment outcome in head and neck cancer with 2-18FDG PET.

The development of alternative treatment regimens in clinical oncology has increased the need for early prediction of cancer therapy outcome. The aim of this study was, early in the treatment phase, to identify patients with advanced head and neck cancer, responding or not responding to initiated therapy. The tumour metabolic rate of glucose (MRgl) examined by 2-18FDG-PET was determined in 17 patients before and after the first weeks of either radiotherapy (16-35 Gy) or one course of combination chemotherapy. Metabolic values uptake values normalized to plasma activity integrals--were correlated to loco-regional outcome, as evaluated 5-6 weeks after completion of treatment. Initial low tumour MRgl (<20 micromol/min/100 g tissue), in primary lesions or regional metastases, predicted a local complete response. When a high initial tumour MRgl was found, the magnitude of the reduction of MRgl in the second PET examination might be an adjunct in predicting local tumour response.

Use of pulse transit time as a measure of inspiratory effort in patients with obstructive sleep apnoea.

Pulse transit time (PTT) is the time taken for the arterial pulse pressure wave to travel from the aortic valve to a peripheral site. For convenience, it is usually measured from the R wave on the electrocardiogram to the pulse wave arrival at the finger. Pulse transit time is inversely proportional to blood pressure, and the falls in blood pressure which occur with inspiration (pulsus paradoxus) correspond to rises (lengthening) in pulse transit time. In awake normal subjects, the size of these inspiratory rises in pulse transit time correlate well with the degree of inspiratory effort. The aim of this study was to investigate whether inspiratory rises in pulse transit time could provide a quantitative measure of inspiratory effort in patients with obstructive sleep apnoea. Eight patients with obstructive sleep apnoea, attending the laboratory for institution of nasal continuous positive airway pressure, took part in the study. Once asleep, airway pressure was varied between optimal treatment level and minimum pressure, to produce a range of inspiratory efforts whilst continuous recordings of oesophageal pressure and pulse transit time were made. There was an excellent correlation between the size of the swings in oesophageal pressure and the size of the swings in pulse transit time (mean r = 0.94). Pulse transit time may, therefore, provide a clinically useful noninvasive and quantitative measure of inspiratory effort in patients with sleep-related breathing disorders.