Photoelectron spectroscopic study of the oxyallyl diradical

The photoelectron spectrum of the oxyallyl (OXA) radical anion has been measured. The radical anion has been generated in the reaction of the atomic oxygen radical anion (O center dot-) with acetone. Three low-lying electronic states of OXA have been observed in the spectrum. Electronic structure calculations have been performed for the triplet states (B-3(2) and B-3(1)) of OXA and the ground doublet state ((2)A(2)) of the radical anion using density, functional theory (DFT). Spectral simulations have been carried out for the triplet statics based on the results of the DFT calculations. The simulation identifies a vibrational progression of the CCC bending mode of the B-3(2) state of OXA in the lower electron binding energy (eBE) portion of the spectrum. On top of the B-3(2) feature, however, the experimental spectrum exhibits additional photoelectron peaks whose angular distribution is distinct from that for the vibronic peaks of the B-3(2) state. Complete active space self-consistent field (CASSCF) method and second-order perturbation theory based on the CASSCF wave function (CASPT2) have been employed to study the lowest singlet state ((1)A(1)) of OXA. The simulation based on the results of these electronic structure calculations establishes that the overlapping peaks represent the vibrational ground level of the (1)A(1) state and its vibrational progression of the CO stretching mode. The A, state is the lowest electronic state of,OXA, and the electron affinity (EA) of OXA is 1.940 +/- 0.010 eV. The B-3(2) state is the first excited state with an electronic term energy of 55 +/- 2 meV. The widths of the vibronic peaks of the (X) over tilde (1)A(1) state are much broader than those of the (a) over tilde B-3(2) state, implying that the (1)A(1) state is indeed a transition state. The CASSCF and CASPT2 calculations suggest that the (1)A(1) state is at a potential maximum along the nuclear coordinate representing disrotatory motion of the two methylene groups, which leads to three-membered-ring formation, i.e., cydopropanone. The simulation of (b) over tilde B-3(1) OXA reproduces the higher eBE portion of the spectrum very well. The term energy of the B-3(1) state is 0.883 +/- 0.012 eV. Photoelectron spectroscopic measurements have also been conducted for the other ion products of the O center dot- reaction with acetone. The photoelectron imaging spectrum of the acetylcarbene (AC) radical anion exhibits a broad, structureless feature, which is assigned to the (X) over tilde (3)A '' state of AC. The ground ((2)A '') and first excited ((2)A') states of the 1-methylvinoxy (1-MVO) radical have been observed in the photoelectron spectrum of the 1-MVO ion, and their vibronic structure has been analyzed.

Differentiation state and invasiveness of human breast cancer cell lines

Eighteen breast cancer cell lines were examined for expression of markers of epithelial and fibroblastic differentiation: E-cadherin, desmoplakins, ZO- 1, vimentin, keratin and β1 and β4 integrins. The cell lines were distributed along a spectrum of differentiation from epithelial to fibroblastic phenotypes. The most well-differentiated, epithelioid cell lines contained proteins characteristic of desmosomal, adherens and tight junctions, were adherent to one another on plastic and in the basement membrane matrix Matrigel and were keratin-positive and vimentin-negative. These cell lines were all weakly invasive in an in vitro chemoinvasion assay. The most poorly-differentiated, fibroblastic cell lines were E-cadherin-, desmoplakin- and ZO-1-negative and formed branching structures in Matrigel. They were vimentin-positive, contained only low levels of keratins and were highly invasive in the in vitro chemoinvasion assay. Of all of the markers analyzed, vimentin expression correlated best with in vitro invasive ability and fibroblastic differentiation. In a cell line with unstable expression of vimentin, T47D(CO), the cells that were invasive were of the fibroblastic type. The differentiation markers described here may be useful for analysis of clinical specimens and could potentially provide a more precise measure of differentiation grade yielding more power for predicting prognosis.

Applications of Spreadsheets in Education : The Amazing Power of a Simple Tool

This e-book is devoted to the use of spreadsheets in the service of education in a broad spectrum of disciplines: science, mathematics, engineering, business, and general education. The effort is aimed at collecting the works of prominent researchers and educators that make use of spreadsheets as a means to communicate concepts with high educational value. The e-book brings some of the most recent applications of spreadsheets in education and research to the fore. To offer the reader a broad overview of the diversity of applications, carefully chosen articles from engineering (power systems and control), mathematics (calculus, differential equations, and probability), science (physics and chemistry), and education are provided. Some of these applications make use of Visual Basic for Applications (VBA), a versatile computer language that further expands the functionality of spreadsheets. The material included in this e-book should inspire readers to devise their own applications and enhance their teaching and/or learning experience.

On natures of sub-gap photoelectric and optical spectra in nitrogen-contaminated nanocrystalline diamond

Experimentally observed optical and photoelectrical spectra of nitrogen-contaminated (unintentionally doped) nano-crystalline CVD diamond films are simulated using semi-empirical adiabatic General Skettrup Model (GSM), which presumes dominant contributions of defect states from sp 3-coordinated intra-granular carbon atoms to intra-band single electron spectrum N(E) of the material. This picture disagrees with a common viewpoint that the N(E) spectrum of the gap states in diamond powders and polycrystalline CVD films mainly originates from π and π* bonds of sp2-coordinated carbon atoms, which are distributed nearly uniformly over outer surfaces and/or interfaces of the diamond grains. The GSM predicts as well strong effect of granular morphology on the density of intra-band defect states in polycrystalline diamonds.

A digital airport experience : design-led innovation in support of airport strategy

The digital era is proving to be one of disruption, where new technologies matched with innovative business models can be harnessed to attack even the most established of companies. For businesses with the relative certainty of captive customer bases, such as airports, the ability to digitally diversify offers the opportunity to venture into new modes of operation. For an airport, this opportunity can also be leveraged to sustain superior customer support regardless of a customer’s location in the world. This research paper presents a case study of the development of an Australian Airport Corporation’s mobile application as part of a greater digital strategy initiative using a design-led approach to innovate. An action research method provides the platform for an intensive embedded practice and study of design-led innovation within the major Australian Airport Corporation. The findings reveal design-led innovation to be a crucial in-house idea generation and concept development capability enabling the bridging of distinct corporate domains associated with commercialisation, operations and customer experience. A Digital Innovation Checklist is presented as an output of this research which structures an organizational approach toward digital channel innovation. The practitioner’s checklist is designed to aid in the future development of digital channels within the broader spectrum of strategy by addressing business assumptions.

In pursuit of an architecture realism

The noble idea of studying seminal works to ‘see what we can learn’ has turned in the 1990s into ‘let’s see what we can take’ and in the last decade a more toxic derivative ‘what else can’t we take’. That is my observation as a student of architecture in the 1990s, and as a practitioner in the 2000s. In 2010, the sense that something is ending is clear. The next generation is rising and their gaze has shifted. The idea of classification (as a means of separation) was previously rejected by a generation of Postmodernists; the usefulness of difference declined. It’s there in the presence of plurality in the resulting architecture, a decision to mine history and seize in a willful manner. This is a process of looking back but never forward. It has been a mono-culture of absorption. The mono-culture rejected the pursuit of the realistic. It is a blanket suffocating all practice of architecture in this country from the mercantile to the intellectual. Independent reviews of Australia’s recent contributions to the Venice Architecture Biennales confirm the malaise. The next generation is beginning to reconsider classification as a means of unification. By acknowledging the characteristics of competing forces it is possible to bring them into a state of tension. Seeking a beautiful contrast is a means to a new end. In the political setting, this is described by Noel Pearson as the radical centre[1]. The concept transcends the political and in its most essential form is a cultural phenomenon. It resists the compromised position and suggests that we can look back while looking forward. The radical centre is the only demonstrated opportunity where it is possible to pursue a realistic architecture. A realistic architecture in Australia may be partially resolved by addressing our anxiety of permanence. Farrelly’s built desires[2] and Markham’s ritual demonstrations[3] are two ways into understanding the broader spectrum of permanence. But I think they are downstream of our core problem. Our problem, as architects, is that we are yet to come to terms with this place. Some call it landscape others call it country. Australian cities were laid out on what was mistaken for a blank canvas. On some occasions there was the consideration of the landscape when it presented insurmountable physical obstacles. The architecture since has continued to work on its piece of a constantly blank canvas. Even more ironic is the commercial awards programs that represent a claim within this framework but at best can only establish a dialogue within itself. This is a closed system unable to look forward. It is said that Melbourne is the most European city in the southern hemisphere but what is really being described there is the limitation of a senseless grid. After all, if Dutch landscape informs Dutch architecture why can’t the Australian landscape inform Australian architecture? To do that, we would have to acknowledge our moribund grasp of the meaning of the Australian landscape. Or more precisely what Indigenes call Country[4]. This is a complex notion and there are different ways into it. Country is experienced and understood through the senses and seared into memory. If one begins design at that starting point it is not unreasonable to think we can arrive at an end point that is a counter trajectory to where we have taken ourselves. A recent studio with Masters students confirmed this. Start by finding Country and it would be impossible to end up with a building looking like an Aboriginal man’s face. To date architecture in Australia has overwhelmingly ignored Country on the back of terra nullius. It can’t seem to get past the picturesque. Why is it so hard? The art world came to terms with this challenge, so too did the legal establishment, even the political scene headed into new waters. It would be easy to blame the budgets of commerce or the constraints of program or even the pressure of success. But that is too easy. Those factors are in fact the kind of limitations that opportunities grow out of. The past decade of economic plenty has, for the most part, smothered the idea that our capitals might enable civic settings or an architecture that is able to looks past lot line boundaries in a dignified manner. The denied opportunities of these settings to be prompted by the Country they occupy is criminal. The public realm is arrested in its development because we refuse to accept Country as a spatial condition. What we seem to be able to embrace is literal and symbolic gestures usually taking the form of a trumped up art installations. All talk – no action. To continue to leave the public realm to the stewardship of mercantile interests is like embracing derivative lending after the global financial crisis.Herein rests an argument for why we need a resourced Government Architect’s office operating not as an isolated lobbyist for business but as a steward of the public realm for both the past and the future. New South Wales is the leading model with Queensland close behind. That is not to say both do not have flaws but current calls for their cessation on the grounds of design parity poorly mask commercial self interest. In Queensland, lobbyists are heavily regulated now with an aim to ensure integrity and accountability. In essence, what I am speaking of will not be found in Reconciliation Action Plans that double as business plans, or the mining of Aboriginal culture for the next marketing gimmick, or even discussions around how to make buildings more ‘Aboriginal’. It will come from the next generation who reject the noxious mono-culture of absorption and embrace a counter trajectory to pursue an architecture of realism.

The cytochrome P-450 isoenzyme CYP2E1 in the biological processing of industrial chemicals : consequences for occupational and environmental medicine

The importance of the isoform CYP2E1 of the human cytochrome P-450 superfamily of enzymes for occupational and environmental medicine is derived from its unique substrate spectrum that includes a number of highly important high-production chemicals, such as aliphatic and aromatic hydrocarbons, solvents and industrial monomers (i.a. alkanes, alkenes, aromatic and halogenated hydrocarbons). Many polymorphic genes, such as CYP2E1, show considerable differences in allelic distribution between different human populations. The polymorphic nature of the human CYP2E1 gene is significant for inter-individual differences in toxicity of its substrates. Since the substrate spectrum of CYP2E1 includes many compounds of basic relevance to industrial toxicology, a rationale for metabolic interactions of different CYP2E1 substrates is provided. In-depth research into the inter-individual phenotypic differences of human CYP2E1 enzyme activities was enabled by the recognition that the 6-hydroxylation of the drug chlorzoxazone is mediated by CYP2E1. Studies on CYP2E1 phenotyping have pointed to inter-individual variations in enzyme activities. There are consistent ethnic differences in CYP2E1 enzyme expression, mostly demonstrated between European and Japanese populations, which point to a major impact of genetic factors. The most frequently studied genetic polymorphisms are the restriction fragment length polymorphisms PstI/RsaI (mutant allele: CYP2E1*5B) located in the 5′-flanking region of the gene, as well as the DraI polymorphism (mutant allele: CYP2E1*6) located in intron 6. These polymorphisms are partly related, as they form the common allele designated CYP2E1*5A. Striking inter-ethnic differences between Europeans and Asians appear with respect to the frequencies of the CYP2E1*5A allele (only approximately 5% of Europeans are heterozygous, but 37% of Asians are, whilst 6% of Asians are homozygous). Available studies indicate a wide variation in human CYP2E1 expression, which are very likely based on complex gene-environment interactions. Major inter-ethnic differences are apparent on the genotyping and the phenotyping levels. Selected cases are presented where inter-ethnic variations of CYP2E1 may provide likely explanations for unexplained findings concerning industrial chemicals that are CYP2E1 substrates. Possible consequences of differential inter-individual and inter-ethnic susceptibilities are related to individual expressions of clinical symptoms of chemical toxicity, to results of biological monitoring of exposed workers, and to the interpretation of results of epidemiological or molecular-epidemiological studies.

Enhancement of the chemoprotective enzymes glucuronosyl transferase and glutathione transferase in specific organs of the rat by the coffee components kahweol and cafestol

The coffee components kahweol and cafestol (K/C) have been reported to protect the colon and other organs of the rat against the formation of DNA adducts by 2-amino-1-methyl-6-phenylimidazo[4,5-b] pyridine (PhIP) and aflatoxin B1. PhIP is a cooked-food mutagen to which significant human exposure and a role in colon cancer etiology are attributed, and, interestingly, such cancers appear to develop at a lower rate in consumers of coffees with high amounts of K/C. Earlier studies in rodent liver have shown that a key role in the chemopreventive effect of K/C is likely to be due to the potential of these compounds to induce the detoxification of xenobiotics by glutathione transferase (GST) and to enhance the synthesis of the corresponding co-factor glutathione. However, mutagens like PhIP may also be detoxified by UDP-glucuronosyl transferase (UDPGT) for which data are lacking regarding a potential effect of K/C. Therefore, in the present study, we investigated the effect of K/C on UDPGT and, concomitantly, we studied overall GST and the pattern of individual GST classes, particularly GST-θ, which was not included in earlier experiments. In addition, we analyzed the organ-dependence of these potentially chemopreventive effects. K/C was fed to male F344 rats at 0.122% in the chow for 10 days. Enzyme activities in liver, kidney, lung, colon, salivary gland, pancreas, testis, heart and spleen were quantified using five characteristic substrates and the hepatic protein pattern of GST classes α, μ, and π was studied with affnity chromatography/HPLC. Our study showed that K/C is not only capable of increasing overall GST and GST classes α, μ, and π but also of enhancing UDGPT and GST-θ. All investigated K/C effects were strongest in liver and kidney, and some response was seen in lung and colon but none in the other organs. In summary, our results show that K/C treatment leads to a wide spectrum of increases in phase II detoxification enzymes. Notably, these effects occurred preferentially in the well perfused organs liver and kidney, which may thus not only contribute to local protection but also to anti-carcinogenesis in distant, less stimulated organs such as the colon.

An SEM, EDS and vibrational spectroscopic study of the silicate mineral meliphanite (Ca,Na)2Be[(Si,Al)2O6(F,OH)]

The mineral meliphanite (Ca,Na)2Be[(Si,Al)2O6(F,OH)] is a crystalline sodium calcium beryllium silicate which has the potential to be used as piezoelectric material and for other ferroelectric applications. The mineral has been characterized by a combination of scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS) and vibrational spectroscopy. EDS analysis shows a material with high concentrations of Si and Ca and low amounts of Na, Al and F. Beryllium was not detected. Raman bands at 1016 and 1050 cm−1 are assigned to the SiO and AlOH stretching vibrations of three dimensional siloxane units. The infrared spectrum of meliphanite is very broad in comparison with the Raman spectrum. Raman bands at 472 and 510 cm−1 are assigned to OSiO bending modes. Raman spectroscopy identifies bands in the OH stretching region. Raman spectroscopy with complimentary infrared spectroscopy enables the characterization of the silicate mineral meliphanite.

A data mining based method for discovery of web services and their compositions

Due to the availability of huge number of web services, finding an appropriate Web service according to the requirements of a service consumer is still a challenge. Moreover, sometimes a single web service is unable to fully satisfy the requirements of the service consumer. In such cases, combinations of multiple inter-related web services can be utilised. This paper proposes a method that first utilises a semantic kernel model to find related services and then models these related Web services as nodes of a graph. An all-pair shortest-path algorithm is applied to find the best compositions of Web services that are semantically related to the service consumer requirement. The recommendation of individual and composite Web services composition for a service request is finally made. Empirical evaluation confirms that the proposed method significantly improves the accuracy of service discovery in comparison to traditional keyword-based discovery methods.

Evolution of sexual segregation in mammalian herbivores: kangaroos as marsupial models

Sexual segregation is best known in sexually dimorphic ungulates. Many hypotheses have been proposed to explain the evolution of sexual segregation in ungulates, but all are reducible to the influence of two factors: body size and sex-specific reproductive strategy. Definitive tests of these hypotheses are lacking in ungulates because these factors are confounded, all males being somewhat larger than females. Kangaroos represent a parallel radiation of terrestrial herbivores, but their populations are composed of a spectrum of adult body sizes, ranging from small males the same size as females to large males more than twice the size. We exploited this heteromorphism to assess the independent influences of size and sex in these ungulate analogues. We conducted a preliminary study of western grey kangaroos (Macropus fuliginosus) in north-western Victoria, Australia. Adult males predominately occupied grassland habitat, whereas females occurred mostly in lakebed, woodland and shrubland. Single-sex groups occurred more often than expected during the non-mating season. The diet of large males had the highest proportion of grass, and females had the least. These initial results indicate that both size and sex influence segregation in this species, confirming the worth of kangaroos as marsupial models for research into the evolution of sexual segregation.

Optical Characterization of the Hole Polaron in a Series of Diketopyrrolopyrrole Polymers Used for Organic Photovoltaics

Abstract: A strategy that is often used for designing low band gap polymers involves the incorporation of electron-rich (donor) and electron-deficient (acceptor) conjugated segments within the polymer backbone. In this paper we investigate such a series of Diketopyrrolopyrrole (DPP)-based co-polymers. The co-polymers consisted of a DPP unit attached to a phenylene, naphthalene, or anthracene unit. Additionally, polymers utilizing either the thiophene-flanked DPP or the furan-flanked DPP units paired with the naphthalene comonomer were compared. As these polymers have been used as donor materials and subsequent hole transporting materials in organic solar cells, we are specifically interested in characterizing the optical absorption of the hole polaron of these DPP based copolymers. We employ chemical doping, electrochemical doping, and photoinduced absorption (PIA) studies to probe the hole polaron absorption spectra. While some donor-acceptor polymers have shown an appreciable capacity to generate free charge carriers upon photoexcitation, no polaron signal was observed in the PIA spectrum of the polymers in this study. The relations between molecular structure and optical properties are discussed. Keywords: organic solar cell; organic photovoltaic; diketopyrrolopyrrole; chemical doping; spectroelectrochemistry; photoinduced absorption; hole polaron

A computer generated model of adenosine receptors rationalising binding and selectivity of receptor ligands

Computer graphic analyses on a broad spectrum of adenosine receptor ligands has shown that both the A1 and A2 adenosine receptors have three binding sites. The spatial relationship of these three binding sites has been defined. Adenosine orientation at A1 and A2 is different.

A vibrational spectroscopic study of the anhydrous phosphate mineral sidorenkite Na3Mn(PO4)(CO3)

Sidorenkite is a very rare low-temperature hydrothermal mineral, formed very late in the crystallization of hyperagpaitic pegmatites in a differentiated alkalic massif (Mt. Alluaiv, Kola Peninsula, Russia). Sidorenkite Na3Mn(PO4)(CO3) is a phosphate–carbonate of sodium and manganese. Such a formula with two oxyanions lends itself to vibrational spectroscopy. The sharp Raman band at 959 cm−1 and 1012 cm−1 are assigned to the PO43− stretching modes, whilst the Raman bands at 1044 cm−1 and 1074 cm−1 are attributed to the CO32− stretching modes. It is noted that no Raman bands at around 800 cm−1 for sidorenkite were observed. The infrared spectrum of sidorenkite shows a quite intense band at 868 cm−1 with other resolved component bands at 850 and 862 cm−1. These bands are ascribed to the CO32− out-of-plane bend (ν2) bending mode. The series of Raman bands at 622, 635, 645 and 704 cm−1 are assigned to the ν4 phosphate bending modes. The observation of multiple bands supports the concept of a reduction in symmetry of the carbonate anion from D3h or even C2v.

Near infrared spectroscopy of marble from Chillagoe, Australia and in comparison with other selected natural carbonates

Marble from the Chillagoe deposits was extensively used in the construction of Australia’s parliament house. Near infrared (NIR) spectroscopy has been applied to study the quality of marble from the Chillagoe marble deposits and to distinguish between different types of marble in the Chillagoe deposits. A comparison of the NIR spectra of marble with dolomite and monohydrocalcite is made. The spectrum of the marble closely resembles that of monohydrocalcite and is different from that of dolomite. The infrared spectra of the minerals are characterised by OH and water stretching vibrations. Both the first and second fundamental overtones of these bands are observed in the NIR spectra. Marble is characterised by NIR bands at 4005, 4268 and 4340 cm–1, attributed to carbonate combination bands and overtones. Marble also shows NIR bands at 5005, 5106, 5234 and 5334 cm–1 assigned to water combination bands. Finally the NIR spectrum of the marble displays broad low-intensity features centred upon 6905 cm–1 attributed to the water first overtones. It appears feasible to identify marble through the use of NIR spectroscopy.