Variable temperature13C MAS NMR of KFe2Mn(CO)12 in the solid state and as aCatalyst precursor on a carbon support

Variable temperature¹³C MAS NMR spectra are reported for¹³CO-enriched KFe₂Mn(CO)₁₂ as a solid and also as dispersed clusters on a carbon support. The spectrum of KFe₂Mn(CO)₁₂ at 300 K agrees with the proposed structure for this cluster and shows that the cluster is static. Two bridging carbonyl resonances are clearly resolved and, by comparison with¹³C MAS NMR spectra of Mn₂(CO)₁₀ and Fe₂(CO)₉, all terminal resonances for the cluster can be assigned. When the cluster is supported on carbon, two broad resonances are observed at room temperature which are assignable to KFe₂Mn(CO)₁₂ and a decomposition product, Mn₂(CO)₁₀. The carbonyl ligands in both supported clusters are completely averaged, and KFe₂Mn(CO)₁₂ on the carbon surface demonstrates fluxional behavior similar to that observed for the cluster in solution. For this fluxional process, activation energies of 0.6 kcal/mol and 0.5 kcal/mol are estimated for carbon-supported KFe₂Mn(CO)₁₂ and Mn₂(CO)₁₀, respectively.     

Designing for video: investigating the contextual cues within viewing situations

The viewing of video increasingly occurs in a wide range of public and private environments via a range of static and mobile devices. The proliferation of content on demand and the diversity of the viewing situations means that delivery systems can play a key role in introducing audiences to contextually relevant content of interest whilst maximising the viewing experience for individual viewers. However, for video delivery systems to do this, they need to take into account the diversity of the situations where video is consumed, and the differing viewing experiences that users desire to create within them. This requires an ability to identify different contextual viewing situations as perceived by users. This paper presents the results from a detailed, multi-method, user-centred field study with 11 UK-based users of video-based content. Following a review of the literature (to identify viewing situations of interest on which to focus), data collection was conducted comprising observation, diaries, interviews and self-captured video. Insights were gained into whether and how users choose to engage with content in different public and private spaces. The results identified and validated a set of contextual cues that characterise distinctive viewing situations. Four archetypical viewing situations were identified: ‘quality time’, ‘opportunistic planning’, ‘sharing space but not content’ and ‘opportunistic self-indulgence’. These can be differentiated in terms of key contextual factors: solitary/shared experiences, public/private spaces and temporal characteristics. The presence of clear contextual cues provides the opportunity for video delivery systems to better tailor content and format to the viewing situation or additionally augment video services through social media in order to provide specific experiences sensitive to both temporal and physical contexts.     

Structural and functional analogy between pneumolysin and proaerolysin

Pneumolysin and proaerolysin are bacterial toxins that form pores in host cells by oligomerization. We propose that they may have similar structures despite a poor sequence identity. The crystal structure of proaerolysin reveals a protein composed of four domains, arranged in the shape of an elongated comma. Electron microscopy of the pneumolysin monomer shows a similar arrangement of domains. The sequence of pneumolysin recognizes the template of proaerolysin from a library of protein folds. A three-dimensional model of pneumolysin has been constructed by the comparative approach using the structure of proaerolysin. This model, together with results on the activity of site- specific mutants and the positions of antigenic sites, has been used to propose functional roles of individual domains.      

Synthetic hydrogels: 3. Hydroxyalkyl acrylate and methacrylate copolymers: surface and mechanical properties

The surface and mechanical properties of copolymers of hydroxyalkyl acrylates and methacrylates have been examined by a variety of techniques. This work is complementary to earlier parts of this series which describe the effect of copolymer structure on water binding properties. Water structure has been demonstrated to exert a profound effect upon mechanical properties whether measured in compression or in tension. In particular, water that is characterized by differential scanning calorimetry as ‘freezing’ water is observed to have a marked plasticizing effect upon the gel, whereas ‘non-freezing’ water has little such effect. Similarly, the ‘freezing’ water produces a more marked effect on thermally induced transitions. Two distinct transition points are observed as a result of its presence. One corresponds to the freezing point of water and the other to a glass transition temperature, whose value depends upon the proportion of ‘freezing’ or ‘plasticizing’ water in the gel. Several predictive and direct measurement techniques have been used to study the surface properties of the copolymers in both hydrated and dehydrated states. Taken together they have established a sound understanding of the way in which polar and dispersive components of surface free energy vary as a function of copolymer composition and water content. Use of protein adsorption and fibroblast cell interaction techniques demonstrate that biological phenomena respond to changes at a molecular level which current macroscopic surface energy techniques are unable to discern.     

A modified consensus approach to mutagenesis inverts the cofactor specificity of Bacillus stearothermophilus lactate dehydrogenase

Lactate dehydrogenase from Bacillus stearothermophilus is specific for NAD+. There have been several attempts to alter the cofactor specificity of this enzyme, but these have yielded enzymes with relatively low activities that still largely prefer NAD+. A modified consensus approach was used to create a library of phylogenetically preferred amino acids situated near the cofactor binding site, and variants were screened for their ability to utilize NMN+. A triple mutant (Mut31) was discovered that proved to be more catalytically efficient than wild-type. Mut31 was also better at utilizing NAD+ than the wild-type enzyme and was weakly active with NADP+ and NMN+. An analysis of single amino acid substitutions suggested that all three mutations worked in a concerted fashion to yield robust cofactor utilization. When two previously identified amino acid substitutions were introduced into the Mut31 background, the resultant quintuply substituted enzyme not only utilized NADP+ far better than the wild-type enzyme, it actually inverted its preference for NAD+ and NADP+.     

The stability and unfolding of an IgG binding protein based upon the B domain of protein A from Staphylococcus aureus probed by tryptophan substitution and fluorescence spectroscopy

The stability and unfolding of an immunoglobulin (Ig) G bindingprotein based upon the B domain of protein A (SpAB) from Staphylococcusaureus were studied by substituting tryptophan residues at strategiclocations within each of the three a-helical regions (al-a3)of the domain. The role of the C-terminal helix, a3, was investigatedby generating two protein constructs, one corresponding to thecomplete SpAB, the other lacking a part of ct3; the Trp substitutionswere made in both one-and two-domain versions of each of theseconstructs. The fluorescence properties of each of the single-tryptophanmutants were studied in the native state and as a function ofguanidine-HCl-mediated unfolding, and their IgG binding activitieswere determined by a competitive enzyme-linked immunosorbentassay. The free energies of folding and of binding to IgG foreach mutant were compared with those for the native domains.The effect of each substitution upon the overall structure andupon the IgG binding interface was modelled by molecular graphicsand energy minimization. These studies indicate that (i) 3 contributesto the overall stability of the domain and to the formationof the IgG binding site in l and 2, and (ii) al unfolds first,followed by 2 and 3 together.     

Differential Display of Investigative Behavior Permits Discrimination of Scent Signatures from Familiar and Unfamiliar Socially Dominant Female Marmoset Monkeys (Callithrix jacchus)

The hypothesis was tested that marmosets have differential displays of investigatory behavior towards circumgenital scent marks from socially dominant females based on degree of familiarity. In a series of two-choice behavioral discrimination bioassays, dominant males together with subordinate and dominant females were presented concurrently with scent secretions from familiar versus unfamiliar dominant females, and their investigative behaviors towards the scent were recorded. Test animals directed significantly different amounts of investigative behaviors towards familiar versus unfamiliar scents when the scent stimuli involved complete circumgenital scent marks, glandular secretion only, or urine only. When animals discriminated between the two scent samples, they did so by directing significantly increased amounts of behavior to scent from unfamiliar females. Chemical cues promoting differential displays of behavior to familiar versus unfamiliar scents appeared to be volatile in nature and were effective in the scent mark for at least one day following deposition. The reliable ability of marmosets to consistently discriminate between odors from familiar versus unfamiliar dominant females provides strong circumstantial evidence that individual female marmosets have distinct chemical signatures. The ability of marmosets to discriminate the odor from familiar versus unfamiliar dominant females may be important in the context of intergroup relations.     

Activated gas plasma surface treatment of polymers for adhesive bonding

Polyethylene, polypropylene, poly(vinyl fluoride) (Tedlar), polystyrene, nylon 6, poly(ethylene terephthalate) (Mylar), polycarbonate, cellulose acetate butyrate, and a poly(oxymethylene) copolymer were treated with activated helium and with activated oxygen. Mechanical strengths of adhesive-bonded specimens prepared from treated and from untreated coupons were compared. Polyethylene (PE) and polypropylene (PP) showed the greatest increases in bond strength. Oxygen and helium were both effective with polyethylene, but polypropylene showed no improvement when treated with activated helium. The results with excited helium parallel the effects of ionizing radiation on these two polymers, as does the appearance of unsaturation bands in the infrared (965 cm^?1 in PE, and 887 and 910 cm^?1 in PP). Active nitrogen produced excellent bond strength with polyethylene but not with polypropylene. Of the remaining polymers examined, Tedlar, polystyrene, and nylon 6 showed the greatest improvement in bondability after treatment, and Mylar showed moderate improvement. Polycarbonate, cellulose acetate butyrate, and the poly(oxymethylene) copolymer gave approximately two-fold increases in lap-shear bond strength. In several cases, significant differences in response to time of treatment and type of excited gas were found.     

Experiences from using heat integration software to determine retrofit opportunities within a refinery process

Heat integration techniques can be used to optimize the energy requirement for both new and retrofit plant designs. Software tools for identifying retrofit options are becoming available. This paper reports our experiences from using heat exchanger network (HEN) optimization software for a retrofit case study of an oil refinery process. The HEN optimization software was used to automate the search for the most beneficial retrofit designs following the twostage process proposed by Asante and Zhu. The software provided three potential retrofit designs. Results from this analysis were used as the basis of a rigorous mass and energy balance simulation of the plant. The simulation corroborated the energy savings, but there were some important differences. The simulation required 20% more heat exchange area. Furthermore, the retrofit design involving one topology change was shown to be less economic than an alternative design. These differences are discussed and a revised methodology is proposed.     

Prevention of water pollution problems in mining: The bactericide technology

In pyritic environments, the bacteriaThiobacillus ferrooxidans catalyze acid formation by increasing the oxidation rate of pyrite by a factor of one million. This acid solubilizes metals and pollutes adjacent streams and lands. Bactericide sprays during mining and waste disposal operations attack the source of the problem by preventing acid formation and metals solubilization. Used in conjunction with current water treatment systems, bactericides can dramatically reduce operating costs. Controlled release bactericides contribute to successful reclamation by providing assurance against revegetation failure and post-reclamation water quality problems that can necessitate perpetual water treatment. While inhibitingT. ferrooxidans these organic compounds aid in the establishment of beneficial heterotrophic bacteria which support vegetation. These conditions continue to persist after the bactericide is depleted from the controlled release system. Case Studies I and II show that bactericides inhibit acid generation during hard rock and coal mining operations and they are cost effective. Case Studies III and IV illustrate the improvement in water quality and vegetation after reclamation when controlled release bactericides were used. Economic analyses show cost benefits are achieved when controlled-release bactericides are part of the reclamation plan.