Manganese-rhodium nanoparticles: Adsorption on titanium oxide surfaces and catalyst for syngas reactions.

Manganese-rhodium (Mn-Rh) nanoparticles have emerged as a promising candidate for catalytic applications in the production of syngas, a critical precursor for a wide range of industrial processes. This study employs a comprehensive, theoretical, and computational approach to investigate the structural and electronic properties of Mn-Rh nanoparticles, with a specific focus on their interaction with titanium oxide (TiO2) surfaces and their potential as catalysts for syngas reactions. The density functional theory calculations are employed to explore the adsorption behavior of Mn-Rh nanoparticles on TiO2 surfaces. By analyzing the adsorption energies, geometries, and electronic structure at the nanoscale interface, we provide valuable insights into the stability and reactivity of Mn-Rh nanoparticles when immobilized on TiO2 supports. Furthermore, the catalytic performance of Mn-Rh nanoparticles in syngas production is thoroughly examined. Through detailed reaction mechanism studies and kinetic analysis, we elucidate the role of Mn and Rh in promoting syngas generation via carbon dioxide reforming and partial oxidation reactions. The findings demonstrate the potential of Mn-Rh nanoparticles as efficient catalysts for these crucial syngas reactions. This research work not only enhances our understanding of the fundamental properties of Mn-Rh nanoparticles but also highlights their application as catalysts for sustainable and industrially significant syngas production.

Initial stage of atomic layer deposition of 2D-MoS2 on a SiO2 surface: a DFT study.

In this study, we investigate the reactions involving Atomic Layer Deposition (ALD) of 2D-MoS2 from the heteroleptic precursor Mo(NMe2)2(NtBu)2 and H2S as the co-reagent on a SiO2(0001) surface by means of density functional theory (DFT). All dominant reaction pathways from the early stage of adsorption of each ALD reagent to the formation of bulk-like Mo and S at the surface are identified. In the metal pulse, proton transfer from terminal OH groups on the SiO2 to the physisorbed metal precursor increases the Lewis acidity of Mo and Lewis basicity of O, which gives rise to the chemical adsorption of the metal precursor. Proton transfer from the surface to the dimethylamido ligands leads to the formation and desorption of dimethylamine. In contrast, the formation and desorption of tert-butylamine is not energetically favorable. The tert-butylimido ligand can only be partially protonated in the metal pulse. In the sulphur pulse, co-adsorption and dissociation of H2S molecules give rise to the formation and desorption of tert-butylamine. Through the calculated activation energies, the cooperation between H2S molecules ('cooperative' mechanism) is shown to have a profound influence on the formation and desorption of tert-butylamine, which are crucial steps in the initial ALD deposition of 2D-MoS2 on SiO2. The cyclic ALD reactions give rise to the formation of a buffer layer which might have important consequences for the electrical and optical properties on the 2D layer formed in the subsequent homodeposition.

Early primary biliary cholangitis is characterised by brain abnormalities on cerebral magnetic resonance imaging.

BACKGROUND: Brain change can occur in primary biliary cholangitis (PBC), potentially as a result of cholestatic and/or inflammatory processes. This change is linked to systemic symptoms of fatigue and cognitive impairment. AIM: To identify whether brain change occurs early in PBC. If the change develops early and is progressive, it may explain the difficulty in treating these symptoms. METHODS: Early disease brain change was explored in 13 patients with newly diagnosed biopsy-proven precirrhotic PBC using magnetisation transfer, diffusion-weighted imaging and 1 H magnetic resonance spectroscopy. Results were compared to 17 healthy volunteers. RESULTS: Cerebral magnetisation transfer ratios were reduced in early PBC, compared to healthy volunteers, in the thalamus, putamen and head of caudate with no greater reduction in patients with greater symptom severity. Mean apparent diffusion coefficients were increased in the thalamus only. No 1 H magnetic resonance spectroscopy abnormalities were seen. Serum manganese levels were elevated in all PBC patients, but no relationship was seen with imaging or symptom parameters. There were no correlations between neuroimaging data, laboratory data, symptom severity scores or age. CONCLUSIONS: This is the first study to be performed in this precirrhotic patient population, and we have highlighted that neuroimaging changes are present at a much earlier stage than previously demonstrated. The neuroimaging abnormalities suggest that the brain changes seen in PBC occur early in the pathological process, even before significant liver damage has occurred. If such changes are linked to symptom pathogenesis, this could have important implications for the timing of second-line-therapy use.

Sub-nanometer dimensions control of core/shell nanoparticles prepared by atomic layer deposition.

Bimetallic core/shell nanoparticles (NPs) are the subject of intense research due to their unique electronic, optical and catalytic properties. Accurate and independent control over the dimensions of both core and shell would allow for unprecedented catalytic performance. Here, we demonstrate that both core and shell dimensions of Pd/Pt core/shell nanoparticles (NPs) supported on Al2O3 substrates can be controlled at the sub-nanometer level by using a novel strategy based on atomic layer deposition (ALD). From the results it is derived that the main conditions for accurate dimension control of these core/shell NPs are: (i) a difference in surface energy between the deposited core metal and the substrate to obtain island growth; (ii) a process yielding linear growth of the NP cores with ALD cycles to obtain monodispersed NPs with a narrow size distribution; (iii) a selective ALD process for the shell metal yielding a linearly increasing thickness to obtain controllable shell growth exclusively on the cores. For Pd/Pt core/shell NPs it is found that a minimum core diameter of 1 nm exists above which the NP cores are able to catalytically dissociate the precursor molecules for shell growth. In addition, initial studies on the stability of these core/shell NPs have been carried out, and it has been demonstrated that core/shell NPs can be deposited by ALD on high aspect ratio substrates such as nanowire arrays. These achievements show therefore that ALD has significant potential for the preparation of tuneable heterogeneous catalyst systems.

The use of atomic layer deposition in advanced nanopatterning.

Atomic layer deposition (ALD) is a method that allows for the deposition of thin films with atomic level control of the thickness and an excellent conformality on 3-dimensional surfaces. In recent years, ALD has been implemented in many applications in microelectronics, for which often a patterned film instead of full area coverage is required. This article reviews several approaches for the patterning of ALD-grown films. In addition to conventional methods relying on etching, there has been much interest in nanopatterning by area-selective ALD. Area-selective approaches can eliminate compatibility issues associated with the use of etchants, lift-off chemicals, or resist films. Moreover, the use of ALD as an enabling technology in advanced nanopatterning methods such as spacer defined double patterning or block copolymer lithography is discussed, as well as the application of selective ALD in self-aligned fabrication schemes.

Experimental determination of the radial dose distribution in high gradient regions around 192Ir wires: comparison of electron paramagnetic resonance imaging, films, and Monte Carlo simulations.

PURPOSE: The experimental determination of doses at proximal distances from radioactive sources is difficult because of the steepness of the dose gradient. The goal of this study was to determine the relative radial dose distribution for a low dose rate 192Ir wire source using electron paramagnetic resonance imaging (EPRI) and to compare the results to those obtained using Gafchromic EBT film dosimetry and Monte Carlo (MC) simulations. METHODS: Lithium formate and ammonium formate were chosen as the EPR dosimetric materials and were used to form cylindrical phantoms. The dose distribution of the stable radiation-induced free radicals in the lithium formate and ammonium formate phantoms was assessed by EPRI. EBT films were also inserted inside in ammonium formate phantoms for comparison. MC simulation was performed using the MCNP4C2 software code. RESULTS: The radical signal in irradiated ammonium formate is contained in a single narrow EPR line, with an EPR peak-to-peak linewidth narrower than that of lithium formate (approximately 0.64 and 1.4 mT, respectively). The spatial resolution of EPR images was enhanced by a factor of 2.3 using ammonium formate compared to lithium formate because its linewidth is about 0.75 mT narrower than that of lithium formate. The EPRI results were consistent to within 1% with those of Gafchromic EBT films and MC simulations at distances from 1.0 to 2.9 mm. The radial dose values obtained by EPRI were about 4% lower at distances from 2.9 to 4.0 mm than those determined by MC simulation and EBT film dosimetry. CONCLUSIONS: Ammonium formate is a suitable material under certain conditions for use in brachytherapy dosimetry using EPRI. In this study, the authors demonstrated that the EPRI technique allows the estimation of the relative radial dose distribution at short distances for a 192Ir wire source.

[Potential place of FDG-PET for the GTV delineation in head and neck and lung cancers]. / Rôle potentiel de la TEP-FDG pour la définition du volume tumoral macroscopique (GTV) des cancers des voies aérodigestives supérieures et du poumon.

The recent progresses performed in imaging, computational and technological fields bring new opportunities to achieve high precision radiation dose delivery. However, IMRT requires a particular attention at the target delineation step to avoid inadequate dosage to TVs/OARs. In this context, the biological information provided by PET might advantageously complete CT-Scan to refine the target delineation in HNSCC and lung cancer. Integrating PET into the treatment planning however requires the use and validation of accurate and reproducible segmentation methods, which adequately integrate the PET image properties such as the blur effect and the high level of noise. In this context, we developed specific tools, i.e. edge-preserving filters for denoising and deconvolution algorithms for deblurring that allowed the detection of gradient intensity peaks. Our gradient-based method has been validated on phantom and patient materials, and proved to be more accurate than threshold-based approaches. With this tool in hand, we demonstrated that the use of FDG-PET resulted in smaller TVs than the CT-based TVs, on both pre- and per-treatment images, and significantly improved the dose distributions to the TVs/OARs. This opens avenues for dose escalation strategies that might potentially improve the tumor local control.

An easy-to-use phantom and protocol for weekly PET quality assessment: a multicenter study.

The authors have developed a simple phantom and dedicated software for the quality assessment of positron emission tomography (PET) scanners. The phantom is a parallelepiped box filled with a relatively low activity 18FDG solution and in which simple test objects are placed. Various image quality parameters are checked, including signal-to-noise ratio, image uniformity, slice thickness, slice sensitivity profile, spatial resolution, and dose calibration accuracy. Automatic image analysis consists in detecting surfaces and objects, defining regions of interest, acquiring reference point coordinates, and establishing gray-scale profiles. The total time needed for quality assessment (preparation and image acquisition) is less than 15 min with 37 MBq (1 mCi) 18FDG. The system's ease of use encourages frequent image quality assessment-for example, the comparison of PET scanners in interdepartment studies and the monitoring and evaluation of possible drifts over time. By way of an example, the authors present weekly quality assessment results obtained over up to 7 months at four PET facilities.

Renovascular hypertension associated with neurofibromatosis: a case report.

Although vascular involvement in type 1 neurofibromatosis (NF1) is rare, it may lead to renal artery stenosis and renovascular hypertension (RVH). RVH may be treated using antihypertensive drugs, percutaneous transluminal renal angioplasty (PTRA), surgical reconstruction of the renal artery, or nefrectomy. In NF1 the results of PTRA are less predictable than in cases of fibromuscular dysplasia and atherosclerosis. We report a case of RVH associated with NF1. Despite administration of multiple antihypertensive drugs blood pressure remained uncontrolled. Selective left renal arteriography demonstrated two consecutive high-grade stenotic lesions with post-stenotic aneurysmal dilatation treated successfully with balloon dilatation. During the ensuing 2 year follow up complete normalization of blood pressure was observed. This case illustrates that endovascular therapy may be beneficial and should be considered a reasonable first option in these patients. However vascular involvement in NF may be progressive and therefore always requires continuing follow up.

Aortopulmonary artery fistula in atherosclerotic pseudoaneurysm presenting with congestive heart failure after aortic valve replacement.

An exceptional case of a giant pseudoaneurysm of the atherosclerotic ascending aorta complicated by aortopulmonary fistulization twelve years after aortic valve replacement is presented. The patient underwent successful surgical repair. In patients with a marked atherosclerotic thoracic aorta presenting with congestive heart failure and an acquired continuous systolo-diastolic murmur, aortopulmonary fistula should be considered and differentiated from ruptured sinus of valsalva aneurysm. Multi-slice computed tomography was the most useful diagnostic tool in planning surgical strategy and approach. Surgery is the treatment of choice for this serious albeit rare entity.

Cerebral blood flow and glucose metabolism in hypothyroidism: a positron emission tomography study.

Hypothyroidism is often associated with defective memory, psychomotor slowing, and depression. However, the relationship between thyroid status and cognitive or psychiatric disturbances remains unclear. Using psychometric scales, 10 patients who had undergone total thyroidectomy for thyroid carcinoma were evaluated for depression, anxiety, and psychomotor slowing; they were examined both when euthyroid and hypothyroid after thyroid hormone withdrawal. Positron emission tomography was used, with oxygen-15-labeled water and fluorine-18F-labeled 2-deoxy-2fluoro-D-glucose as the tracers, to correlate the regional cerebral blood flow and cerebral glucose metabolism with the mental state in patients. Two different image analysis techniques (regions of interest and statistical parametric maps) were applied. In hypothyroidism, there was a generalized decrease in regional cerebral blood flow (23.4%, P < 0.001) and in cerebral glucose metabolism (12.1%, P < 0.001) and there were no specific local defects. Patients were also significantly more depressed (P < 0.001), anxious (P < 0.001) and psychomotor slowed (P < 0.005) in hypo than in euthyroid status. These results indicate that the brain activity was globally reduced in severe hypothyroidism of short duration without the regional modifications usually observed in primary depression.

Positron emission tomography using(18)F-fluoro-deoxyglucose and euglycaemic hyperinsulinaemic glucose clamp: optimal criteria for the prediction of recovery of post-ischaemic left ventricular dysfunction. Results from the European Community Concerted Action Multicenter study on use of(18)F-fluoro-deoxyglucose Positron Emission Tomography for the Detection of Myocardial Viability.

AIMS: To assess the accuracy of positron emission tomography to predict recovery of global cardiac function after revascularization in patients with coronary artery disease. METHODS AND RESULTS: One hundred and seventy-eight patients (157 male, 58+/-10 years) with coronary artery disease and left ventricular dysfunction (mean ejection fraction 39+/-14%) were enrolled in six European centres. They underwent a common protocol for the assessment of viability using(18)F-fluoro-2-deoxyglucose (FDG) positron emission tomography during a standardized euglycaemic hyperinsulinaemic glucose clamp before revascularization by either surgery (n=140) or angioplasty (n=38). Seven patients were excluded because of incomplete revascularization of a dysfunctional region. Based on the recovery of global ejection fraction 2-6 months after revascularization, patients were classified into two groups: 82 patients who had a >5% improvement in ejection fraction postoperatively, and 89 patients without postoperative ejection fraction improvement. Optimal cut-off points for postoperative improvement of global cardiac function were computed, using receiver operating curve analysis. The highest sensitivity (79%) and specificity (55%) for predicting postoperative ejection fraction improvement by positron emission tomography was found when three or more dysfunctional segments had a relative FDG uptake >45% of normal remote myocardium (overall accuracy 67%). CONCLUSIONS: In a large cohort of coronary patients with impaired ejection fraction, FDG positron emission tomography demonstrated high sensitivity and moderate specificity to predict improvement of cardiac function after coronary revascularization.

Comparison of regional cerebral blood flow and glucose metabolism in the normal brain: effect of aging.

The regional cerebral blood flow (rCBF) and metabolic rate for glucose (rCMRGlc) are associated with functional activity of the neural cells. The present work reports a comparison study between rCBF and rCMRGlc in a normal population as a function of age. 10 young (25.9+/-5.6 years) and 10 old (65.4+/-6.1 years) volunteers were similarly studied at rest. In each subject, rCBF and rCMRGlc were measured in sequence, during the same session. Both rCBF and rCMRGlc values were found to decrease from young (mean rCBF=43.7 ml/100 g per min; mean rCMRGlc=40.6 micromol/100 g per min) to old age (mean rCBF=37.3 ml/100 g per min; mean rCMRGlc=35.2 micromol/100 g per min), resulting in a drop over 40 years of 14.8% (0.37%/year) and 13.3% (0.34%/year), respectively. On a regional basis, the frontal and the visual cortices were observed to have, respectively, the highest and the lowest reduction in rCBF, while, for rCMRGlc, these extremes were observed in striatum and cerebellum. Despite these differences, the ratio of rCBF to rCMRGlc was found to have a similar behavior in all brain regions for young and old subjects as shown by a correlation coefficient of 88%. This comparative study indicates a decline in rCBF and rCMRGlc values and a coupling between CBF and CMRGlc as a function of age.

[11C]flumazenil metabolite measurement in plasma is not necessary for accurate brain benzodiazepine receptor quantification.

In this work, a mathematical correction for metabolites has been validated which estimates the relative amount of [11C]flumazenil ([11C]FMZ) in the total plasma curve from the tissue kinetic data without the need for direct metabolite measurement in blood plasma samples. Kinetic data were obtained using a 90-min three-injection protocol on five normal volunteers. First, the relative amount of [11C]FMZ in plasma was modelled by a two-parameter exponential function. The parameters were estimated either directly by fitting this model to the blood plasma metabolite measurements, or indirectly from the simultaneous fitting of tissue time activity curves from several brain regions with a non-linear FMZ kinetic model. Second, the direct and indirect metabolite corrections were fixed and the FMZ compartmental parameters were determined on a regional basis in the brain. The validation was performed by comparing the regional values of benzodiazepine receptor density Bmax and equilibrium dissociation constant Kd obtained with the direct metabolite correction with those values obtained with the indirect correction. For Bmax, the correlation coefficient r2 was above 0.97 for all subjects and the slope values of the linear regression were within the interval [0.97, 1.2]. For Kd, r2 was above 0.96, and the slope values of the linear regression were within the interval [0.99, 1.1]. Simulation studies were performed in order to evaluate whether this metabolite correction method could be used in a clinical protocol where only a single [11C]FMZ injection and a linear compartmental model are used. The resulting [11C]FMZ distribution volume estimates were found to be linearly correlated with the true values, with r2=1.0 and a slope value of 1.1. The mathematical metabolite correction proved to be a feasible and reliable method to estimate the relative amount of [11C]FMZ in plasma and the compartmental model parameters for three-injection protocols. Although validation with real data is necessary, simulation results suggest that our analysis method may also be applied to single-injection protocols.

Functional imaging of visual semantic processing in the human brain.

Previous neuroimaging studies have identified a large network of cortical areas involved in semantic processing in the human brain, which includes left occipito-temporal and inferofrontal areas. Most studies, however, investigated exclusively the associative/functional semantic knowledge by using mainly words and/or language related tasks, and this factor may have contributed to the large left hemisphere superiority found in semantic processing and to the controversial involvement of left prefrontal structures. The present study investigates the neural basis of visual objects knowledge, accessed exclusively through pictorial information. Regional cerebral blood flow (rCBF) was assessed using positron emission tomography (PET) during 3 conditions in right-handed normal volunteers: resting with eyes closed, retrieval of semantic information related to visual properties of objects (real size), and visual categorization based on physical properties of the image. Confirming previous experiments and neuropsychological findings, most activations were found in left occipito-temporal areas during retrieval of visual semantic knowledge. The absence of any activation in the left prefrontal inferior cortex for visual semantic processing confirms recent observations which suggest that this region would not be involved in retrieval of visual semantic knowledge from living entities. Rather, such knowledge about visual properties of objects, situated closely to cortical regions mediating perception of the visual attributes, can be retrieved directly from these regions when visual images are used as entry level stimuli.

Improvement of myocardial blood flow to ischemic regions by angiotensin-converting enzyme inhibition with quinaprilat IV: a study using [15O] water dobutamine stress positron emission tomography.

OBJECTIVES: This study was designed to analyze the effects of acute angiotensin-converting enzyme (ACE) inhibition on myocardial blood flow (MBF) in control and ischemic regions. BACKGROUND: Although animal studies indicate an improvement of MBF to ischemic regions after ACE inhibition, this effect has not been conclusively demonstrated in patients with coronary artery disease. METHODS: Myocardial blood flow was analyzed in ischemic and nonischemic regions of 10 symptomatic patients with coronary artery disease using repetitive [15O] water positron emission tomography at rest and during maximal dobutamine stress before and after ACE inhibition with quinaprilat 10 mg i.v. To exclude the possibility that repetitive ischemia may cause an increase in MBF, eight patients underwent the same protocol without quinaprilat (placebo patients). RESULTS: Rate pressure product in control and quinaprilat patients was comparable. In placebo patients, repetitive dobutamine stress did not change MBF to ischemic regions (1.41 +/- 0.17 during the first stress vs. 1.39 +/- 0.19 ml/min/g during the second stress, p = 0.93). In contrast, MBF in ischemic regions increased significantly after acute ACE inhibition with quinaprilat during repetitive dobutamine stress (1.10 +/- 0.13 vs. 1.69 +/- 0.17 ml/min/g, p < 0.015). Dobutamine coronary reserve in ischemic regions remained unchanged in placebo patients (1.07 +/- 0.11 vs. 1.10 +/- 0.16, p = 0.92), but increased significantly after quinaprilat (0.97 +/- 0.10 vs. 1.44 +/- 0.14, p < 0.002). Total coronary resistance decreased after ACE inhibition (123 +/- 19 vs. 71 +/- 10 mm Hg x min x g/ml, p < 0.02). CONCLUSIONS: Angiotensin-converting enzyme inhibition by quinaprilat significantly improves MBF to ischemic regions in patients with coronary artery disease.

A standardized blood sampling scheme in quantitative FDG-PET studies.

Quantitative estimation of brain glucose metabolism (rCMRGlc) with positron emission tomography and fluorodeoxyglucose involves arterial blood sampling to estimate the delivery of radioactivity to the brain. Usually, for an intravenous injection of 30 s duration, an accurate input curve requires a frequency of one sample every 5 s or less to determine the peak activity in arterial plasma during the first 2 min after injection. In this work, 13 standardized sampling times were shown to be sufficient to accurately define the input curve. This standardized input curve was subsequently fitted by a polynomial function for its rising part and by spectral analysis for its decreasing part. Using the measured, the standardized, and the fitted input curves, rCMRGlc was estimated in 32 cerebral regions of interest in 20 normal volunteers. Comparison of rCMRGlc values obtained with the measured and the fitted input curves showed that both procedures gave consistent results, with a maximal relative error in mean rCMRGlc of 1% when using the autoradiographic method and 2% using kinetic analysis of dynamic data. This input-curve-fitting technique, which is not dependent on the peak time occurrence, allows an accurate determination of the input-curve shape from reduced sampling schemes.

Attenuation correction in whole-body FDG oncological studies: the role of statistical reconstruction.

Whole-body fluorine-18 fluoro-2-d-deoxyglucose positron emission tomography (FDG-PET) is widely used in clinical centres for diagnosis, staging and therapy monitoring in oncology. Images are usually not corrected for attenuation since filtered backprojection (FBP) reconstruction methods require a 10 to 15-min transmission scan per bed position on most current PET devices equipped with germanium-68 rod transmission sources. Such an acquisition protocol would increase the total scanning time beyond acceptable limits. The aim of this work is to validate the use of iterative reconstruction methods, on both transmission and emission scans, in order to obtain a fully corrected whole-body study within a reasonable scanning time of 60 min. Five minute emission and 3-min transmission scans are acquired at each of the seven bed positions. The transmission data are reconstructed with OSEM (ordered subsets expectation maximization) and the last iteration is reprojected to obtain consistent attenuation correction factors (ACFs). The emission image is then also reconstructed with OSEM, using the emission scan corrected for normalization, scatter and decay together with the set of consistent ACFs as inputs. The total processing time is about 35 min, which is acceptable in a clinical environment. The image quality, readability and accuracy of uptake quantification were assessed in 38 patients scanned for various malignancies. The sensitivity for tumour detection was the same for the non-attenuation-corrected (NAC-FBP) and the attenuation-corrected (AC-OSEM) images. The AC-OSEM images were less noisy and easier to interpret. The interobserver reproducibility was significantly increased when compared with non-corrected images (96.1% vs 81.1%, P<0.01). Standardized uptake values (SUVs) measured on images reconstructed with OSEM (AC-OSEM) and filtered backprojection (AC-FBP) were similar in all body regions except in the pelvic area, where SUVs were higher on AC-FBP images (mean increase 7.74%, P<0. 01). Our results show that, when statistical reconstruction is applied to both transmission and emission data, high quality quantitative whole-body images are obtained within a reasonable scanning (60 min) and processing time, making it applicable in clinical practice.