Thermochemistry of Alane Complexes for Hydrogen Storage: A Theoretical and Experimental Investigation.

Knowledge of the relative stabilities of alane (AlH(3)) complexes with electron donors is essential for identifying hydrogen storage materials for vehicular applications that can be regenerated by off-board methods; however, almost no thermodynamic data are available to make this assessment. To fill this gap, we employed the G4(MP2) method to determine heats of formation, entropies, and Gibbs free energies of formation for 38 alane complexes with NH(3-n)R(n) (R = Me, Et; n = 0-3), pyridine, pyrazine, triethylenediamine (TEDA), quinuclidine, OH(2-n)R(n) (R = Me, Et; n = 0-2), dioxane, and tetrahydrofuran (THF). Monomer, bis, and selected dimer complex geometries were considered. Using these data, we computed the thermodynamics of the key formation and dehydrogenation reactions that would occur during hydrogen delivery and alane regeneration, from which trends in complex stability were identified. These predictions were tested by synthesizing six amine-alane complexes involving trimethylamine, triethylamine, dimethylethylamine, TEDA, quinuclidine, and hexamine and obtaining upper limits of ΔG° for their formation from metallic aluminum. Combining these computational and experimental results, we establish a criterion for complex stability relevant to hydrogen storage that can be used to assess potential ligands prior to attempting synthesis of the alane complex. On the basis of this, we conclude that only a subset of the tertiary amine complexes considered and none of the ether complexes can be successfully formed by direct reaction with aluminum and regenerated in an alane-based hydrogen storage system

Quantum computation by local measurement

Quantum computation is a novel way of information processing which allows, for certain classes of problems, exponential speedups over classical computation. Various models of quantum computation exist, such as the adiabatic, circuit and measurement-based models. They have been proven equivalent in their computational power, but operate very differently. As such, they may be suitable for realization in different physical systems, and also offer different perspectives on open questions such as the precise origin of the quantum speedup. Here, we give an introduction to the one-way quantum computer, a scheme of measurement-based quantum computation. In this model, the computation is driven by local measurements on a carefully chosen, highly entangled state. We discuss various aspects of this computational scheme, such as the role of entanglement and quantum correlations. We also give examples for ground states of simple Hamiltonians which enable universal quantum computation by local measurements.Comment: 36 pages, single column, 6 figures, not published version (as restricted by the journal), please refer to ARCMP for the final published versio

The Thickness of the Mushy Layer on the Floor of the Skaergaard Magma Chamber at Apatite Saturation

We present a novel way of constraining the thickness of the crystal mush in fractionated layered intrusions using detailed microstructural analysis. The results are combined with geochemical data to create a snapshot of the crystal mush on the floor of the Skaergaard magma chamber in the period immediately before and after the saturation of the bulk liquid in apatite (the UZa–b boundary). The step-change in the fractional latent heat (that part of the total enthalpy budget associated with crystallization) accompanying the arrival of a new liquidus phase is recorded by a step-change in the median clinopyroxene–plagioclase–plagioclase dihedral angle, Θcpp, in fully solidified cumulates. Dihedral angles are formed during the last stages of solidification and hence the change of Θcpp associated with apatite-in marks a point close to the base of the mushy layer at the moment the bulk liquid became saturated in apatite, whereas the first appearance of abundant, homogeneously scattered, cumulus apatite crystals in the stratigraphy marks the top of the mushy layer at this moment. Comparison of the offset between these two markers in five widely spaced drill cores through the Skaergaard Layered Series suggests that the mushy layer was only a few metres thick at the UZa–b boundary in the centre and east of the floor, whereas it was ∼100 m thick on the floor near the western margin. There is no correlation between the efficiency of liquid expulsion (as recorded by bulk-rock P2O5 concentrations and the stratigraphic distribution of reactive symplectites) and the recorded mush thickness at the moment of apatite saturation, suggesting that existing models of adcumulate formation that depend on mush thickness need to be reconsidered.M.B.H. and C.T. acknowledge support from a Royal Society Joint International Grant. M.B.H. was supported by the Natural Environment Research Council (grant numbers NE/F020325/1 and NE/J021520/1). C.T. was supported by the Carlsberg Foundation, the Danish Council of Independent Research, and the Danish National Research Foundation

Evaluation of the Inheritance of the Complex Vertebral Malformation Syndrome by Breeding Studies

To investigate the congenital complex vertebral malformation syndrome (CVM) in Holstein calves, two breeding studies were performed including 262 and 363 cows, respectively. Cows were selected from the Danish Cattle Database based on pedigree and insemination records. Selected cows were progeny of sires with an established heterozygous CVM genotype and pregnant after insemination with semen from another sire with heterozygous CVM genotype. Following calving the breeders should state, if the calf was normal and was requested to submit dead calves for necropsy. In both studies, significantly fewer CVM affected calves than expected were obtained; a finding probably reflecting extensive intrauterine mortality in CVM affected foetuses. The findings illustrate increased intrauterine mortality as a major potential bias in observational studies of inherited disorders

Enhanced roughness of lipid membranes caused by external electric fields

The behavior of lipid membranes in the presence of an external electric field is studied and used to examine the influence of such fields on membrane parameters such as roughness and show that for a micro sized membrane, roughness grows as the field increases. The dependence of bending rigidity on the electric field is also studied and an estimation of thickness of the accumulated charges around lipid membranes in a free-salt solution is presented.Comment: 9 pages, 6 figures, to appear in Computational Materials Scienc

Recreational soccer is an effective health-promoting activity for untrained men

Copyright BMJ publishing GroupTo examine the effects of regular participation in recreational soccer on health profile, 36 healthy untrained Danish men aged 20-43 years were randomised into a soccer group (SO; n=13), a running group (RU; n=12) and a control group (CO; n=11). Training was performed for 1 h two or three times per week for 12 weeks; at an average heart rate of 82% (SEM 2%) and 82% (1%) of HRmax for SO and RU, respectively. During the 12 week period, maximal oxygen uptake increased (p < 0.05) by 13% (3%) and 8% (3%) in SO and RU, respectively. In SO, systolic and diastolic blood pressure were reduced (p < 0.05) from 130 (2) to 122 (2) mm Hg and from 77 (2) to 72 (2) mm Hg, respectively, after 12 weeks, with similar decreases observed for RU. After the 12 weeks of training, fat mass was 3.0% (2.7 (0.6) kg) and 1.8% (1.8 (0.4) kg) lower (p < 0.05) for SO and RU, respectively. Only SO had an increase in lean body mass (1.7 (0.4) kg, p < 0.05), an increase in lower extremity bone mass (41 (8) g, p < 0.05), a decrease in LDL-cholesterol (2.7 (0.2) to 2.3 (0.2) mmol/l; p < 0.05) and an increase (p < 0.05) in fat oxidation during running at 9.5 km/h. The number of capillaries per muscle fibre was 23% (4%) and 16% (7%) higher (p < 0.05) in SO and RU, respectively, after 12 weeks. No changes in any of the measured variables were observed for CO. In conclusion, participation in regular recreational soccer training, organised as small-sided drills, has significant beneficial effects on health profile and physical capacity for untrained men, and in some aspects it is superior to frequent moderate-intensity running

Validation of a HLA-A2 tetramer flow cytometric method, IFNgamma real time RT-PCR, and IFNgamma ELISPOT for detection of immunologic response to gp100 and MelanA/MART-1 in melanoma patients

<p>Abstract</p> <p>Background</p> <p>HLA-A2 tetramer flow cytometry, IFNγ real time RT-PCR and IFNγ ELISPOT assays are commonly used as surrogate immunological endpoints for cancer immunotherapy. While these are often used as research assays to assess patient's immunologic response, assay validation is necessary to ensure reliable and reproducible results and enable more accurate data interpretation. Here we describe a rigorous validation approach for each of these assays prior to their use for clinical sample analysis.</p> <p>Methods</p> <p>Standard operating procedures for each assay were established. HLA-A2 (A*0201) tetramer assay specific for gp100_209(210M)and MART-1_26–35(27L), IFNγ real time RT-PCR and ELISPOT methods were validated using tumor infiltrating lymphocyte cell lines (TIL) isolated from HLA-A2 melanoma patients. TIL cells, specific for gp100 (TIL 1520) or MART-1 (TIL 1143 and TIL1235), were used alone or spiked into cryopreserved HLA-A2 PBMC from healthy subjects. TIL/PBMC were stimulated with peptides (gp100₂₀₉, gp100_pool, MART-1_27–35, or influenza-M1 and negative control peptide HIV) to further assess assay performance characteristics for real time RT-PCR and ELISPOT methods. Validation parameters included specificity, accuracy, precision, linearity of dilution, limit of detection (LOD) and limit of quantification (LOQ). In addition, distribution was established in normal HLA-A2 PBMC samples. Reference ranges for assay controls were established.</p> <p>Results</p> <p>The validation process demonstrated that the HLA-A2 tetramer, IFNγ real time RT-PCR, and IFNγ ELISPOT were highly specific for each antigen, with minimal cross-reactivity between gp100 and MelanA/MART-1. The assays were sensitive; detection could be achieved at as few as 1/4545–1/6667 cells by tetramer analysis, 1/50,000 cells by real time RT-PCR, and 1/10,000–1/20,000 by ELISPOT. The assays met criteria for precision with %CV < 20% (except ELISPOT using high PBMC numbers with %CV < 25%) although flow cytometric assays and cell based functional assays are known to have high assay variability. Most importantly, assays were demonstrated to be effective for their intended use. A positive IFNγ response (by RT-PCR and ELISPOT) to gp100 was demonstrated in PBMC from 3 melanoma patients. Another patient showed a positive MART-1 response measured by all 3 validated methods.</p> <p>Conclusion</p> <p>Our results demonstrated the tetramer flow cytometry assay, IFNγ real-time RT-PCR, and INFγ ELISPOT met validation criteria. Validation approaches provide a guide for others in the field to validate these and other similar assays for assessment of patient T cell response. These methods can be applied not only to cancer vaccines but to other therapeutic proteins as part of immunogenicity and safety analyses.</p

Finding and Resolving Security Misusability with Misusability Cases

Although widely used for both security and usability concerns, scenarios used in security design may not necessarily inform the design of usability, and vice- versa. One way of using scenarios to bridge security and usability involves explicitly describing how design deci- sions can lead to users inadvertently exploiting vulnera- bilities to carry out their production tasks. This paper describes how misusability cases, scenarios that describe how design decisions may lead to usability problems sub- sequently leading to system misuse, address this problem. We describe the related work upon which misusability cases are based before presenting the approach, and illus- trating its application using a case study example. Finally, we describe some findings from this approach that further inform the design of usable and secure systems