Catalytic constructive deoxygenation of lignin-derived phenols: new C-C bond formation processes from imidazole-sulfonates and ether cleavage reactions

Funding: UK Engineering and Physical Sciences Research Council (EPSRC)As part of a programme aimed at exploiting lignin as a chemical feedstock for less oxygenated fine chemicals, several catalytic C-C bond forming reactions utilising guaiacol imidazole sulfonate are demonstrated. These include the cross-coupling of a Grignard, a non-toxic cyanide source, a benzoxazole, and nitromethane. A modified Meyers reaction is used to accomplish a second constructive deoxygenation on a benzoxazole functionalised anisole.Publisher PDFPeer reviewe

The Santa Fe Light Cone Simulation Project: I. Confusion and the WHIM in Upcoming Sunyaev-Zel'dovich Effect Surveys

We present the first results from a new generation of simulated large sky coverage (~100 square degrees) Sunyaev-Zeldovich effect (SZE) cluster surveys using the cosmological adaptive mesh refinement N-body/hydro code Enzo. We have simulated a very large (512^3h^{-3}Mpc^3) volume with unprecedented dynamic range. We have generated simulated light cones to match the resolution and sensitivity of current and future SZE instruments. Unlike many previous studies of this type, our simulation includes unbound gas, where an appreciable fraction of the baryons in the universe reside. We have found that cluster line-of-sight overlap may be a significant issue in upcoming single-dish SZE surveys. Smaller beam surveys (~1 arcmin) have more than one massive cluster within a beam diameter 5-10% of the time, and a larger beam experiment like Planck has multiple clusters per beam 60% of the time. We explore the contribution of unresolved halos and unbound gas to the SZE signature at the maximum decrement. We find that there is a contribution from gas outside clusters of ~16% per object on average for upcoming surveys. This adds both bias and scatter to the deduced value of the integrated SZE, adding difficulty in accurately calibrating a cluster Y-M relationship. Finally, we find that in images where objects with M > 5x10^{13} M_{\odot} have had their SZE signatures removed, roughly a third of the total SZE flux still remains. This gas exists at least partially in the Warm Hot Intergalactic Medium (WHIM), and will possibly be detectable with the upcoming generation of SZE surveys.Comment: 14 pages, 13 figures, version accepted to ApJ. Major revisions mad

Just picking it up? Young children learning with technology at home

We describe a two-year empirical investigation of three- and four-year-old children's uses of technology at home, based on a survey of 346 families and 24 case studies. Using a sociocultural approach, we discuss the range of technologies children encounter in the home, the different forms their learning takes, the roles of adults and other children, and how family practices support this learning. Many parents believed that they do not teach children how to use technology. We discuss parents' beliefs that their children 'pick up' their competences with technology and identify trial and error, copying and demonstration as typical modes of learning. Parents tend to consider that their children are mainly self-taught and underestimate their own role in supporting learning and the extent to which learning with technology is culturally transmitted within the family

A new technique for elucidating β\beta-decay schemes which involve daughter nuclei with very low energy excited states

A new technique of elucidating $\beta$-decay schemes of isotopes with large density of states at low excitation energies has been developed, in which a Broad Energy Germanium (BEGe) detector is used in conjunction with coaxial hyper-pure germanium detectors. The power of this technique has been demonstrated on the example of 183Hg decay. Mass-separated samples of 183Hg were produced by a deposition of the low-energy radioactive-ion beam delivered by the ISOLDE facility at CERN. The excellent energy resolution of the BEGe detector allowed $\gamma$ rays energies to be determined with a precision of a few tens of electronvolts, which was sufficient for the analysis of the Rydberg-Ritz combinations in the level scheme. The timestamped structure of the data was used for unambiguous separation of $\gamma$ rays arising from the decay of 183Hg from those due to the daughter decays

Why We Read Wikipedia

Wikipedia is one of the most popular sites on the Web, with millions of users relying on it to satisfy a broad range of information needs every day. Although it is crucial to understand what exactly these needs are in order to be able to meet them, little is currently known about why users visit Wikipedia. The goal of this paper is to fill this gap by combining a survey of Wikipedia readers with a log-based analysis of user activity. Based on an initial series of user surveys, we build a taxonomy of Wikipedia use cases along several dimensions, capturing users' motivations to visit Wikipedia, the depth of knowledge they are seeking, and their knowledge of the topic of interest prior to visiting Wikipedia. Then, we quantify the prevalence of these use cases via a large-scale user survey conducted on live Wikipedia with almost 30,000 responses. Our analyses highlight the variety of factors driving users to Wikipedia, such as current events, media coverage of a topic, personal curiosity, work or school assignments, or boredom. Finally, we match survey responses to the respondents' digital traces in Wikipedia's server logs, enabling the discovery of behavioral patterns associated with specific use cases. For instance, we observe long and fast-paced page sequences across topics for users who are bored or exploring randomly, whereas those using Wikipedia for work or school spend more time on individual articles focused on topics such as science. Our findings advance our understanding of reader motivations and behavior on Wikipedia and can have implications for developers aiming to improve Wikipedia's user experience, editors striving to cater to their readers' needs, third-party services (such as search engines) providing access to Wikipedia content, and researchers aiming to build tools such as recommendation engines.Comment: Published in WWW'17; v2 fixes caption of Table

The Expression and Activity of Cathepsins D, H and K in Asthmatic Airways

Tumstatin is an anti-angiogenic collagen IV α3 fragment, levels of which are reduced in the airways of asthmatics. Its reduction may be due to the degradation by extracellular matrix (ECM) proteases. Cathepsins play a role in ECM remodelling, with cathepsin D, H and K (CTSD, CTSH and CTSK) being associated with lung diseases. CTSD modulates the NC1 domains of collagen molecules including tumstatin, while CTSH and CTSK are involved in ECM degradation. The role of these cathepsins in the regulation of tumstatin in the lung has not previously been examined. We demonstrated that CTSB, D, F, H, K, L and S mRNA was expressed in the airways. Quantification of immunohistochemistry showed that there is no difference in the global expression of CTSD, CTSH and CTSK between asthmatics and non-asthmatics. CTSD and CTSK, but not CTSH had the capacity to degrade tumstatin. No difference was observed in the activity of CTSD and H in bronchoalveolar lavage fluid of asthmatic and non-asthmatics, while CTSK was undetectable. This indicates that while CTSD possesses the potential to directly regulate tumstatin, and thus angiogenesis through this mechanism however, it is not likely to be involved in the dysregulation of tumstatin found in asthmatic airways. © 2013 Faiz et al

Manipulation and removal of defects in spontaneous optical patterns

Defects play an important role in a number of fields dealing with ordered structures. They are often described in terms of their topology, mutual interaction and their statistical characteristics. We demonstrate theoretically and experimentally the possibility of an active manipulation and removal of defects. We focus on the spontaneous formation of two-dimensional spatial structures in a nonlinear optical system, a liquid crystal light valve under single optical feedback. With increasing distance from threshold, the spontaneously formed hexagonal pattern becomes disordered and contains several defects. A scheme based on Fourier filtering allows us to remove defects and to restore spatial order. Starting without control, the controlled area is progressively expanded, such that defects are swept out of the active area.Comment: 4 pages, 4 figure

Predicting Filipino Mothers\u27 and Fathers\u27 Reported Use of Corporal Punishment From Education, Authoritarian Attitudes, and Endorsement of Corporal Punishment

The relations of education, authoritarian childrearing attitudes, and endorsement of corporal punishment to Filipino parents\u27 reported use of corporal punishment were examined using two waves of data. Structured interviews using self-report questionnaires were conducted with 117 mothers and 98 fathers from 120 families when their children were 8 years old, and when their children were 9 years old. Path analyses showed that, among mothers, higher education predicted lower authoritarian attitudes, which in turn predicted lower reports of corporal punishment use. Among fathers, higher education predicted lower endorsement of corporal punishment, which in turn predicted lower reports of its use. Results suggest that education has an indirect relation to use of corporal punishment through parenting cognitions, and highlight distinctions in Filipino mothers\u27 and fathers\u27 parenting roles

What does supervision help with? a survey of 315 social workers in the UK

What does social work supervision help with? There are many different models of supervision and an increasing amount of research. Much of this is concerned with the content of supervision and how supervisors (and supervisees) should behave — and these are important concerns. But even more important is the question of who or what supervision helps with. Supervision is widely considered to have many different functions but in the context of UK local authority social work, must ultimately prove itself as a method for helping people who use services. This article reports on a survey of 315 social workers from UK local authorities. Most reported that supervision helps primarily with management oversight and accountability. However, the small number of practitioners who received regular group supervision and those who received supervision more frequently said it helped with a much broader range of things