Ir(III) complexes of diamine ligands for asymmetric ketone hydrogenation

The use of a combination of IrCl3 with a series of ligands derived from the C2-symmetric diamine diphenylethanediamine (DPEN) forms a catalyst capable of the asymmetric hydrogenation of ketones in up to 85% ee

Metalinguistic Knowledge and Language Ability in University-Level L2 Learners

Existing research indicates that instructed learners' L2 proficiency and their metalinguistic knowledge are moderately correlated. However, the operationalization of the construct of metalinguistic knowledge has varied somewhat across studies. Metalinguistic knowledge has typically been operationalized as learners' ability to correct, describe, and explain L2 errors. More recently, this operationalization has been extended to additionally include learners' L1 language-analytic ability as measured by tests traditionally used to assess components of language learning aptitude. This article reports on a study which employed a narrowly focused measure of L2 proficiency and incorporated L2 language-analytic ability into a measure of metalinguistic knowledge. It was found that the linguistic and metalinguistic knowledge of advanced university-level L1 English learners of L2 German correlated strongly. Moreover, the outcome of a principal components analysis suggests that learners' ability to correct, describe, and explain highlighted L2 errors and their L2 language-analytic ability may constitute components of the same construct. The theoretical implications of these findings for the concept of metalinguistic knowledge in L2 learning are considered. © Oxford University Press 2007

Challenges to implementing the new homelessness prevention agenda in Wales

Devolution presented an opportunity for the Welsh Government to introduce changes to housing and homelessness policy, and the subsequent homelessness reforms are seen as one of the best examples to date of the Welsh Government using its powers. However, devolved governments in small countries face a number of challenges in terms of realising their housing policy ambitions. In this article we argue that there is inevitable dissonance between the policy behind the Welsh Government legislation (prevention) and practice (implementation) associated with structural challenges (for example austerity and budget restrictions, Welfare Reform and the availability of affordable accommodation). In response we propose a number of actions the Welsh Government might undertake to attempt to mitigate such structural challenges which also resonate in the English context where welfare retrenchment and homelessness prevention policies operate simultaneously

Análise da estrutura fatorial dos Testes de Torrance em estudantes portugueses

In order to verify the factorial structures of the Torrance verbal and figural tests, two activities of each instrument were applied with 193 students from the 10th and 12th years of education in Portugal. We tried to demonstrate that the collinearity of the fluency and flexibility variables could create methodological artifacts that hinder the understanding of the internal structure underlying the test. The principal component analysis without control of collinearity indicated a solution composed of four basic factors that separeted activities. Controlling for collinearity, we found a new solution, which also contained four factors that, unlike the previous result, grouped variables with similar processes but of different activities. The verbal and figural content is also an important element in the factor structure. This new arrangement makes more sense with the theory that underlies the instruments separating the different processes and content which are being measured by the activities.Com a finalidade de verificar a estrutura fatorial dos testes de Torrance, duas atividades verbais e duas figurais foram aplicadas em 193 estudantes do 10º e 12º ano do ensino secundário de Portugal. Tentou-se demonstrar que a colinearidade das variáveis fluência e flexibilidade podem criar artefatos metodológicos que dificultam o entendimento da estrutura interna subjacente ao teste. A análise fatorial dos componentes principais, sem controle da colinearidade, indicou uma solução composta por quatro fatores que separam basicamente as atividades. Controlando-se a colinearidade, encontrou-se uma nova solução, também composta por quatro fatores, que, diferentemente da anterior, organizou variáveis com processos semelhantes, mas de diferentes atividades. O tipo de conteúdo, verbal e figural, mostrou-se ainda um importante elemento na organização dos fatores. Esse novo arranjo fez mais sentido diante da teoria que embasa os instrumentos, ao separar os diferentes processos e conteúdos por eles avaliados

Extraordinary absorption of sound in porous lamella-crystals

We present the design of a structured material supporting complete absorption of sound with a broadband response and functional for any direction of incident radiation. The structure which is fabricated out of porous lamellas is arranged into a low-density crystal and backed by a reflecting support. Experimental measurements show that strong all-angle sound absorption with almost zero reflectance takes place for a frequency range exceeding two octaves. We demonstrate that lowering the crystal filling fraction increases the wave interaction time and is responsible for the enhancement of intrinsic material dissipation, making the system more absorptive with less material.The work was supported by the Spanish Ministry of Science and Innovation and European Union FEDER through project FIS2011-29734-C02-01. J.C. gratefully acknowledges financial support from the Danish Council for Independent Research and a Sapere Aude grant (12-134776). V. R. G. gratefully acknowledges financial support from the ''Contratos Post-Doctorales Campus Excelencia Internacional'' UPV CEI-01-11.Christensen, J.; Romero García, V.; Picó Vila, R.; Cebrecos Ruiz, A.; Garcia De Abajo, FJ.; Mortensen, NA.; Willatzen, M.... (2014). Extraordinary absorption of sound in porous lamella-crystals. Scientific Reports. 4(4674). https://doi.org/10.1038/srep04674S44674Mei, J. et al. Dark acoustic metamaterials as super absorbers for low-frequency sound. Nat. Commun. 3, 756 (2012).Leroy, V., Strybulevych, A., Scanlon, M. G. & Page, J. Transmission of ultrasound through a single layer of bubbles. Eur. Phys. J. E 29, 123 (2009).Leroy, V., Bretagne, A., Fink, M. H. W., Tabeling, P. & Tourin, A. Design and characterization of bubble phononic crystals. Appl. Phys. Lett. 95, 171904 (2009).Thomas, E. L. Applied physics: Bubbly but quiet. Nature 462, 990 (2009).Romero-García, V., Sánchez-Pérez, J. V. & Garcia-Raffi, L. M. Tunable wideband bandstop acoustic filter based on two-dimensional multiphysical phenomena periodic systems. J. Appl. Phys. 110, 014904 (2011).Garcia-Chocano, V. M., Cabrera, S. & Sanchez-Dehesa, J. Broadband sound absorption by lattices of microperforated cylindrical shells. Appl. Phys. Lett. 101, 184101 (2012).Kushwaha, M. S., Halevi, P., Dobrzynski, L. & Djafari-Rouhani, B. Acoustic band structure of periodic elastic composites. Phys. Rev. Lett. 71, 2022 (1993).Vasseur, J. O. et al. Experimental and Theoretical Evidence for the Existence of Absolute Acoustic Band Gaps in Two-Dimensional Solid Phononic Crystals. Phys. Rev. Lett. 86, 3012 (2001).Liu, Z. et al. Locally Resonant Sonic Materials. Science 289, 1734 (2000).Christensen, J., Martin-Moreno, L. & Garcia-Vidal, F. J. All-angle blockage of sound by an acoustic double-fishnet metamaterial. Appl. Phys. Lett. 97, 134106 (2010).Botten, L. C., Craig, M. S., McPhedran, R. C., Adams, J. L. & Andrewartha, J. R. The finitely conducting lamellar diffraction grating. Optica Acta 28, 1087 (1981).McPhedran, R. C., Botten, L. C., Craif, M. S., Neviere, M. & Maystre, D. Lossy lamellar gratings in the quasistatic limit. Optica Acta 29, 289 (1982).Kravets, V. G., Schedin, F. & Grigorenko, A. N. Plasmonic blackbody: Almost complete absorption of light in nanostructured metallic coatings. Phys. Rev. B 78, 205405 (2008).Sondergaard, T. et al. Plasmonic black gold by adiabatic nanofocusing and absorption of light in ultra-sharp convex grooves. Nat. Commun. 3, 969 (2012).Clapham, P. B. & Hurtley, M. C. Reduction of Lens Reflexion by the Moth Eye Principle. Nature Vol. 244, 281 (1973).Garcia-Vidal, F. J., Pitarke, J. M. & Pendry, J. B. Effective Medium Theory of the Optical Properties of Aligned Carbon Nanotubes. Phys. Rev. Lett. 78, 4289 (1997).Yang, Z., Ci, L., Bur, J. A., Lin, S. & Ajayan, P. M. Experimental Observation of an Extremely Dark Material Made By a Low-Density Nanotube Array. Nano Lett. 8, 446 (2008).Garcia-Vidal, F. J. Metamaterials: Towards the dark side. Nat. Photonics 2, 215 (2008).Mizunoa, K. et al. A black body absorber from vertically aligned single-walled carbon nanotubes. Proc. Natl. Acad. Sci. USA 106, 6044 (2009).Lidorkis, E. & Ferrari, A. C. Photonics with Multiwall Carbon Nanotube Arrays. ACS Nano 3, 1238 (2009).Beenakker, C. W. J. & Brouwer, P. W. Distribution of the reflection eigenvalues of a weakly absorbing chaotic cavity. Physica E 9, 463 (2001).Lafarge, D., Lemarinier, P., Allard, J. F. & Tarnow, V. Dynamic compressibility of air in porous structures at audible frequencies. J. Acoust. Soc. Am. 102, 1995 (1997), With the macroscopic parameters: ϕ = 0.94, α∞ = 1, σ = 20000 Nm−4s and Λ = Λ′ = 0.41 μm.García de Abajo, F. J. Colloquium: Light scattering by particle and hole arrays. Rev. Mod. Phys. 79, 1267–1290 (2007)

Rebels and parties: the impact of armed insurgency on representation in the Central African Republic

This paper analyses the declining importance of political parties in the Central African Republic (CAR). The country can be considered an extreme example of the lack of viability of a state in general, and democracy in particular. However, the quality of elections has exceeded the average in the sub-region over a substantial time-span. Hopes for a democratic future only faded in recent years. The paper hypothesises that both political parties and rebel movements are failing to adequately represent (ethnoregional) interests, but that parties are suffering more in the course of the enduring war and the peace process. Patterns of elite behaviour are presented as the main explanation for the resulting crisis of representation, with international actors' preference for inclusionary power-sharing deals seen as the main aggravating factor

Catalytic Hydrogen Production by Ruthenium Complexes from the Conversion of Primary Amines to Nitriles: Potential Application as a Liquid Organic Hydrogen Carrier

The potential application of the primary amine/nitrile pair as a liquid organic hydrogen carrier (LOHC) has been evaluated. Ruthenium complexes of formula [(p-cym)Ru(NHC)Cl2] (NHC=N-heterocyclic carbene) catalyze the acceptorless dehydrogenation of primary amines to nitriles with the formation of molecular hydrogen. Notably, the reaction proceeds without any external additive, under air, and under mild reaction conditions. The catalytic properties of a ruthenium complex supported on the surface of graphene have been explored for reutilization purposes. The ruthenium-supported catalyst is active for at least 10 runs without any apparent loss of activity. The results obtained in terms of catalytic activity, stability, and recyclability are encouraging for the potential application of the amine/nitrile pair as a LOHC. The main challenge in the dehydrogenation of benzylamines is the selectivity control, such as avoiding the formation of imine byproducts due to transamination reactions. Herein, selectivity has been achieved by using long-chain primary amines such as dodecylamine. Mechanistic studies have been performed to rationalize the key factors involved in the activity and selectivity of the catalysts in the dehydrogenation of amines. The experimental results suggest that the catalyst resting state contains a coordinated amine.The authors thank the financial support from MINECO (CTQ2015-69153-C2-2-R), Generalitat Valenciana (AICO/2015/ 039), and the UniversitatJaume I(P1.1B2015-09).The authors are very grateful to the “Serve is Centrals d’Instr umentac ij Cien- t&fica (SCIC)” of the Universitat Jaume I

Asymmetric reduction of 2,2-dimethyl-6-(2-oxoalkyl/oxoaryl)-1,3-dioxin-4-ones and application to the synthesis of (+)-yashabushitriol

The asymmetric transfer hydrogenation of a series of 2,2-dimethyl-6-(2-oxoalkyl)-1,3-dioxin-4-ones and 2,2-dimethyl-6-(2-oxoaryl)-1,3-dioxin-4-ones was achieved in high enantiomeric excess using a Ru(II) catalyst. The aryl substrates were most compatible with the methodology and this process facilitated a total synthesis of enantiomerically pure (+)-yashabushitriol

Did aid promote democracy in Africa?: the role of technical assistance in Africa’s transitions

Did foreign aid impede or catalyze democratization in Africa in the 1990s? We argue that after the Cold War, donors increased their use of technical assistance in aid packages, improving their monitoring capacity and thus reducing autocrats’ ability to use aid for patronage. To remain in power, autocrats responded by conceding political rights to their opponents—from legalizing opposition parties to staging elections. We test our theory with panel data for all sub-Saharan African countries. While other factors played pivotal roles in Africa’s political liberalization, we find technical assistance helps to explain the timing and extent of Africa’s democratization