(1)H NMR spectroscopy as a tool to determine accurate photoisomerization quantum yields of stilbene-like ligands coordinated to rhenium(I) polypyridyl complexes

In this work, the use of proton nuclear magnetic resonance, (1)H NMR, was fully described as a powerful tool to follow a photoreaction and to determine accurate quantum yields, so called true quantum yields (Phi(true)), when a reactant and photoproduct absorption overlap. For this, Phi(true) for the trans-cis photoisomerization process were determined for rhenium(I) polypyridyl complexes, fac-[Re(CO)(3)(NN)(trans-L)](+) (NN = 1,10-phenanthroline, phen, or 4,7-diphenyl-1,10-phenanthroline, ph(2)phen, and L = 1,2-bis(4-pyridyl) ethylene, bpe, or 4-styrylpyridine, stpy). The true values determined at 365 nm irradiation (e. g. Phi(NMR) = 0.80 for fac-[Re(CO)(3)(phen)(trans-bpe)](+)) were much higher than those determined by absorption spectral changes (Phi(UV-Vis) = 0.39 for fac-[Re(CO)(3)(phen)(trans-bpe)](+)). Phi(NMR) are more accurate in these cases due to the distinct proton signals of trans and cis-isomers, which allow the actual determination of each component concentration under given irradiation time. Nevertheless when the photoproduct or reactant contribution at the probe wavelength is negligible, one can determine Phi(true) by regular absorption spectral changes. For instance, Phi(313) nm for free ligand photoisomerization determined both by absorption and (1)H NMR variation are equal within the experimental error (bpe: Phi(UV-Vis) = 0.27, Phi(NMR) = 0.26; stpy: Phi(UV-Vis) = 0.49, Phi(NMR) = 0.49). Moreover, (1)H NMR data combined with electronic spectra allowed molar absorptivity determination of difficult to isolate cis-complexes. (C) 2009 Elsevier B. V. All rights reserved.

Investigating the Nature of Noble Gas-Copper Bonds by the Quantum Theory of Atoms in Molecules

We investigated noble gas copper bonds in linear complexes represented by the NgCuX general formula in which Ng and X stand for a noble gas (neon, argon, krypton, or xenon) and a halogen (fluorine, chlorine or bromine), respectively, by coupled cluster methods and modified cc-pVQZ basis sets. The quantum theory of atoms in molecules (QTAIM) shows a linear relation between the dissociation energy or noble gas-copper bonds and the amount of electronic charge transferred mainly from the noble gas to copper during complexation. Large changes in the QTAIM quadrupole moments of copper and noble gases resulting from this bonding and a comparison between NgCuX and NgNaCl systems indicate that these noble gas-copper bonds should be better interpreted as predominantly covalent. Finally, QTAIM atomic dipoles of noble gases in NgNaCl systems agree satisfactorily with atomic dipoles given by a simple model for these NgNa van der Waals bonds.

A quantum chemical study on a set of non-imidazole H(3) antihistamine molecules

Molecular orbital calculations were carried out on a set of 28 non-imidazole H(3) antihistamine compounds using the Hartree-Fock method in order to investigate the possible relationships between electronic structural properties and binding affinity for H3 receptors (pK(i)). It was observed that the frontier effective-for-reaction molecular orbital (FERMO) energies were better correlated with pK(i) values than highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy values. Exploratory data analysis through hierarchical cluster (HCA) and principal component analysis (PCA) showed a separation of the compounds in two sets, one grouping the molecules with high pK(i) values, the other gathering low pK(i) value compounds. This separation was obtained with the use of the following descriptors: FERMO energies (epsilon(FERMO)), charges derived from the electrostatic potential on the nitrogen atom (N(1)), electronic density indexes for FERMO on the N(1) atom (Sigma((FERMO))c(i)(2)). and electrophilicity (omega`). These electronic descriptors were used to construct a quantitative structure-activity relationship (QSAR) model through the partial least-squares (PLS) method with three principal components. This model generated Q(2) = 0.88 and R(2) = 0.927 values obtained from a training set and external validation of 23 and 5 molecules, respectively. After the analysis of the PLS regression equation and the values for the selected electronic descriptors, it is suggested that high values of FERMO energies and of Sigma((FERMO))c(i)(2), together with low values of electrophilicity and pronounced negative charges on N(1) appear as desirable properties for the conception of new molecules which might have high binding affinity. 2010 Elsevier Inc. All rights reserved.

A quantum chemical study on the formation of phosphorus mononitride

The chemical mechanism of the (1)PN formation was successfully studied by using the CCSD(T)/6-311++G(3df,3pd) level of theory. The (1)NH(3) + (3)PH and (4)P + NH(3) reaction paths are not energetically favorable to form the (1)PN molecule. However, the (3)NH + (3)PH, (4)N + (3)PH(3), (4)N + (3)PH, (4)P + (3)NH, and (4)P + (2)NH(2) reaction paths to form the (1)PN molecule are only energetically favorable by taking place through specific transition states to form the (1)PN molecule. The NH(3) + (3)PH, (4)N + (1)PH(3), NH(3) + (4)P, and (4)N + (2)PH(2) reactions are spin-forbidden and the probability of hopping for these reactions was estimated to be 0 by the Landau-Zener theory. This is the first detailed study on the chemical mechanism for the (1)PN formation. (C) 2009 Elsevier B.V. All rights reserved.

Cloud computing - Moving to the cloud

Cloud computing innebär användning av datorresurser som är tillgängliga via ett nätverk, oftast Internet och är ett område som har vuxit fram i snabb takt under de senaste åren. Allt fler företag migrerar hela eller delar av sin verksamhet till molnet. Sogeti i Borlänge har behov av att migrera sina utvecklingsmiljöer till en molntjänst då drift och underhåll av dessa är kostsamma och tidsödande. Som Microsoftpartners vill Sogeti använda Microsoft tjänst för cloud computing, Windows Azure, för detta syfte. Migration till molnet är ett nytt område för Sogeti och de har inga beskrivningar för hur en sådan process går till. Vårt uppdrag var att utveckla ett tillvägagångssätt för migration av en IT-lösning till molnet. En del av uppdraget blev då att kartlägga cloud computing, dess beståndsdelar samt vilka för- och nackdelar som finns, vilket har gjort att vi har fått grundläggande kunskap i ämnet. För att utveckla ett tillvägagångssätt för migration har vi utfört flera migrationer av virtuella maskiner till Windows Azure och utifrån dessa migrationer, litteraturstudier och intervjuer dragit slutsatser som mynnat ut i ett generellt tillvägagångssätt för migration till molnet. Resultatet har visat att det är svårt att göra en generell men samtidigt detaljerad beskrivning över ett tillvägagångssätt för migration, då scenariot ser olika ut beroende på vad som ska migreras och vilken typ av molntjänst som används. Vi har dock utifrån våra erfarenheter från våra migrationer, tillsammans med litteraturstudier, dokumentstudier och intervjuer lyft vår kunskap till en generell nivå. Från denna kunskap har vi sammanställt ett generellt tillvägagångssätt med större fokus på de förberedande aktiviteter som en organisation bör genomföra innan migration. Våra studier har även resulterat i en fördjupad beskrivning av cloud computing. I vår studie har vi inte sett att någon tidigare har beskrivit kritiska framgångsfaktorer i samband med cloud computing. I vårt empiriska arbete har vi dock identifierat tre kritiska framgångsfaktorer för cloud computing och i och med detta täckt upp en del av kunskapsgapet där emellan.

Anomalous spin-related quantum phase in mesoscopic hole rings

We have obtained numerically exact results for the spin-related geometric quantum phases that arise in p-type semiconductor ring structures. The interplay between gate-controllable (Rashba) spin splitting and quantum-confinement-induced mixing between hole-spin states causes a much higher sensitivity of magnetoconductance oscillations to external parameters than previously expected. Our results imply a much-enhanced functionality of hole-ring spin-interference devices and shed new light on recent experimental findings.

Effects of a quantum measurement on the electric conductivity : Application to graphene

We generalize the standard linear-response (Kubo) theory to obtain the conductivity of a system that is subject to a quantum measurement of the current. Our approach can be used to specifically elucidate how back-action inherent to quantum measurements affects electronic transport. To illustrate the utility of our general formalism, we calculate the frequency-dependent conductivity of graphene and discuss the effect of measurement-induced decoherence on its value in the dc limit. We are able to resolve an ambiguity related to the parametric dependence of the minimal conductivity.

Ubiquitous computing in education : a SWOT analysis by students and teachers

Learning from anywhere anytime is a contemporary phenomenon in the field of education that is thought to be flexible, time and cost saving. The phenomenon is evident in the way computer technology mediates knowledge processes among learners. Computer technology is however, in some instances, faulted. There are studies that highlight drawbacks of computer technology use in learning. In this study we aimed at conducting a SWOT analysis on ubiquitous computing and computer-mediated social interaction and their affect on education. Students and teachers were interviewed on the mentioned concepts using focus group interviews. Our contribution in this study is, identifying what teachers and students perceive to be the strength, weaknesses, opportunities and threats of ubiquitous computing and computer-mediated social interaction in education. We also relate the findings with literature and present a common understanding on the SWOT of these concepts. Results show positive perceptions. Respondents revealed that ubiquitous computing and computer-mediated social interaction are important in their education due to advantages such as flexibility, efficiency in terms of cost and time, ability to acquire computer skills. Nevertheless disadvantages where also mentioned for example health effects, privacy and security issues, noise in the learning environment, to mention but a few. This paper gives suggestions on how to overcome threats mentioned.

Soft computing in biometrics : a pragmatic appraisal

The ever increasing spurt in digital crimes such as image manipulation, image tampering, signature forgery, image forgery, illegal transaction, etc. have hard pressed the demand to combat these forms of criminal activities. In this direction, biometrics - the computer-based validation of a persons' identity is becoming more and more essential particularly for high security systems. The essence of biometrics is the measurement of person’s physiological or behavioral characteristics, it enables authentication of a person’s identity. Biometric-based authentication is also becoming increasingly important in computer-based applications because the amount of sensitive data stored in such systems is growing. The new demands of biometric systems are robustness, high recognition rates, capability to handle imprecision, uncertainties of non-statistical kind and magnanimous flexibility. It is exactly here that, the role of soft computing techniques comes to play. The main aim of this write-up is to present a pragmatic view on applications of soft computing techniques in biometrics and to analyze its impact. It is found that soft computing has already made inroads in terms of individual methods or in combination. Applications of varieties of neural networks top the list followed by fuzzy logic and evolutionary algorithms. In a nutshell, the soft computing paradigms are used for biometric tasks such as feature extraction, dimensionality reduction, pattern identification, pattern mapping and the like.

An Architectural Description Language for Enterprise Computing

Architectural description languages (ADLs) are used to specify high-level, compositional view of a software application. ADLs usually come equipped with a rigourous state-transition style semantics, facilitating specification and analysis of distributed and event-based systems. However, enterprise system architectures built upon newer middleware (implementations of Java’s EJB specification, or Microsoft’s COM+/ .NET) require additional expressive power from an ADL. The TrustME ADL is designed to meet this need. In this paper, we describe several aspects of TrustME that facilitate specification and anlysis of middleware-based architectures for the enterprise.