Determination of beta-19-nortestosterone and its metabolite alpha-19-nortestosterone in biological samples at the sub parts per billion level by high-performance liquid chromatography with on-line immunoaffinity sample pretreatment

An immunoaffinity precolumn (immuno precolumn) packed with Sepharose-immobilized polyclonal antibodies against the anabolic hormone 17 beta-19-nortestosterone (beta-19-NT) was used for the selective on-line pretreatment of raw extracts of urine, bile and tissue samples by high-performance liquid chromatography. Using UV detection (247 nm), beta-19-NT and its metabolite 17 alpha-19-nortestosterone (alpha-19-NT) can be determined in biological samples with a detection limit of 0.05 microgram/kg. Owing to the high clean-up efficiency of the immuno precolumn and the large sample volumes used, confirmation by gas chromatography-mass spectrometry is possible at this level. In urine samples from a calf treated with 19-nortestosterone 17 beta-laurate, the maximum concentrations of beta-19-NT (1.3 micrograms/l) and alpha-19-NT (3.1 micrograms/l) were found seven days after intramuscular administration. In a bile sample from this calf only alpha-19-NT (55 microgram/l) was detected. In meat samples from three treated calves, the concentration of beta-19-NT varied from 0.1 to 1.6 micrograms/kg and no alpha-19-NT could be detected. In liver samples from these calves, the concentrations of beta-19-NT and alpha-19-NT were less than 0.05-0.1 and 0.5-0.9 micrograms/kg, respectively. In the corresponding kidney samples, the concentrations of beta-19-NT and alpha-19-NT were 0.4-0.5 and 0.5-1.6 micrograms/kg, respectively. The application of the same immuno precolumn to the determination of 17 beta- and 17 alpha-trenbolone, two structurally related steroids, is also demonstrated.     

Photochemical functionalization of hydrogen-terminated diamond surfaces: a structural and mechanistic study

Hydrogen-terminated diamond surfaces can be covalently modified with molecules bearing a terminal vinyl (C=C) group via a photochemical process using sub-band-gap light at 254 nm. We have investigated the photochemical modification of hydrogen-terminated surfaces of nanocrystalline and single-crystal diamond (111) to help understand the structure of the films and the underlying mechanism of photochemical functionalization. A comparison of the rates of photochemical modification of single-crystal diamond and nanocrystalline diamond films shows no significant difference in reactivity, demonstrating that the modification process is not controlled by grain boundaries or other structures unique to polycrystalline films. We find that both single-crystal and polycrystalline hydrogen-terminated diamond samples exhibit negative electron affinity and are functionalized at comparable rates, while oxidized surfaces with positive electron affinity undergo no detectable reaction. Gas chromatography-mass spectrometry (GC-MS) analysis shows the formation of new chemical products in the liquid phase that are formed only when the alkenes are illuminated in direct contact with H-terminated diamond, while control experiments with other surfaces and in the dark show no reaction. Our results show that the functionalization is a surface-mediated photochemical reaction and suggest that modification is initiated by the photoejection of electrons from the diamond surfaces into the liquid phase.     

Sequencing games with repeated players

Two classes of one machine sequencing situations are considered in which each job corresponds to exactly one player but a player may have more than one job to be processed, so called RP(repeated player) sequencing situations. In max-RP sequencing situations it is assumed that each player’s cost function is linear with respect to the maximum completion time of his jobs, whereas in min-RP sequencing situations the cost functions are linear with respect to the minimum completion times. For both classes, following explicit procedures to go from the initial processing order to an optimal order for the coalition of all players, equal gain splitting rules are defined. It is shown that these rules lead to core elements of the associated RP sequencing games. Moreover, it is seen that min-RP sequencing games are convex. We thank two referees for their valuable suggestions for improvement. Financial support for P. Calleja has been given by the Ministerio de Educación y Ciencia and FEDER under grant SEJ2005-02443/ECON, and by the Generalitat de Catalunya through a BE grant from AGAUR and grant 2005SGR00984.     

Cooperative game theoretic centrality analysis of terrorist networks: The cases of Jemaah Islamiyah and Al Qaeda

The identification of key players in a terrorist organization aids in preventing attacks, the efficient allocation of surveillance measures, and the destabilization of the corresponding network. In this paper, we introduce a game theoretic approach to identify key players in terrorist networks. In particular we use the Shapley value as a measure of importance in cooperative games that are specifically designed to reflect the context of the terrorist organization at hand. The advantage of this approach is that both the structure of the terrorist network, which usually reflects a communication and interaction structure, as well as non-network features, i.e., individual based parameters such as financial means or bomb building skills, can be taken into account. The application of our methodology to the analysis results in rankings of the terrorists in the network. We illustrate our methodology through two case studies: Jemaah Islamiyah’s Bali bombing and Al Qaedas 9/11 attack, which lead to new insights in the operational networks responsible for these attacks.     

Thin film silicon modules on plastic superstrates

The aim of this research is to fabricate high efficiency a-Si/μc-Si tandem solar cell modules on flexible (polymer) superstrates using the Helianthos concept. As a first step we began by depositing the top cell which contains an amorphous silicon (a-Si:H) i-layer of ～350 nm made by VHF PECVD at 50 MHz in a high vacuum multichamber system called ASTER, with hydrogen to silane gas flow ratio of 1:1. Such amorphous cells on-foil showed an initial active area (0.912 cm²) efficiency of 7.69% (V_oc = 0.834 V, FF = 0.71). These cells were light soaked with white light at a controlled temperature of 50 °C. The efficiency degradation was predominantly due to degradation of FF that amounted to only 11% after 1000 h of light soaking. The cell-on-foil data prove that thin film silicon modules of high stability on cheap plastics can be made at a reasonable efficiency within 30 min of deposition time. A minimodule of 8 × 7.5 cm² area (consisting of 8 cells interconnected in series) with the same single junction a-Si:H p–i–n structure had an initial efficiency of 6.7% (V_oc = 6.32 V, FF = 0.65).     

Photochemical functionalization of gallium nitride thin films with molecular and biomolecular layers

We demonstrate that photochemical functionalization can be used to functionalize and photopattern the surface of gallium nitride crystalline thin films with well-defined molecular and biomolecular layers. GaN(0001) surfaces exposed to a hydrogen plasma will react with organic molecules bearing an alkene (C=C) group when illuminated with 254 nm light. Using a bifunctional molecule with an alkene group at one end and a protected amine group at the other, this process can be used to link the alkene group to the surface, leaving the protected amine exposed. Using a simple contact mask, we demonstrate the ability to directly pattern the spatial distribution of these protected amine groups on the surface with a lateral resolution of <12 mum. After deprotection of the amines, single-stranded DNA oligonucleotides were linked to the surface using a bifunctional cross-linker. Measurements using fluorescently labeled complementary and noncomplementary sequences show that the DNA-modified GaN surfaces exhibit excellent selectivity, while repeated cycles of hybridization and denaturation in urea show good stability. These results demonstrate that photochemical functionalization can be used as an attractive starting point for interfacing molecular and biomolecular systems with GaN and other compound semiconductors.     

Covalent photochemical functionalization of amorphous carbon thin films for integrated real-time biosensing

Recent studies have demonstrated that carbon, in the form of diamond, can be functionalized with molecular and/or biomolecular species to yield interfaces exhibiting extremely high stability and selectivity in binding to target biomolecules in solution. However, diamond and most other crystalline forms of carbon involve high-temperature deposition or processing steps that restrict their ability to be integrated with other materials. Here, we demonstrate that photochemical functionalization of amorphous carbon films followed by covalent immobilization of DNA yields highly stable surfaces with excellent biomolecular recognition properties that can be used for real-time biological detection. Carbon films deposited onto substrates at 300 K were functionalized with organic alkenes bearing protected amine groups and characterized using X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. The functionalized carbon surfaces were covalently linked to DNA oligonucleotides. Measurements show very high selectivity for binding to the complementary sequence, and a high density of hybridizing DNA molecules. Samples repeatedly hybridized and denatured 25 times showed no significant degradation. The ability to use amorphous carbon films as a basis for real-time biosensing is demonstrated by coating quartz crystal microbalance (QCM) crystals with a thin carbon film and using this for covalent modification with DNA. Measurements of the resonance frequency show the ability to detect DNA hybridization in real time with a detection limit of <3% of a monolayer, with a high degree of reversibility. These results demonstrate that functionalized films of amorphous carbon can be used as a chemically stable platform for integrated biosensing using only room-temperature processing steps.