Band Edge Engineering of Oxide Photoanodes for Photoelectrochemical Water Splitting: Integration of Subsurface Dipoles with Atomic‐Scale Control

One of the crucial parameters dictating the efficiency of photoelectrochemical water‐splitting is the semiconductor band edge alignment with respect to hydrogen and oxygen redox potentials. Despite the importance of metal oxides in their use as photoelectrodes, studies to control the band edge alignment in aqueous solution have been limited predominantly to compound semiconductors with modulation ranges limited to a few hundred mV. The ability to modulate the flat band potential of oxide photoanodes by as much as 1.3 V, using the insertion of subsurface electrostatic dipoles near a Nb‐doped SrTiO₃/aqueous electrolyte interface is reported. The tunable range achieved far exceeds previous reports in any semiconductor/aqueous electrolyte system and suggests a general design strategy for highly efficient oxide photoelectrodes.     

Seasonal Dynamics of the Airborne Bacterial Community and Selected Viruses in a Children’s Daycare Center

Children’s daycare centers appear to be hubs of respiratory infectious disease transmission, yet there is only limited information about the airborne microbial communities that are present in daycare centers. We have investigated the microbial community of the air in a daycare center, including seasonal dynamics in the bacterial community and the presence of specific viral pathogens. We collected filters from the heating, ventilation, and air conditioning (HVAC) system of a daycare center every two weeks over the course of a year. Amplifying and sequencing the 16S rRNA gene revealed that the air was dominated by Proteobacteria, Firmicutes, Actinobacteria, and Bacteroidetes that are commonly associated with the human skin flora. Clear seasonal differences in the microbial community were not evident; however, the community structure differed when the daycare center was closed and unoccupied for a 13-day period. These results suggest that human occupancy, rather than the environment, is the major driver in shaping the microbial community structure in the air of the daycare center. Using PCR for targeted viruses, we detected a seasonal pattern in the presence of respiratory syncytial virus that included the period of typical occurrence of the disease related to the virus; however, we did not detect the presence of adenovirus or rotavirus at any time.     

The Hofer-Moest decarboxylation of D-glucuronic acid and D-glucuronosides

Research was undertaken to effect the oxidative decarboxylation of glycuronosides. Experiments with free D-glucuronic acid and aldonic acids were also executed. Both anodic decarboxylation and variants of the Ruff degradation reaction were investigated. Anodic decarboxylation was found to be the only successful method for the decarboxylation of glucuronosides. It was, therefore, proposed that glycuronosides can only undergo a one-electron oxidation to form an acyloxy radical, which decomposes to form carbon dioxide and a C-5 radical, that is, a Hofer-Moest decarboxylation. The radical is subsequently oxidized to a cation by means of a second one-electron oxidation. The cation undergoes nucleophilic attack from the solvent (water), whose product (a hemiacetal) undergoes a spontaneous hydrolysis to yield a dialdose (xylo-pentodialdose from D-glucuronosides).     

Pleiotropic effects on mandibular morphology II: differential epistasis and genetic variation in morphological integration

The evolution of morphological modularity through the sequestration of pleiotropy to sets of functionally and developmentally related traits requires genetic variation in the relationships between traits. Genetic variation in relationships between traits can result from differential epistasis, where epistatic relationships for pairs of loci are different for different traits. This study maps relationship quantitative trait loci (QTLs), specifically QTLs that affect the relationship between individual mandibular traits and mandible length, across the genome in an F2 intercross of the LG/J and SM/J inbred mouse strains (N = 1045). We discovered 23 relationship QTLs scattered throughout the genome. All mandibular traits were involved in one or more relationship QTL. When multiple traits were affected at a relationship QTL, the traits tended to come from a developmentally restricted region of the mandible, either the muscular processes or the alveolus. About one-third of the relationship QTLs correspond to previously located trait QTLs affecting the same traits. These results comprise examples of genetic variation necessary for an evolutionary response to selection on the range of pleiotropic effects.     

A nuclear protein in Schizosaccharomyces pombe with homology to the human tumour suppressor Fhit has decapping activity

A number of eukaryotic proteins are already known to orchestrate key steps of mRNA metabolism and translation via interactions with the 5' m7GpppN cap. We have characterized a new type of histidine triad (HIT) motif protein (Nhm1) that co-purifies with the cap-binding complex eIF4F of Schizosaccharomyces pombe. Nhm1 is an RNA-binding protein that binds to m7GTP-Sepharose, albeit with lower specificity and affinity for methylated GTP than is typical for the cap-binding protein known as eukaryotic initiation factor 4E. Sequence searches have revealed that proteins with strong sequence similarity over all regions of the new protein exist in a wide range of eukaryotes, yet none has been characterized up to now. However, other proteins that share specific motifs with Nhm1 include the human Fhit tumour suppressor protein and the diadenosine 5', 5"'-P1, P4-tetraphosphate asymmetrical hydrolase of S. pombe. Our experimental work also reveals that Nhm1 inhibits translation in a cell-free extract prepared from S. pombe, and that it is therefore a putative translational modulator. On the other hand, purified Nhm1 manifests mRNA decapping activity, yet is physically distinct from the Saccharomyces cerevisiae decapping enzyme Dcp1. Moreover, fluorescence and immunofluorescence microscopy show that Nhm1 is predominantly, although not exclusively, nuclear. We conclude that Nhm1 has evolved as a special branch of the HIT motif superfamily that has the potential to influence both the metabolism and the translation of mRNA, and that its presence in S. pombe suggests the utilization of a novel decapping pathway.     

Investigating centre of mass stabilisation as the goal of posture and movement coordination during human whole body reaching

In the light of experimental results showing significant forward centre of mass (CoM) displacements within the base of support, this study investigated if whole body reaching movements can be executed whilst keeping the CoM fixed in the horizontal axis. Using kinematic simulation techniques, angular configurations were recreated from experimental data imposing two constraints: a constant horizontal position of the CoM and an identical trajectory of the hand to grasp an object. The comparison between recorded and simulated trials showed that stabilisation of the CoM was associated with greater backward hip displacements, which became more marked with increasing object distance. This was in contrast to recorded trials showing reductions in backward hip displacements with increasing distance. Results also showed that modifications to angular displacements were necessary only at the shoulder and hip joints, but that these modifications were within the limits of joint mobility. The analysis of individual joint torques revealed that the pattern and timing of simulated trials were similar to those recorded experimentally. Peak joint torque values showed particularly that keeping the CoM at a constant horizontal position resulted in significantly smaller ankle peak flexor and extensor torques. It may be concluded from this study that `stabilising' the CoM during human whole body reaching represents a feasible strategy, but not the one chosen by subjects under experimental conditions. Our results also do not support the idea of the CoM as the stabilised reference value for the coordination between posture and goal-directed movements. Received: 22 September 1998 / Accepted in revised form: 2 June 1999