Kinetics of H2 Adsorption at the Metal-Support Interface of Au/TiO2 Catalysts Probed by Broad Background IR Absorbance.

H2 adsorption on Au catalysts is weak and reversible, making it difficult to quantitatively study. We demonstrate H2 adsorption on Au/TiO2 catalysts results in electron transfer to the support, inducing shifts in the FTIR background. This broad background absorbance (BBA) signal is used to quantify H2 adsorption; adsorption equilibrium constants are comparable to volumetric adsorption measurements. H2 adsorption kinetics measured with the BBA show a lower Eapp value (23 kJ mol-1 ) for H2 adsorption than previously reported from proxy H/D exchange (33 kJ mol-1 ). We also identify a previously unreported H-O-H bending vibration associated with proton adsorption on electronically distinct Ti-OH metal-support interface sites, providing new insight into the nature and dynamics of H2 adsorption at the Au/TiO2 interface.

Water Poisons H2 Activation at the Au-TiO2 Interface by Slowing Proton and Electron Transfer between Au and Titania.

Understanding the dynamic changes at the active site during catalysis is a fundamental challenge that promises to improve catalytic properties. While performing Arrhenius studies during H2 oxidation over Au/TiO2 catalysts, we found different apparent activation energies (Eapp) depending on the feedwater pressure. This is partially attributed to changing numbers of metal-support interface (MSI) sites as water coverage changes with temperature. Constant water coverage studies showed two kinetic regimes: fast heterolytic H2 activation directly at the MSI (Eapp ∼ 25 kJ/mol) and significantly slower heterolytic H2 activation mediated by water (Eapp ∼ 45 kJ/mol). The two regimes had significantly different kinetics, suggesting a complicated mechanism of water poisoning. Density functional theory (DFT) showed water has minor effects on the reaction thermodynamics, primarily attributable to intrinsic differences in surface reactivity of different Au sites in the DFT model. The DFT model suggested significant surface restructuring of the TiO2 support during heterolytic H2 adsorption; evidence for this phenomenon was observed during in situ infrared spectroscopy experiments. A monolayer of water on the hydroxylated TiO2 surface increased the H2 dissociation activation barrier by ∼0.2 eV, in good agreement the difference in experimentally measured values. DFT calculations suggested H2 activation goes through a proton-coupled electron-transfer-like mechanism. During proton transfer to a basic support hydroxyl group, electron density is distributed through the gold nanorod and partially localized on the protonated support hydroxyl group. Water slows H2 activation by slowing this H+ transfer, forcing negative charge buildup on the Au and increasing the transition state energy.

CO Oxidation Kinetics over Au/TiO2 and Au/Al2O3 Catalysts: Evidence for a Common Water-Assisted Mechanism.

The mechanism of CO oxidation over supported gold catalysts has long been debated, with two prevailing mechanisms dominating the discussion: a water-assisted mechanism and a mechanism involving O-defect sites. In this study, we directly address this debate through a kinetic and mechanistic investigation of the role of water in CO oxidation over Au/TiO2 and Au/Al2O3 catalysts; the results clearly indicate a common water-assisted mechanism to be at work. Water adsorption isotherms were determined with infrared spectroscopy; the extracted equilibrium constant was essentially the same for both catalysts. Added water decreases CO adsorption on Au/TiO2, likely by blocking CO binding sites at the metal-support interface. Reaction kinetics (CO, O2, and H2O reaction orders) were essentially the same for both catalysts, as were measured O-H(D) kinetic isotope effects. These data indicate that the two catalysts operate by essentially the same mechanism under the conditions of these experiments (ambient temperature, significant amounts of water available). A reaction mechanism incorporating the kinetic and thermodynamic data and accounting for different CO and O2/COOH binding sites is proposed. The mechanism and kinetic data are treated with an active site (Michaelis-Menten) approach. This indicated that water adsorption does not significantly affect reaction rate constants, only the number of active sites available at a given water pressure. Extracted water and O2 binding constants are similar on both catalysts and consistent with previous DFT calculations. Water adsorption constants are also similar to independently determined equilibrium constants measured by IR spectroscopy. The likely roles of water, surface carbonates, and oxygen vacancies at the metal-support interface are discussed. The results definitively show that, at least in the presence of added water, O vacancies cannot play an important role in the room-temperature catalysis, and that the water-assisted mechanism is far more consistent with the preponderance of the kinetic data.

H2 Oxidation over Supported Au Nanoparticle Catalysts: Evidence for Heterolytic H2 Activation at the Metal-Support Interface.

Water adsorbed at the metal-support interface (MSI) plays an important role in multiple reactions. Due to its importance in CO preferential oxidation (PrOx), we examined H2 oxidation kinetics in the presence of water over Au/TiO2 and Au/Al2O3 catalysts, reaching the following mechanistic conclusions: (i) O2 activation follows a similar mechanism to that proposed in CO oxidation catalysis; (ii) weakly adsorbed H2O is a strong reaction inhibitor; (iii) fast H2 activation occurs at the MSI, and (iv) H2 activation kinetics are inconsistent with traditional dissociative H2 chemisorption on metals. Density functional theory (DFT) calculations using a supported Au nanorod model suggest H2 activation proceeds through a heterolytic dissociation mechanism, resulting in a formal hydride residing on the Au and a proton bound to a surface TiOH group. This potential mechanism was supported by infrared spectroscopy experiments during H2 adsorption on a deuterated Au/TiO2 surface, which showed rapid H-D scrambling with surface hydroxyl groups. DFT calculations suggest that the reaction proceeds largely through proton-mediated pathways and that typical Brønsted-Evans Polanyi behavior is broken by introducing weak acid/base sites at the MSI. The kinetics data were successfully reinterpreted in the context of the heterolytic H2 activation mechanism, tying together the experimental and computational evidence and rationalizing the observed inhibition by physiorbed water on the support as blocking the MSI sites required for heterolytic H2 activation. In addition to providing evidence for this unusual H2 activation mechanism, these results offer additional insight into why water dramatically improves CO PrOx catalysis over Au.

Surface Hydroxyl Chemistry of Titania- and Alumina-Based Supports: Quantitative Titration and Temperature Dependence of Surface Brønsted Acid-Base Parameters.

Surface hydroxyl groups on metal oxides play significant roles in catalyst synthesis and catalytic reactions. Despite the importance of surface hydroxyls in broader material applications, quantitative measurements of surface acid-base properties are not regularly reported. Here, we describe direct methods to quantify fundamental properties of surface hydroxyls on several titania- and alumina-based supports. Comparing commercially available anatase, rutile, P25, and P90 titania, thermogravimetric analysis (TGA) indicated that the total surface hydroxyl density varied by a factor of 2, and each surface hydroxyl is associated with approximately one weakly adsorbed water molecule. Proton-exchange site densities, determined at 25 °C with slurry acid-base titrations, led to several conclusions: (i) the intrinsic acidity/basicity of surface hydroxyls were similar regardless of the titania source; (ii) differences in the surface isoelectric point (IEP) were primarily attributable to differences in the surface concentration of acid and base sites; (iii) rutile has a higher surface concentration of basic hydroxyls, leading to a higher IEP; and (iv) P25 and P90 titania have slightly higher surface concentrationsof acidic hydroxyls relative to anatase or rutile. Temperature effects on surface acid-base properties are rarely reported yet are significant: from 5 to 65 °C, IEP values change by roughly one pH unit. The IEP changes were associated with large changes to the intrinsic acid-base equilibrium constants over this temperature range, rather than changes in the composition or concentration of the surface sites.

Plasma Lp-PLA(2) mass and apoB-lipoproteins that carry Lp-PLA(2) decrease after sodium.

BACKGROUND: Lipoprotein-associated phospholipase A(2) (Lp-PLA(2) ) is a novel cardiovascular risk marker, which is predominantly complexed to apolipoprotein (apo) B-containing lipoproteins in human plasma. As increasing dietary sodium intake may decrease plasma apoB-containing lipoproteins, we tested whether a sodium challenge lowers plasma Lp-PLA(2) mass, as well as the levels of apoB-containing lipoprotein particles carrying Lp-PLA(2) (apoB-Lp-PLA(2) ), employing a newly developed enzyme-linked immunosorbent assay. MATERIALS AND METHODS: In 45 women and 31 men (mean age 44 ± 14 years), plasma Lp-PLA(2) mass (turbidimetric immunoassay), the level of apoB-Lp-PLA(2) , expressed in apoB concentration and lipoproteins were measured in response to a 3-day challenge with 9 g sodium chloride tablets daily. RESULTS: Urinary sodium excretion increased from 165 ± 60 to 321 ± 70 mmol/24 h (P<0.001) after salt loading. Plasma Lp-PLA(2) mass decreased from 618 (493-719) to 588 (465-698) µg/L (P<0.001), and apoB-Lp-PLA(2) decreased from 0.276 (0.200-0.351) to 0.256 (0.189-0.328) g LDL protein/L (P=0.004) in response to the sodium challenge together with decreases in plasma total cholesterol, nonhigh-density lipoprotein (HDL) cholesterol, low-density lipoprotein (LDL) cholesterol, apolipoprotein B and the total cholesterol/HDL cholesterol ratio (P<0.01 for all). Changes in plasma Lp-PLA(2) mass were correlated positively with changes in total cholesterol, LDL cholesterol and non-HDL cholesterol (r=0.260-0.276, P<0.05 to P<0.02), whereas changes in apoB-Lp-PLA(2) were correlated positively with changes in non-HDL cholesterol and in the total cholesterol/HDL cholesterol ratio (r=0.232-0.385, P<0.05-0.01). CONCLUSION: Both plasma Lp-PLA(2) mass levels and apoB-Lp-PLA(2) decrease in response to a short-term oral sodium challenge.

Statin and fibrate combination does not additionally lower plasma cholesteryl ester transfer in type 2 diabetes mellitus.

BACKGROUND: Plasma cholesteryl ester transfer (CET) from high density lipoproteins (HDL) to very low and low density lipoproteins (VLDL+LDL) may predict (subclinical) atherosclerosis. We tested the extent to which plasma CET and cholesterol esterification (EST) are decreased by statin and fibrate combination therapy compared to statin and fibrate administration alone in type 2 diabetic patients. METHODS: Plasma CET and EST were measured by isotope assays in 14 type 2 diabetic patients, in whom a randomized placebo-controlled crossover study was carried out (8 weeks treatment with simvastatin (40 mg daily), bezafibrate (400 mg daily) and their combination). Plasma CET and EST from diabetic patients were compared with 42 non-diabetic control subjects with similar triglyceride levels. RESULTS: Plasma CET and EST were elevated in diabetic patients at baseline compared to control subjects (p < 0.01), and were correlated positively with non-HDL cholesterol and triglycerides in non-diabetic subjects and in diabetic patients at baseline (p < 0.01). Decreases in CET during combined treatment (p < 0.05) were not greater than the changes during simvastatin and bezafibrate monotherapy (p > 0.20). EST only decreased during bezafibrate therapy (p < 0.05). Changes in CET during treatment were correlated positively with changes in non-HDL cholesterol (p < 0.05) and triglycerides (p < 0.001). Changes in HDL cholesterol were related inversely to changes in CET (p < 0.05). CONCLUSIONS: Diabetes-associated plasma CET elevations are ameliorated by statin and fibrate monotherapy, but combined lipid lowering drug treatment does not additively lower CET. CET lowering likely contributes to HDL cholesterol changes during statin and fibrate administration.

Prostate-Specific Membrane Antigen Targeted Pet/CT Imaging in Patients with Colon, Gastric and Pancreatic Cancer.

Current imaging modalities frequently misjudge disease stage in colorectal, gastric and pancreatic cancer. As treatment decisions are dependent on disease stage, incorrect staging has serious consequences. Previous preclinical research and case reports indicate that prostate-specific membrane antigen (PSMA)-targeted PET/CT imaging might provide a solution to some of these challenges. This prospective clinical study aims to assess the feasibility of [18F]DCFPyL PET/CT imaging to target and visualize primary colon, gastric and pancreatic cancer. In this prospective clinical trial, patients with colon, gastric and pancreatic cancer were included and underwent both [18F]DCFPyL and [18F]FDG PET/CT scans prior to surgical resection or (for gastric cancer) neoadjuvant therapy. Semiquantitative analysis of immunohistochemical PSMA staining was performed on the surgical resection specimens, and the results were correlated to imaging parameters. The results of this study demonstrate detection of the primary tumor by [18F]DCFPyL PET/CT in 7 out of 10 patients with colon, gastric and pancreatic cancer, with a mean tumor-to-blood pool ratio (TBR) of 3.3 and mean SUVmax of 3.6. However, due to the high surrounding uptake, visual distinction of these tumors was difficult, and the SUVmax and TBR on [18F]FDG PET/CT were significantly higher than on [18F]DCFPyL PET/CT. In addition, no correlation between PSMA expression in the resection specimen and SUVmax on [18F]DCFPyL PET/CT was found. In conclusion, the detection of several gastrointestinal cancers using [18F]DCFPyL PET/CT is feasible. However, low tumor expression and high uptake physiologically in organs/background hamper the clear distinction of the tumor. As a result, [18F]FDG PET/CT was superior in detecting colon, gastric and pancreatic cancers.

A single-substrate model to interpret intra-annual stable isotope signals in tree-ring cellulose.

The carbon and oxygen stable isotope composition of wood cellulose (delta(13)C(cellulose) and delta(18)O(cellulose), respectively) reveal well-defined seasonal variations that contain valuable records of past climate, leaf gas exchange and carbon allocation dynamics within the trees. Here, we present a single-substrate model for wood growth to interpret seasonal isotopic signals collected in an even-aged maritime pine plantation growing in South-west France, where climate, soil and flux variables were also monitored. Observed seasonal patterns in delta(13)C(cellulose) and delta(18)O(cellulose) were different between years and individuals, and mostly captured by the model, suggesting that the single-substrate hypothesis is a good approximation for tree ring studies on Pinus pinaster, at least for the environmental conditions covered by this study. A sensitivity analysis revealed that the model was mostly affected by five isotopic discrimination factors and two leaf gas-exchange parameters. Modelled early wood signals were also very sensitive to the date when cell wall thickening begins (t(wt)). Our model could therefore be used to reconstruct t(wt) time series and improve our understanding of how climate influences this key parameter of xylogenesis.

Antioxidant role of plasma carotenoids in bronchopulmonary dysplasia in preterm infants.

OBJECTIVES: Oxidative stress is implicated in the pathogenesis of bronchopulmonary dysplasia (BPD) and consequently, it might be theorized that sufficient antioxidant defenses are needed to prevent BPD. We hypothesized that, except for vitamins E and A, carotenoids may be important in this defense. Carotenoids are present in human milk; however, they are not added to parenteral nutrition, the main food source of preterm infants in the first week of life. AIM: To evaluate prospectively the role of carotenoids in BPD in a cohort of preterm infants. METHODS: The plasma concentrations of F(2alpha)-isoprostane, alpha- and beta-carotene, lycopene, lutein, vitamin A, and the vitamin E/cholesterol ratio were studied at days 1, 3, and 7 in a cohort of 109 preterm infants, of whom 19 had BPD. RESULTS: When comparing the BPD and control group, infants in the BPD group were younger (p<0.001) and beta-carotene (day 7, p<0.01) and vitamin A concentrations were lower (days 3 and 7, p<0.001). Lycopene, lutein, alpha-carotene, vitamin E, and F(2alpha)-isoprostane concentrations did not differ between groups. CONCLUSIONS: Plasma beta-carotene and vitamin A concentrations are lower in BPD infants which may result in a reduction of their antioxidant protection.

Kinetic evaluation of highly active supported gold catalysts prepared from monolayer-protected clusters: an experimental Michaelis-Menten approach for determining the oxygen binding constant during CO oxidation catalysis.

Thiol monolayer-protected Au clusters (MPCs) were prepared using dendrimer templates, deposited onto a high-surface-area titania, and then the thiol stabilizers were removed under H2/N2. The resulting Au catalysts were characterized with transmission electron microscopy, X-ray photoelectron spectroscopy, and infrared spectroscopy of adsorbed CO. The Au catalysts prepared via this route displayed minimal particle agglomeration during the deposition and activation steps. Structural data obtained from the physical characterization of the Au catalysts were comparable to features exhibited from a traditionally prepared standard Au catalyst obtained from the World Gold Council (WGC). A differential kinetic study of CO oxidation catalysis by the MPC-prepared Au and the standard WGC catalyst showed that these two catalyst systems have essentially the same reaction order and Arrhenius apparent activation energies (28 kJ/mol). However, the MPC-prepared Au catalyst shows 50% greater activity for CO oxidation. Using a Michaelis-Menten approach, the oxygen binding constants for the two catalyst systems were determined and found to be essentially the same within experimental error. To our knowledge, this kinetic evaluation is the first experimental determination of oxygen binding by supported Au nanoparticle catalysts under working conditions. The values for the oxygen binding equilibrium constant obtained from the Michaelis-Menten treatment (ca. 29-39) are consistent with ultra-high-vacuum measurements on model catalyst systems and support density functional theory calculations for oxygen binding at corner or edge atoms on Au nanoparticles and clusters.

Prognostic value of troponin after elective percutaneous coronary intervention: A meta-analysis.

BACKGROUND: Although the prognostic importance of troponin in patients with anacute coronary syndrome is clear, the significance of troponin elevation after elective percutaneous coronary intervention (PCI) is a subject of debate. However, most studies up to now had a small sample size and insufficient events during follow-up. METHODS: Electronic and manual searches were performed of studies reporting on prognosis of troponin after elective PCI. A meta-analysis was done of all suitable studies, with death in follow-up as primary endpoint and the combination of death or nonfatal myocardial infarction in follow-up as secondary endpoint. RESULTS: 20 studies involving 15,581 patients were included. These studies were published between 1998 and 2007. Overall, troponin was elevated after elective PCI in 32.9% of patients. The follow-up period varied between 3 and 67 months (mean 16.3). Increased mortality was significantly associated with troponin elevation after PCI (4.4% vs. 3.3%, P = 0.001; OR 1.35). Furthermore, the combined endpoint of mortality or nonfatal myocardial infarction also occurred more often in patients with post-procedural troponin elevation (8.1% vs. 5.2%, P < 0.001; OR 1.59). CONCLUSIONS: According to this meta-analysis, troponin elevation after elective PCI provides important prognostic information.

Evaluating differences in the active-site electronics of supported Au nanoparticle catalysts using Hammett and DFT studies.

Supported metal catalysts, which are composed of metal nanoparticles dispersed on metal oxides or other high-surface-area materials, are ubiquitous in industrially catalysed reactions. Identifying and characterizing the catalytic active sites on these materials still remains a substantial challenge, even though it is required to guide rational design of practical heterogeneous catalysts. Metal-support interactions have an enormous impact on the chemistry of the catalytic active site and can determine the optimum support for a reaction; however, few direct probes of these interactions are available. Here we show how benzyl alcohol oxidation Hammett studies can be used to characterize differences in the catalytic activity of Au nanoparticles hosted on various metal-oxide supports. We combine reactivity analysis with density functional theory calculations to demonstrate that the slope of experimental Hammett plots is affected by electron donation from the underlying oxide support to the Au particles.

Tuning supported catalyst reactivity with dendrimer-templated Pt-Cu nanoparticles.

The effects of particle composition on heterogeneous catalysis were studied using dendrimer-encapsulated nanoparticles (DENs) as precursors to supported Pt-Cu catalysts. Bimetallic Pt-Cu DENs with varying Pt/Cu ratios were prepared in an anaerobic aqueous solution and deposited onto a high-purity commercial alumina support. The dendrimer template was then thermally removed to yield supported nanoparticle catalysts, which were studied with toluene hydrogenation and CO oxidation catalysis as well as infrared spectroscopy of adsorbed CO. Incorporating Cu into Pt nanoparticles had opposite effects on the two test reactions. Cu acted as a mild promoter for CO oxidation catalysis, and the promoting effect was independent of the amount of Cu present. Conversely, Cu acted as a strong poison for toluene hydrogenation catalysis, and the normalized rate tracked inversely with Cu content. Infrared spectroscopy of the supported nanoparticles indicated that electronic effects (electron donation from Cu to Pt) were minimal for these materials. Consequently, the catalysis results are interpreted in terms of potential structural differences as a function of Cu incorporation and reaction conditions.

Factors associated with early opioid prescription among workers with low back injuries.

UNLABELLED: Prescription of opioids for nonmalignant musculoskeletal pain has increased substantially in recent years, but there is little information on the incidence of, or factors associated with, such prescription for work-related back pain. In a prospective cohort study (N = 1,067), we examined associations between worker sociodemographic and other characteristics and opioid prescription within six weeks of the first medical visit for workers' compensation claims for work loss due to back injury. We examined administrative, pharmacy, and worker-reported data. In bivariate logistic regression models, Hispanics were less likely than non-Hispanic whites to receive opioid prescriptions, and very high body mass index, daily tobacco use, greater pain and physical disability, pain radiating below the knee, injury severity categorizations (from medical records) of major sprain and radiculopathy, and worse mental health were associated with opioid prescription. Adjusting for demographics, pain intensity, and physical disability, opiate prescription was significantly associated with daily tobacco use, pain radiating below the knee, and injury severity categories (major sprain and radiculopathy). Knowledge of worker characteristics associated with early opioid prescription may be useful in future studies of the role of early pain treatment in influencing subsequent course of pain and disability among workers with back injuries. PERSPECTIVE: Little is known about patient characteristics that may influence physicians' decisions concerning prescription of opioids for acute back pain. Not surprisingly, workers with more severe back injuries are more likely to be prescribed opioids, but reasons for prescription disparities based on ethnicity and tobacco use warrant further study.

Controlling activity and selectivity using water in the Au-catalysed preferential oxidation of CO in H2.

Industrial hydrogen production through methane steam reforming exceeds 50 million tons annually and accounts for 2-5% of global energy consumption. The hydrogen product, even after processing by the water-gas shift, still typically contains ∼1% CO, which must be removed for many applications. Methanation (CO + 3H2 → CH4 + H2O) is an effective solution to this problem, but consumes 5-15% of the generated hydrogen. The preferential oxidation (PROX) of CO with O2 in hydrogen represents a more-efficient solution. Supported gold nanoparticles, with their high CO-oxidation activity and notoriously low hydrogenation activity, have long been examined as PROX catalysts, but have shown disappointingly low activity and selectivity. Here we show that, under the proper conditions, a commercial Au/Al2O3 catalyst can remove CO to below 10 ppm and still maintain an O2-to-CO2 selectivity of 80-90%. The key to maximizing the catalyst activity and selectivity is to carefully control the feed-flow rate and maintain one to two monolayers of water (a key CO-oxidation co-catalyst) on the catalyst surface.

Optimizing an online SPE-HPLC method for analysis of (R)-[11C]1-(2-chlorophenyl)-N-methyl-N-(1-methylpropyl)-3-isoquinolinecarboxamide [(R)-[11C]PK11195] and its metabolites in humans.

(R)-[11C]PK11195 is used as a positron emission tomography tracer for activated microglia in several neurological disorders. Quantification of specific binding requires a metabolite-corrected plasma input function. In this study, a high-performance liquid chromatography (HPLC) procedure with online solid phase extraction was modified for analyzing (R)-[11C]PK11195 plasma samples, yielding total sample recoveries of more than 98%. When applied to human studies, the use of two HPLC systems enabled analysis of up to seven plasma samples under regular conditions. Online radioactivity detection was compared with offline sample measurements of HPLC profiles. Offline measurements provided the most reliable results especially for late plasma samples. In 10 patients, an average decrease of parent compound from 94.6% at 2.5 min to 45.2% at 1 h after administration was observed.

Intra-annual variations in climate influence growth and wood density of Norway spruce.

Intra-annual radial growth variations of two Norway spruce trees (Picea abies (L.) Karst.) were monitored over 4 years, at four heights up the stem, by means of point-dendrometers. The trees were then felled and radial wood samples were cut from the radii that had been monitored by the dendrometers and analyzed for density. From the radial growth measurements recorded by the dendrometers, we related positions within the rings to dates, thus making possible investigation of the relationships between changes within the rings in wood density and fluctuations in climate or growth rate. Radial growth started in early April and ended, with large intra-annual differences, in August or September. Short-term variations in growth rate were related to fluctuations in climate parameters and soil water reserves. The sensitivity of radial growth to climate decreased with stem height. Wood density responded strongly to drought events, and a dry period in June 1996 induced false-ring formation. Wood density was relatively independent of growth rate and climatic conditions during the first part of the growing season, but increased with decreasing radial growth rate later in the growing season.

Sternal uptake on bone scintigraphy: age-related variants.

BACKGROUND: When reporting bone scans, it is important to distinguish between normal variants and skeletal pathology involving the sternum. There are only limited reports dealing with age-related normal variants of the sternum on bone scintigraphy. METHODS: We have studied the age-related variants of sternal uptake on bone scintigraphy. In a prospective study, 152 consecutive patients (66 males and 86 females) undergoing whole-body bone scanning, and who had no symptoms associated with the sternum, were evaluated for patterns of normal sternal uptake. Three hours after intravenous injection of (99m)Tc-methylene diphosphonate ((99m)Tc-MDP), whole-body bone scans in the anterior and posterior projections were acquired. Patterns of sternal uptake, including the sites and distribution of increased and decreased uptake, were analysed using age-related groups. RESULTS: Three patterns of tracer uptake in the sternum were recognized: a uniform pattern was most common in children (< or =12 years); a heterogeneous uptake pattern was frequently seen in adolescents, young adult and adult groups; and a segmented pattern was commonly seen in the geriatric group (>60 years). A predominant focal finding was a hot spot at the angle of Louis. In addition, there were focal spots of decreased tracer uptake in the lower sternum, just above the xiphoid process, and spots of increased tracer uptake in the body of the sternum. Such focal spots were not seen in subjects of less than 12 years of age. CONCLUSION: Evolutionary changes of the sternum appear to exist throughout life. There are age-related normal variants of sternal uptake on bone scintigraphy.

Membrane protein reconstitution and crystallization by controlled dilution.

Efficient reconstitution of membrane proteins for functional analyses can be achieved by dilution of a ternary mixture containing proteins, lipids and detergents. Once the dilution reaches the point where the free detergent concentration would become lower than the critical micellar concentration, detergent is recruited from the bound detergent pool, and association of proteins and lipids is initiated. Here we show that dilution is also suitable for the assembly of two-dimensional crystals. A device has been designed that allows controlled dilution of a protein-lipid-detergent mixture to induce formation of densely packed or crystalline proteoliposomes. Turbidity is used to monitor the progress of reconstitution on-line, while dilution is achieved by computer-controlled addition of buffer solution in sub-microliter steps. This system has mainly been tested with porin OmpF, a typical beta-barrel protein, and aquaporin-1, a typical alpha-helical protein. The results demonstrate that large, highly ordered two-dimensional crystals can be produced by the dilution method.