Ruthenium-thymine acetate binding modes: Experimental and theoretical studies

Ruthenium complexes have proved to exhibit antineoplastic activity, related to the interaction of the metal ion with DNA. In this context, synthetic and theoretical studies on ruthenium binding modes of thymine acetate (THAc) have been focused to shed light on the structure-activity relationship. This report deals with the reaction between dihydride ruthenium mer-[Ru(H)2(CO)(PPh3)3], 1 and the thymine acetic acid (THAcOH) selected as model for nucleobase derivatives. The reaction in refluxing toluene between 1 and THAcOH excess, by H2 release affords the double coordinating species k1-(O)THAc-, k2-(O,O)THAc-[Ru(CO)(PPh3)2], 2. The X-ray crystal structure confirms a simultaneous monohapto, dihapto- THAc coordination in a reciprocal facial disposition. Stepwise additions of THAcOH allowed to intercept the monohapto mer-k1(O)THAc-Ru(CO)H(PPh3)3] 3 and dihapto trans(P,P)-k2(O,O)THAc-[Ru(CO)H(PPh3)2] 4 species. Nuclear magnetic resonance (NMR) studies, associated with DFT (Density Function Theory)-calculations energies and analogous reactions with acetic acid, supported the proposed reaction path. As evidenced by the crystal supramolecular hydrogen-binding packing and 1H NMR spectra, metal coordination seems to play a pivotal role in stabilizing the minor [(N=C(OH)] lactim tautomers, which may promote mismatching to DNA nucleobase pairs as a clue for its anticancer activity

thermodynamic properties of pb3u11o36

Abstract In order to progress in the development of Lead-cooled Fast Reactors, from the safety point of view it is essential to understand the chemical compatibility between liquid lead and uranium oxide. In the present work, entropy and heat capacity of Pb3U11O36, a possible ternary compound coming from fuel-coolant chemical interaction, were determined for the first time. Entropy at 298.15 K was obtained from low temperature heat capacity measurements using the Physical Property Measurement System (PPMS) in the temperature range 2–300 K, while the high temperature heat capacity has been measured by a drop calorimeter from 373 K to 1200 K. The experimental thermodynamic properties were compared with the values computed by means of DFT-GGA simulations, obtaining a very good agreement

Lixiviação e volatilização de nitrogênio em um Argissolo cultivado com videira submetida à adubação nitrogenada.

O nitrogênio (N) aplicado na superfície do solo em vinhedos pode ser perdido por volatilização ou lixiviação, sendo uma das possíveis explicações para o baixo aproveitamento de N pelas videiras. O trabalho objetivou avaliar as perdas de N por volatilização e lixiviação do N mineral em solo cultivado com videira submetida à adubação nitrogenada. Foram instalados dois experimentos em um vinhedo de Cabernet Sauvignon, em Rosário do Sul (RS), Brasil. No experimento 1, foram instalados lisímetros no solo que recebeu a aplicação de 0, 40, 80 e 120kg de N ha-1 ano-1 na forma de ureia e, durante o período de agosto a dezembro de 2009, foi coletada a solução do solo para a análise de N mineral. No experimento 2, foram instaladas câmaras coletoras no solo que recebeu, em agosto de 2010, a aplicação de 0, 20, 40, e 80kg de N ha-1 ano-1 na forma de ureia, 40kg de N ha-1 ano-1 de composto orgânico e 40kg de N ha-1 ano-1 de ureia revestida com polímeros, para avaliar a volatilização de N-NH3 do momento da aplicação até 80 horas depois da aplicação. As maiores concentrações de nitrogênio mineral na solução lixiviada foram encontradas nas doses mais elevadas de fertilizante mineral aplicado e ao longo da brotação e florescimento das videiras, o que pode diminuir o aproveitamento do nutriente pelas plantas. Os maiores fluxos e perdas de amônia do solo cultivado com videira para a atmosfera aconteceram nas doses mais elevadas de nitrogênio mineral aplicado, especialmente, depois de 44 horas da sua aplicação sobre a superfície do solo. A aplicação de ureia revestida com polímeros e composto orgânico promoveram as menores perdas de amônia por volatilização, o que pode estimular o aproveitamento de nitrogênio pelas videiras

Education for sustainable development: A study in adolescent perception changes towards sustainability following a strategic planning-based intervention-the young persons' plan for the planet program

© 2019 by the authors. In 2016, the United Nations (UN) launched the 17 Sustainable Development Goals (SDGs) as a framework for sustainable development and a sustainable future. However, the global challenge has been to engage, connect, and empower communities, particularly young people, to both understand and deliver the 17 SDGs. In this study, we show the benefit of a strategic planning-based experiential learning tool, the Young Persons' Plan for the Planet (YPPP) Program, to improve the underlying competencies of Australian and Mauritian adolescents in increasing understanding and delivering the SDGs. The study was conducted with 300 middle to senior high school students, in 25 schools throughout Australia and Mauritius, over an 18-month period. The intervention included the development of research, strategic planning, management, STEM (Science Technology, Engineering, Maths) and global competency skills in the students, to enable them to build and deliver regional and national SDG plans. Research methods included pre- and post-intervention testing of the attitudes of these students to sustainable development outcomes and compared these attitudes to subsets of scientists and the Australian national population. Our results, from both qualitative and quantitative evidence, demonstrate significant improvements in these adolescents' appreciation of, and attitudes towards, the SDGs and sustainable outcomes, across a range of key parameters. The results from the 76 students who attended the International Conference in Mauritius in December 2018 demonstrate significant improvements in mean levels of understanding, and attitudes of the students towards the SDGs awareness (+85%), understanding/engagement (+75%), motivation (+57%), and action orientation/empowerment (+66%). These changes were tested across a range of socio-demographic, geographic, and cultural parameters, with consistent results. These findings have significant implications for the challenge of sustainable education and achieving community engagement and action towards the SDGs in Australia and Mauritius, particularly for young people. As the intervention can be replicated and scaled, the findings also highlight the opportunity to extend both the research and this type of experiential learning intervention across both broader geographies and other generation and community segments

Gluon polarization in the nucleon from quasi-real photoproduction of high-pT hadron pairs

We present a determination of the gluon polarization Delta G/G in the nucleon, based on the helicity asymmetry of quasi-real photoproduction events, Q^2<1(GeV/c)^2, with a pair of large transverse-momentum hadrons in the final state. The data were obtained by the COMPASS experiment at CERN using a 160 GeV polarized muon beam scattered on a polarized 6-LiD target. The helicity asymmetry for the selected events is = 0.002 +- 0.019(stat.) +- 0.003(syst.). From this value, we obtain in a leading-order QCD analysis Delta G/G=0.024 +- 0.089(stat.) +- 0.057(syst.) at x_g = 0.095 and mu^2 =~ 3 (GeV}/c)^2.Comment: 10 pages, 3 figure

First Measurement of the Transverse Spin Asymmetries of the Deuteron in Semi-Inclusive Deep Inelastic Scattering

First measurements of the Collins and Sivers asymmetries of charged hadrons produced in deep-inelastic scattering of muons on a transversely polarized 6-LiD target are presented. The data were taken in 2002 with the COMPASS spectrometer using the muon beam of the CERN SPS at 160 GeV/c. The Collins asymmetry turns out to be compatible with zero, as does the measured Sivers asymmetry within the present statistical errors.Comment: 6 pages, 2 figure

Measurement of the Spin Structure of the Deuteron in the DIS Region

We present a new measurement of the longitudinal spin asymmetry A_1^d and the spin-dependent structure function g_1^d of the deuteron in the range 1 GeV^2 < Q^2 < 100 GeV^2 and 0.004< x <0.7. The data were obtained by the COMPASS experiment at CERN using a 160 GeV polarised muon beam and a large polarised 6-LiD target. The results are in agreement with those from previous experiments and improve considerably the statistical accuracy in the region 0.004 < x < 0.03.Comment: 10 pages, 6 figures, subm. to PLB, revised: author list, Fig. 4, details adde

Deciphering the Structure, Growth and Assembly of Amyloid-Like Fibrils Using High-Speed Atomic Force Microscopy

Formation of fibrillar structures of proteins that deposit into aggregates has been suggested to play a key role in various neurodegenerative diseases. However mechanisms and dynamics of fibrillization remains to be elucidated. We have previously established that lithostathine, a protein overexpressed in the pre-clinical stages of Alzheimer's disease and present in the pathognomonic lesions associated with this disease, form fibrillar aggregates after its N-terminal truncation. In this paper we visualized, using high-speed atomic force microscopy (HS-AFM), growth and assembly of lithostathine protofibrils under physiological conditions with a time resolution of one image/s. Real-time imaging highlighted a very high velocity of elongation. Formation of fibrils via protofibril lateral association and stacking was also monitored revealing a zipper-like mechanism of association. We also demonstrate that, like other amyloid ß peptides, two lithostathine protofibrils can associate to form helical fibrils. Another striking finding is the propensity of the end of a growing protofibril or fibril to associate with the edge of a second fibril, forming false branching point. Taken together this study provides new clues about fibrillization mechanism of amyloid proteins