The deposition of metal nanoparticles on carbon surfaces: the role of specific functional groups.

The enormous complexity of a typical heterogeneous catalyst makes understanding the development and properties of any active nanoparticles present extremely challenging. In the case of carbon based catalysts that difficulty is compounded by the variability of the carbon powders used. We have previously developed a strategy that addresses these problems by mimicking the catalyst preparation conditions very closely but using highly ordered pyrolytic graphite crystals (HOPG) as a model surface. This enables us to examine the effects of specific functional groups on nanoparticle formation. We report here an extension of our work characterising functional groups on the HOPG surface, using XPS and AFM to explore the deposition of gold from aqueous solution onto HOPG surfaces treated in a variety of ways to alter the surface functionality. The structure and oxidation state of the resulting nanoparticles depend critically on the nature of the functional groups present and offers some insight into the development of catalysts based on these materials. Hydroxyls are identified as key functional species, reducing gold ions to their metallic state whilst being oxidised themselves to carbonyls. Carbonyls meanwhile promote the nucleation of Au3+, creating a network of islands at the HOPG surface. The results have relevance not only to catalysts using activated carbons but also the new generation of materials based on graphene and carbon nanotubes.

Adverse outcomes after planned surgery with anticipated intensive care admission in out-of-office-hours time periods: a multicentre cohort study.

BACKGROUND: Increasing mortality for patients admitted to hospitals during the weekend is a contentious but well described phenomenon. However, it remains uncertain whether adverse outcomes, including prolonged hospital length-of-stay (LOS), may also occur after patients undergoing major planned surgery are admitted to an intensive care unit (ICU) out-of-office-hours, either during weeknights (after 18:00) or on weekends. METHODS: All planned surgical admissions requiring admission to one of 183 ICUs across Australia and New Zealand between 2006 and 2016 were included in this retrospective population-based cohort study. Primary outcomes were hospital LOS and hospital mortality. RESULTS: Of the total 504 713 planned postoperative ICU admissions, 33.6% occurred during out-of-office-hours. After adjusting for available risk factors, out-of-office-hours ICU admissions were associated with a significant increase in hospital LOS [+2.6 days, 95% confidence interval (CI) 2.5-2.6], mortality [odd ratio (OR) 1.5, 95%CI 1.4-1.6], and a reduced chance of being directly discharged home (OR 0.8, 95%CI 0.8-0.8). The strongest association for adverse outcomes occurred with weekend ICU admissions (hospital LOS: +3.0 days, 95%CI 3.2-3.6; hospital mortality: OR 1.7, 95%CI 1.6-1.8). Clustering of adverse outcomes by hospitals was not observed in the generalised estimating equation analyses. CONCLUSIONS: Despite a greater clinical staff availability and higher monitoring levels, planned surgery requiring anticipated out-of-office-hours ICU admission was associated with a prolonged hospital LOS, reduced discharge directly home, and increased mortality compared with in-office-hours admissions. Our findings have potential clinical, economic and health policy implications on how complex planned surgery should be planned and managed.

PdZn catalysts for CO2 hydrogenation to methanol using chemical vapour impregnation (CVI).

The formation of PdZn bimetallic alloys on ZnO, TiO2 and Al2O3 supports was investigated, together with the effect of alloy formation on the CO2 hydrogenation reaction. The chemical vapour impregnation (CVI) method produced PdZn nanoparticles with diameters of 3-6 nm. X-ray photoelectron spectroscopy and X-ray diffraction revealed the changes in the structure of the PdZn alloy that help stabilise formate intermediates during methanol synthesis. PdZn supported on TiO2 exhibits high methanol productivity of 1730 mmol kgcat-1 h-1 that is associated with the high dispersion of the supported PdZn alloy.

Spectrum of hot methane in astronomical objects using a comprehensive computed line list.

Hot methane spectra are important in environments ranging from flames to the atmospheres of cool stars and exoplanets. A new spectroscopic line list, 10to10, for (12)CH4 containing almost 10 billion transitions is presented. This comprehensive line list covers a broad spectroscopic range and is applicable for temperatures up to 1,500 K. Previous methane data are incomplete, leading to underestimated opacities at short wavelengths and elevated temperatures. Use of 10to10 in models of the bright T4.5 brown dwarf 2MASS 0559-14 leads to significantly better agreement with observations and in studies of the hot Jupiter exoplanet HD 189733b leads to up to a 20-fold increase in methane abundance. It is demonstrated that proper inclusion of the huge increase in hot transitions which are important at elevated temperatures is crucial for accurate characterizations of atmospheres of brown dwarfs and exoplanets, especially when observed in the near-infrared.

Incidence and risk factors for intensive care unit admission after bariatric surgery: a multicentre population-based cohort study.

BACKGROUND: With increasing rates of bariatric surgery and the consequential involvement of increasingly complex patients, uncertainty remains regarding the use of intensive care unit (ICU) services after bariatric surgery. Our objective was to define the incidence, indications, and outcomes of patients requiring ICU admission after bariatric surgery and assess whether unplanned ICU admission could be predicted using preoperative factors. METHODS: All adult bariatric surgery patients between 2007 and 2011 in Western Australia were identified from the Department of Health Data Linkage Unit database and merged with a separate database encompassing all subsequent ICU admissions pertaining to bariatric surgery. The minimal and mean follow-up periods were 12 months and 3.4 yr, respectively. RESULTS: Of the 12 062 patients who underwent bariatric surgery during the study period, 590 patients (4.9%; 650 ICU admissions) were admitted to an ICU after their bariatric surgery. Patients admitted to the ICU were older (48 vs 43 yr, P<0.001), more likely to be male (49.7 vs 20.2%, P<0.001), and more likely to require revisional bariatric surgery (14.4 vs 7.1%, P<0.001). One hundred and seventy-six patients required an emergent unplanned ICU admission, with 51 requiring multiple ICU admissions. Revisional or open surgery, diabetes mellitus, chronic respiratory disease, and obstructive apnoea were the strongest preoperative factors associated with unplanned ICU admission. CONCLUSIONS: Intensive care unit admission after bariatric surgery was uncommon (4.9% of all patients), with 30.9% of all referrals being unplanned. A nomogram and smartphone application based on five important preoperative factors may assist anaesthetists to conduct preoperative planning for high-risk bariatric surgical patients.

Predictors of early treatment discontinuation in a cohort of patients treated with boceprevir-based therapy for hepatitis C infection.

In this real-world cohort, 49% of patients stopped boceprevir-based hepatitis C therapy early, with only 20% stopping due to treatment futility. Having more comorbidities was significantly associated with early discontinuation. Tolerability of boceprevir-based regimens may be substantially worse than reported in clinical trials, particularly for patients with comorbidities.

Combinations of High Intensity Light Pulses and Thermosonication for the inactivation of Escherichia coli in orange juice.

The non-thermal technologies High Intensity Light Pulses (HILP) and Thermosonication (TS) were applied alone and in combination to study their effect on Escherichia coli inactivation in orange juice. Two different energy settings were chosen in the current study, 'Low' (L) and 'High' (H), being the combinations applied: HILP(L) (4.03 J/cm(2)), HILP(H) (5.1 J/cm(2)), TS(L) (2.8 min residence time at 40 °C) and TS(H) (5 min residence time at 50 °C). Both the individual technologies and their combinations (HILP&TS and TS&HILP) were studied. Results showed inactivation ranging from 1.10 (TS(H)) to 2.42 (HILP(H)) log cfu/ml for the hurdles when applied individually and from 2.5 (HILP(L)&TS(H)) to 3.93 (HILP(H)&TS(L)) log cfu/ml for the combined treatments. Similar reductions in E. coli populations were achieved in orange juice by all treatment combinations irrespective of the sequence in which they were applied.

Effectiveness of High Intensity Light Pulses (HILP) treatments for the control of Escherichia coli and Listeria innocua in apple juice, orange juice and milk.

High Intensity Light Pulses (HILP) represent an emerging processing technology which uses short (100-400 µs) light pulses (200-1100 nm) for product decontamination. In this study, model and real foods of differing transparencies (maximum recovery diluent (MRD), apple and orange juices and milk) were exposed to HILP in a batch system for 0, 2, 4 or 8 s at a frequency of 3 Hz. After treatment, inactivation of Escherichia coli or Listeria innocua was evaluated in pre-inoculated samples. Sensory and other quality attributes (colour, pH, Brix, titratable acidity, non-enzymatic browning, total phenols and antioxidant capacity (TEAC)) were assessed in apple juice. Microbial kill decreased with decreasing transparency of the medium. In apple juice (the most transparent beverage) E. coli decreased by 2.65 and 4.5 after exposure times of 2 or 4 s, respectively. No cell recovery was observed after 48 h storage at 4°C. No significant differences were observed in quality parameters, excepting TEAC and flavour score, where 8 s exposure caused a significant decrease (p<0.05). Based on these results, HILP with short exposure times could represent a potential alternative to thermal processing to eliminate undesirable microorganisms, while maintaining product quality, in transparent fruit juices.

Risk factors for transmission of carbapenem-resistant Enterobacterales to healthcare personnel gloves and gowns in the USA.

BACKGROUND: Hospitals are sources for acquisition of carbapenem-resistant Entero-bacterales (CRE), and it is believed that the contamination of healthcare personnel (HCP) hands and clothing play a major role in patient-to-patient transmission of antibiotic-resistant bacteria. AIM: The aim of this study was to determine which HCP types, HCP-patient interactions, and patient characteristics are associated with greater transmission of CRE to HCP gloves and gowns in the hospital. METHODS: This was a prospective observational cohort study that enrolled patients with recent surveillance or clinical cultures positive for CRE at five hospitals in four states in the USA. HCP gloves and gown were cultured after patient care. Samples were also obtained from patients' stool, perianal area, and skin of the chest and arm to assess bacterial burden. FINDINGS: Among 313 CRE-colonized patients and 3070 glove and gown cultures obtained after patient care, HCP gloves and gowns were found to be contaminated with CRE 7.9% and 4.3% of the time, respectively. Contamination of either gloves or gowns occurred in 10.0% of interactions. Contamination was highest (15.3%) among respiratory therapists (odds ratio: 3.79; 95% confidence interval: 1.61-8.94) and when any HCP touched the patient (1.52; 1.10-2.12). Associations were also found between CRE transmission to HCP gloves or gown and: being in the intensive care unit, having a positive clinical culture, and increasing bacterial burden on the patient. CONCLUSION: CRE transmission to HCP gloves and gown occurred frequently. These findings may inform evidence-based policies about what situations and for which patients contact precautions are most important.

Experimental and Theoretical Study of the Electronic Structures of Lanthanide Indium Perovskites LnInO3.

Ternary lanthanide indium oxides LnInO3 (Ln = La, Pr, Nd, Sm) were synthesized by high-temperature solid-state reaction and characterized by X-ray powder diffraction. Rietveld refinement of the powder patterns showed the LnInO3 materials to be orthorhombic perovskites belonging to the space group Pnma, based on almost-regular InO6 octahedra and highly distorted LnO12 polyhedra. Experimental structural data were compared with results from density functional theory (DFT) calculations employing a hybrid Hamiltonian. Valence region X-ray photoelectron and K-shell X-ray emission and absorption spectra of the LnInO3 compounds were simulated with the aid of the DFT calculations. Photoionization of lanthanide 4f orbitals gives rise to a complex final-state multiplet structure in the valence region for the 4f n compounds PrInO3, NdInO3, and SmInO3, and the overall photoemission spectral profiles were shown to be a superposition of final-state 4f n-1 terms onto the cross-section weighted partial densities of states from the other orbitals. The occupied 4f states are stabilized in moving across the series Pr-Nd-Sm. Band gaps were measured using diffuse reflectance spectroscopy. These results demonstrated that the band gap of LaInO3 is 4.32 eV, in agreement with DFT calculations. This is significantly larger than a band gap of 2.2 eV first proposed in 1967 and based on the idea that In 4d states lie above the top of the O 2p valence band. However, both DFT and X-ray spectroscopy show that In 4d is a shallow core level located well below the bottom of the valence band. Band gaps greater than 4 eV were observed for NdInO3 and SmInO3, but a lower gap of 3.6 eV for PrInO3 was shown to arise from the occupied Pr 4f states lying above the main O 2p valence band.

Antimicrobial effect and shelf-life extension by combined thermal and pulsed electric field treatment of milk.

AIMS: The impact of a combined hurdle treatment of heat and pulsed electric fields (PEF) was studied on native microbiota used for the inoculation of low-fat ultra-high temperature (UHT) milk and whole raw milk. Microbiological shelf-life of the latter following hurdle treatment or thermal pasteurization was also investigated. METHODS AND RESULTS: UHT milk was preheated to 30 degrees C, 40 degrees C or 50 degrees C over a 60-s period, pulsed for 50 micros or 60 micros at a field strength of 40 kV cm(-1) or for 33 micros at 50 kV cm(-1). Heat and PEF reduced the microbial count by a maximum of 6.4 log in UHT milk (50 degrees C; 50 kV cm(-1), 33 micros) compared to 6.0 log (P > or = 0.05) obtained by thermal pasteurization (26 s, 72 degrees C). When raw milk was treated with a combination of hurdles (50 degrees C; 40 kV cm(-1), 60 micros) a 6.0 log inactivation of microbiota was achieved and microbiological milk shelf-life was extended to 21 days under refrigeration (4 degrees C) vs 14 days in thermally pasteurized milk. Native microbiota was decreased by 6.7 log following conventional pasteurization. CONCLUSIONS: The findings suggest that heat and PEF achieved similar inactivation of native microbiota in milk and longer stabilization of microbiological shelf-life than thermal pasteurization. SIGNIFICANCE AND IMPACT OF THE STUDY: A hurdle approach of heat and PEF could represent a valid milk processing alternative to conventional pasteurization. Hurdle treatment might also preserve native milk quality better due to less thermal exposure.

Profound hypocalcaemia in a patient being anticoagulated with citrate for continuous renal replacement therapy.

Citrate, as an anticoagulant for continuous renal replacement therapy in critically ill patients, has some potential advantages over heparin, including a prolonged dialysis filter life and reduced risk of bleeding. The key parameter involved in monitoring the adequacy and safety of citrate anticoagulation during continuous renal replacement therapy pertains to the ionised and total plasma calcium levels. We report a case of severe systemic hypocalcaemia during continuous renal replacement therapy with citrate anticoagulation resulting from relentless sequestration of calcium due to undiagnosed evolving rhabdomyolysis. Although excessive systemic citrate accumulation can also cause hypocalcaemia, this complication was not observed in our patient. While an acceptable lower limit of ionised calcium remains unknown, severe rhabdomyolysis needs to be considered when a patient's ionised calcium levels are not responsive to standard calcium replacement therapy during continuous renal replacement therapy using citrate anticoagulation in critically ill patients.

Effect of low temperatures (-18 to +5°C) on the texture of beef lean.

The textural properties of beef over the temperature range -18 to +5°C were measured using Warner Bratzler (WB) and tensile techniques. In addition, the effects of rapid radio frequency (RF) tempering and slower conventional air tempering on texture were compared. Temperature showed a significant effect (P<0.05) on WB and tensile shear force, with higher values obtained at temperatures on or below -5°C. Work to fracture values showed two peaks at -15 and -3°C. Sample thickness and muscle fibre direction were also important factors affecting shear force, with samples cut across fibres showing higher values. Tempering method showed no effect (P⩾0.05) on the textural properties measured. In light of the rapid nature of RF tempering, these findings will be of interest to the meat industry.

A comparison of conventional and radio frequency defrosting of lean beef meats: Effects on water binding characteristics.

The effect of defrosting rate (slow conventional air vs. fast radio frequency (RF) method) on water holding properties of lean beef meat (whole, minced and comminuted) was investigated using a conventional centrifugation method (drip loss), nuclear magnetic resonance relaxometry (NMR) and dielectric spectroscopy. Tempering by radio frequency (RF) or a conventional air method had no subsequent effect (P⩾0.05) on drip loss. However, thawing by RF resulted in a significant decrease in drip loss (P<0.05) when compared to air thawing. Micronutrient loss (µg/mL of drip) was also greater in air thawed samples (P<0.05). NMR T(2) distributions did not show any marked difference between thawing methods. The dielectric properties of lean beef, measured from 0.01-20GHz at 5°C, were higher following RF thawing. Increased comminution reduced dielectric values, while fine comminution gave an additional fraction in the NMR T(2) distribution. These results provide valuable information on water binding in meat following RF tempering/thawing.

When ascites is not ascites.

The case is reported of a patient presenting with ascites and acute renal failure resulting from spontaneous rupture of the urinary bladder, 30 years after the successful initial treatment of childhood rhabdomyosarcoma. The delay in the presentation until the patient began to experience the symptoms due to urinary ascites, the diagnostic dilemma because of the rarity of the condition, and the possible aetiologies are discussed.

Retention of heroin and morphine-6 beta-glucuronide analgesia in a new line of mice lacking exon 1 of MOR-1.

Morphine produces analgesia by activating mu opioid receptors encoded by the MOR-1 gene. Although morphine-6 beta-glucuronide (M6G), heroin and 6-acetylmorphine also are considered mu opioids, recent evidence suggests that they act through a distinct receptor mechanism. We examined this question in knockout mice containing disruptions of either the first or second coding exon of MOR-1. Mice homozygous for either MOR-1 mutation were insensitive to morphine. Heroin, 6-acetylmorphine and M6G still elicited analgesia in the exon-1 MOR-1 mutant, which also showed specific M6G binding, whereas M6G and 6-acetylmorphine were inactive in the exon-2 MOR-1 mutant. These results provide genetic evidence for a unique receptor site for M6G and heroin analgesia.

Dielectric and thermophysical properties of different beef meat blends over a temperature range of -18 to +10°C.

Dielectric and thermophysical properties of three different beef meat blends (lean, fat and 50:50 mixture) were evaluated over a range of temperatures from -18 to +10°C. In the region of thawing (-3 to -1°C), dielectric constant (ε') and dielectric loss factor (ε') values for radio frequency (RF) and microwave (MW) were significantly higher (P<0.05) than at other measured temperatures for the three blends. In the same region, thermal conductivity (k), specific heat (c) and thermal diffusivity (α) also showed significant changes (P<0.05). k and α values were significantly lower, while c values were significantly higher in this region than at other measured temperatures for the three blends. RF (27.12MHz) vs. MW (896 and 2450MHz) frequencies had an important effect (P<0.05) on the measured dielectric properties of the beef meat blends, with a general tendency towards higher values at the RF frequency. Finally, composition significantly influenced (P<0.05) the measured dielectric and thermophysical properties at all temperatures used. These data are of potential value to food technologists in the context of rapid defrosting of meat products.

A comparison of conventional and radio frequency tempering of beef meats: Effects on product temperature distribution.

This study aimed to develop radio frequency (RF) pilot-scale protocols for tempering beef meat blends (4kg blocks) to achieve average temperatures between -2 and -5°C. Post-tempering temperature distribution in these blocks was compared to products tempered by conventional methods. The optimum RF power-time combination for tempering lean and 50:50 lean:fat mixtures to the target range was 500W for 11min which produced respective means of -3.6°C (s.d. 1.1) and -3.4°C (s.d. 1.5). In contrast, 400W for 11min was optimum for fat (mean -4.9°C, s.d. 2.1). This study shows the principal advantages of RF over conventional tempering as an approximate 30 fold tempering time reduction and a greater uniformity of end point temperature distribution under the conditions employed. Furthermore, power consumption was reduced approximately ninefold with RF compared to conventional tempering. More uniform temperature distribution was achieved in samples that were comminuted to a greater extent.