Stable Isolated Metal Atoms as Active Sites for Photocatalytic Hydrogen Evolution

The process of using solar energy to split water to produce hydrogen assisted by an inorganic semiconductor is crucial for solving our energy crisis and environmental problems in the future. However, most semiconductor photocatalysts would not exhibit excellent photocatalytic activity without loading suitable co-catalysts. Generally, the noble metals have been widely applied as co-catalysts, but always agglomerate during the loading process or photocatalytic reaction. Therefore, the utilization efficiency of the noble co-catalysts is still very low on a per metal atom basis if no obvious size effect exists, because heterogeneous catalytic reactions occur on the surface active atoms. Here, for the first time, we have synthesized isolated metal atoms (Pt, Pd, Rh, or Ru) stably by anchoring on TiO2, a model photocatalystic system, by a facile one-step method. The isolated metal atom based photocatalysts show excellent stability for H-2 evolution and can lead to a 6-13-fold increase in photocatalytic activity over the metal clusters loaded on TiO2 by the traditional method. Furthermore, the configurations of isolated atoms as well as the originality of their unusual stability were analyzed by a collaborative work from both experiments and theoretical calculations.

Young, Old, and Weathered Carbon—Part 2: Using Radiocarbon and Stable Isotopes to Identify Terrestrial Carbon Support of the Food Web in an Alkaline, Humic Lake

Carbon (C) and nitrogen (N) stable isotope analysis (SIA) has been used to identify the terrestrial subsidy of freshwater food webs. However, SIA fails to differentiate between the contributions of old and recently fixed terrestrial C and consequently cannot fully determine the source, age, and biochemical quality of terrestrial carbon. Natural abundance radiocarbon (∆14C) was used to examine the age and origin of carbon in Lower Lough Erne, Northern Ireland. 14C and stable isotope values were obtained from invertebrate, algae, and fish samples, and the results indicate that terrestrial organic C is evident at all trophic levels. High winter δ15N values in calanoid zooplankton (δ15N = 24‰) relative to phytoplankton and particulate organic matter (δ15N = 6‰ and 12‰, respectively) may reflect several microbial trophic levels between terrestrial C and calanoid invertebrates. Winter and summer calanoid ∆14C values show a seasonal switch between autochthonous and terrestrial carbon sources. Fish ∆14C values indicate terrestrial support at the highest trophic levels in littoral and pelagic food webs. 14C therefore is useful in attributing the source of carbon in freshwater in addition to tracing the pathway of terrestrial carbon through the food web.

Using radiocarbon and stable isotopes to identify sediment carbon sources in an alkaline, humic lake.

We present a pilot study that uses the radiocarbon (∆14C) method to determine the source of carbon buried in the surface sediment of Lough Erne, a humic, alkaline lake in northwest Ireland. ∆14C, δ13C and δ15N values were measured from phytoplankton, dissolved inorganic, dissolved organic and particulate organic carbon. A novel radiocarbon method, Stepped Combustion1 was used to estimate the degree of the burial of terrestrial carbon in surface sediment. The ∆14C values of the low temperature fractions were comparable to algal ∆14C, while the high temperature fractions were 14C-depleted (older than bulk sediment). The ∆14C end-member model indicated that ~64% of carbon in surface sediment was derived from detrital terrestrial carbon. The use of ∆14C in conjunction with stepped combustion allows the quantification of the pathways of terrestrial carbon in the system, which has implications for regional and global carbon burial.
1McGeehin, J., Burr, G.S., Jull, A.J.T., Reines, D., Gosse, J., Davis, P.T., Muhs, D., and Southon, J.R., 2001, Stepped-combustion C-14 dating of sediment: A comparison with established techniques: Radiocarbon, v. 43, p. 255-261.

Thermodynamically stable amorphous drug dispersions in amorphous hydrophilic polymers engineered by hot melt extrusion.

In this study thermodynamically stable dispersions of amorphous quinine, a model BCS class 2 therapeutic agent, within an amorphous polymeric platform (HPC), termed a solid-in-solid dispersion, were produced using hot melt extrusion. Characterisation of the pre-extrudates and extrudates was performed using hyper-differential scanning calorimetry (DSC), powder X-ray diffraction (PXRD) and Raman spectroscopy. Water uptake by the raw materials was determined using dynamic vapour sorption (DVS) analysis. Furthermore, the presence or absence of crystalline drug following storage at 25 °C/60% relative humidity and 40 °C/75% relative humidity in a sealed glass jar, and at 40 °C/75% relative humidity in an open glass jar for 3 months was determined using PXRD. Amorphous quinine was generated in situ during extrusion from both quinine base (5%, 10%, 20% w/w drug loading) and from quinine hydrochloride (5%, 10% w/w drug loading) and remained thermodynamically stable as a solid-in-solid dispersion within the HPC extrudates. When processed with HPC, quinine hydrochloride (20% w/w) was converted to amorphous quinine hydrochloride. Whilst stable for up to 3 months when stored under sealed conditions, this amorphous form was unstable, resulting in recrystallisation of the hydrochloride salt following storage for 1 month at 40 °C/75% relative humidity in an open glass jar. The behaviour of the amorphous quinine hydrochloride (20% w/w) HPC extrudate was related, at least in part, to the lower stability and the hygroscopic properties of this amorphous form.

Cement As a Waste Form for Nuclear Fission Products: The Case of 90Sr and Its Daughters

One of the main challenges faced by the nuclear industry is the long-term confinement of nuclear waste. Because it is inexpensive and easy to manufacture, cement is the material of choice to store large volumes of radioactive materials, in particular the low-level medium-lived fission products. It is therefore of utmost importance to assess the chemical and structural stability of cement containing radioactive species. Here, we use ab initio calculations based on density functional theory (DFT) to study the effects of ⁹⁰Sr insertion and decay in C-S-H (calcium-silicate-hydrate) in order to test the ability of cement to trap and hold this radioactive fission product and to investigate the consequences of its β-decay on the cement paste structure. We show that ⁹⁰Sr is stable when it substitutes the Ca²⁺ ions in C-S-H, and so is its daughter nucleus ⁹⁰Y after β-decay. Interestingly, ⁹⁰Zr, daughter of ⁹⁰Y and final product in the decay sequence, is found to be unstable compared to the bulk phase of the element at zero K but stable when compared to the solvated ion in water. Therefore, cement appears as a suitable waste form for ⁹⁰Sr storage.

Dietary Micronutrient Intake and Micronutrient Status in Patients With Chronic Stable Heart Failure: An Observational Study.

BACKGROUND: Observational studies suggest that patients with heart failure have a tendency to a reduced status of a number of micronutrients and that this may be associated with an adverse prognosis. A small number of studies also suggest that patients with heart failure may have reduced dietary intake of micronutrients, a possible mechanism for reduced status.

OBJECTIVE: The aims of this study were to assess dietary micronutrient intake and micronutrient status in a group of patients with heart failure.

METHODS: Dietary intake was assessed in 79 outpatients with chronic stable heart failure with a reduced ejection fraction using a validated food frequency questionnaire. Blood concentrations of a number of micronutrients, including vitamin D, were measured in fasting blood samples, drawn at the time of food frequency questionnaire completion.

RESULTS: More than 20% of patients reported intakes less than the reference nutrient intake or recommended intake for riboflavin, vitamin D, vitamin A, calcium, magnesium, potassium, zinc, copper, selenium, and iodine. More than 5% of patients reported intakes less than the lower reference nutrient intake or minimum recommended intake for riboflavin, vitamin D, vitamin A, calcium, magnesium, potassium, zinc, selenium, and iodine. Vitamin D deficiency (plasma total 25-hydroxy-vitamin D concentration <50 nmol/L) was observed in 75.6% of patients.

CONCLUSIONS: Vitamin D deficiency was common in this group of patients with heart failure. Based on self-reported dietary intake, a substantial number of individuals may not have been consuming enough vitamin D and a modest number of individuals may not have been consuming enough riboflavin, vitamin A, calcium, magnesium, potassium, zinc, copper, selenium, or iodine to meet their dietary needs.

Community dynamics and the lower airway microbiota in stable chronic obstructive pulmonary disease, smokers and healthy non-smokers

RATIONALE: The role bacteria play in the progression of COPD has increasingly been highlighted in recent years. However, the microbial community complexity in the lower airways of patients with COPD is poorly characterised.

OBJECTIVES: To compare the lower airway microbiota in patients with COPD, smokers and non-smokers.

METHODS: Bronchial wash samples from adults with COPD (n=18), smokers with no airways disease (n=8) and healthy individuals (n=11) were analysed by extended-culture and culture-independent Illumina MiSeq sequencing. We determined aerobic and anaerobic microbiota load and evaluated differences in bacteria associated with the three cohorts. Culture-independent analysis was used to determine differences in microbiota between comparison groups including taxonomic richness, diversity, relative abundance, 'core' microbiota and co-occurrence.

MEASUREMENT AND MAIN RESULTS: Extended-culture showed no difference in total load of aerobic and anaerobic bacteria between the three cohorts. Culture-independent analysis revealed that the prevalence of members of Pseudomonas spp. was greater in the lower airways of patients with COPD; however, the majority of the sequence reads for this taxa were attributed to three patients. Furthermore, members of Bacteroidetes, such as Prevotella spp., were observed to be greater in the 'healthy' comparison groups. Community diversity (α and β) was significantly less in COPD compared with healthy groups. Co-occurrence of bacterial taxa and the observation of a putative 'core' community within the lower airways were also observed.

CONCLUSIONS: Microbial community composition in the lower airways of patients with COPD is significantly different to that found in smokers and non-smokers, indicating that a component of the disease is associated with changes in microbiological status.