2,395 research outputs found

    “My journey map”: Developing a qualitative approach to mapping young people’s progress in residential rehabilitation

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    Young people with substance misuse issues are at risk of harm from significant negative health and life events. Contemporary research notes both a historical failure to recognize the unique needs of adolescents, and the ongoing need for dedicated adolescent treatment programs and outcome measures. It is concerning that there is so little literature assessing the quality, availability, and effectiveness of adolescent-focused treatment programs, and no adolescent-specific measurement tools centered on a young person’s progress in residential treatment. This article reports on the process of developing a qualitative approach to mapping progress in treatment over time. The research seeks to develop an approach that captures, at three points in time and from multiple viewpoints, the progress of young people in four residential rehabilitation services located in New South Wales and Western Australia, across several dimensions of the personal and social aspects of life. Our aim is to develop an approach that is accessible to the alcohol and other drug workforce, and that informs the development of a psychometrically robust quantitative measure of progress that is meaningful and useful both to practitioners and to the young people themselves

    Selective acetyl- and butyrylcholinesterase inhibitors reduce amyloid-β ex vivo activation of peripheral chemo-cytokines from Alzheimer's disease subjects: exploring the cholinergic anti-inflammatory pathway

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    Increasing evidence suggests that elevated production and/or reduced clearance of amyloid-β peptide (Aβ) drives the early pathogenesis of Alzheimer's disease (AD). Aβ soluble oligomers trigger a neurotoxic cascade that leads to neuronal dysfunction, neurodegeneration and, ultimately, clinical dementia. Inflammation, both within brain and systemically, together with a deficiency in the neurotransmitter acetylcholine (ACh) that underpinned the development of anticholinesterases for AD symptomatic treatment, are invariable hallmarks of the disease. The inter-relation between Aβ, inflammation and cholinergic signaling is complex, with each feeding back onto the others to drive disease progression. To elucidate these interactions plasma samples and peripheral blood mononuclear cells (PBMCs) were evaluated from healthy controls (HC) and AD patients. Plasma levels of acetylcholinesterase (AChE), butyrylcholinesterase (BuChE) and Aβ were significantly elevated in AD vs. HC subjects, and ACh showed a trend towards reduced levels. Aβ challenge of PBMCs induced a greater release of inflammatory cytokines interleukin-1β (IL-1β), monocyte chemotactic protein-1 (MCP-1) and tumor necrosis factor-alpha (TNF-α) from AD vs. HC subjects, with IL-10 being similarly affected. THP-1 monocytic cells, a cell culture counterpart of PBMCs and brain microglial cells, responded similarly to Aβ as well as to phytohaemagglutinin (PHA) challenge, to allow preliminary analysis of the cellular and molecular pathways underpinning Aβ-induced changes in cytokine expression. As amyloid-β precursor protein expression, and hence Aβ, has been reported regulated by particular cytokines and anticholinesterases, the latter were evaluated on Aβ- and PHA-induced chemocytokine expression. Co-incubation with selective AChE/BuChE inhibitors, (-)-phenserine (AChE) and (-)-cymserine analogues (BuChE), mitigated the rise in cytokine levels and suggest that augmentation of the cholinergic anti-inflammatory pathway may prove valuable in AD

    Testing Reactive Probabilistic Processes

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    We define a testing equivalence in the spirit of De Nicola and Hennessy for reactive probabilistic processes, i.e. for processes where the internal nondeterminism is due to random behaviour. We characterize the testing equivalence in terms of ready-traces. From the characterization it follows that the equivalence is insensitive to the exact moment in time in which an internal probabilistic choice occurs, which is inherent from the original testing equivalence of De Nicola and Hennessy. We also show decidability of the testing equivalence for finite systems for which the complete model may not be known

    Tuning Carbon Dioxide Adsorption Affinity of Zinc(II) MOFs by Mixing Bis(pyrazolate) Ligands with N-Containing Tags

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    The four zinc(II) mixed-ligand metal-organic frameworks (MIXMOFs) Zn(BPZ)x(BPZNO2)1-x, Zn(BPZ)x(BPZNH2)1-x, Zn(BPZNO2)x(BPZNH2)1-x, and Zn(BPZ)x(BPZNO2)y(BPZNH2)1-x-y (H2BPZ = 4,4′-bipyrazole; H2BPZNO2 = 3-nitro-4,4′-bipyrazole; H2BPZNH2 = 3-amino-4,4′-bipyrazole) were prepared through solvothermal routes and fully investigated in the solid state. Isoreticular to the end members Zn(BPZ) and Zn(BPZX) (X = NO2, NH2), they are the first examples ever reported of (pyr)azolate MIXMOFs. Their crystal structure is characterized by a three-dimensional open framework with one-dimensional square or rhombic channels decorated by the functional groups. Accurate information about ligand stoichiometric ratio was determined (for the first time on MIXMOFs) through integration of selected ligands skeleton resonances from 13C cross polarized magic angle spinning solid-state NMR spectra collected on the as-synthesized materials. Like other poly(pyrazolate) MOFs, the four MIXMOFs are thermally stable, with decomposition temperatures between 708 and 726 K. As disclosed by N2 adsorption at 77 K, they are micro-mesoporous materials with Brunauer-Emmett-Teller specific surface areas in the range 400-600 m2/g. A comparative study (involving also the single-ligand analogues) of CO2 adsorption capacity, CO2 isosteric heat of adsorption (Qst), and CO2/N2 selectivity in equimolar mixtures at p = 1 bar and T = 298 K cast light on interesting trends, depending on ligand tag nature or ligand stoichiometric ratio. In particular, the amino-decorated compounds show higher Qst values and CO2/N2 selectivity vs the nitro-functionalized analogues; in addition, tag "dilution" [upon passing from Zn(BPZX) to Zn(BPZ)x(BPZX)1-x] increases CO2 adsorption selectivity over N2. The simultaneous presence of amino and nitro groups is not beneficial for CO2 uptake. Among the compounds studied, the best compromise among uptake capacity, Qst, and CO2/N2 selectivity is represented by Zn(BPZ)x(BPZNH2)1-x

    Stratigraphic framework of the late Miocene Pisco Formation at Cerro Los Quesos (Ica Desert, Peru)

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    The enormous concentration of marine vertebrates documented within the Pisco Formation is unique for Peru and South America and places this unit among the prime fossil Lagerstätten for Miocene to Pliocene marine mammals worldwide. In order to provide a robust stratigraphic framework for the fossil-bearing locality of Cerro Los Quesos, this study presents a 1:10,000 scale geological map covering an area of about 21 km2, a detailed measured section spanning 290 m of strata, and a refined chronostratigraphy for the studied succession well constrained by diatom biostratigraphy and high-resolution 40Ar/39Ar isotopic dating of three interbedded ash layers. Within the apparently monotonous, diatomite-dominated sedimentary section, the Pisco Formation has been subdivided into six local members, with stratigraphic control over the different outcrops facilitated by the establishment of a detailed marker bed stratigraphy based on fifteen readily distinguishable sediment layers of different nature

    Cobalt(II) Bipyrazolate Metal-Organic Frameworks as Heterogeneous Catalysts in Cumene Aerobic Oxidation: A Tag-Dependent Selectivity

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    "This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c00481"[EN] Three metal-organic frameworks with the general formula Co(BPZX) (BPZX(2-) = 3-X-4,4'-bipyrazolate, X = H, NH2, NO2) constructed with ligands having different functional groups on the same skeleton have been employed as heterogeneous catalysts for aerobic liquid-phase oxidation of cumene with O-2 as oxidant. O-2 adsorption isotherms collected at p(O2) = 1 atm and T = 195 and 273 K have cast light on the relative affinity of these catalysts for dioxygen. The highest gas uptake at 195 K is found for Co(BPZ) (3.2 mmol/g (10.1 wt % O-2)), in line with its highest BET specific surface area (926 m(2)/g) in comparison with those of Co(BPZNH(2)) (317 m(2)/g) and Co(BPZNO(2)) (645 m(2)/g). The O-2 isosteric heat of adsorption (Q(2)) trend follows the order Co(BPZ) > Co(BPZNH(2)) > Co(BPZNO(2)). Interestingly, the selectivity in the cumene oxidation products was found to be dependent on the tag present in the catalyst linker: while cumene hydroperoxide (CHP) is the main product obtained with Co(BPZ) (84% selectivity to CHP after 7 h, p(O2) = 4 bar, and T = 363 K), further oxidation to 2-phenyl-2-propanol (PP) is observed in the presence of Co(BPZNH(2)) as the catalyst (69% selectivity to PP under the same experimental conditions).S.G., R.V., and M.M. acknowledge Universita dell'Insubria for partial funding. G.G. thanks the Italian MIUR through the PRIN 2017 Project Multi-e: Multielectron Transfer for the Conversion of Small Molecules: an Enabling Technology for the Chemical Use of Renewable Energy (20179337R7) for financial support. G.G. thanks the TRAINER project (Catalysts for Transition to Renewable Energy Future) ref. ANR-17-MPGA-0017 for support. C.P. thanks the University of Camerino and the Italian MIUR throughout the PRIN 2015 Project Towards a Sustainable Chemistry (20154 x 9ATP_002). This project has also received funding from the European Union's Horizon 2020 research and innovation program under the Marie Sklodowska-Curie grant agreement No. 641887 (project acronym: DEFNET) and the Spanish Government through projects MAT2017-82288-C2-1-P and Severo Ochoa (SEV-2016-0683). Professor Norberto Masciocchi (University of Insubria, Como, Italy) is acknowledged for fruitful discussions. The authors are also grateful to Dr. Giulia Tuci (CNR-ICCOM Florence, Italy) for help with the XPS curve fitting. The Microscopy Service of the Universitat Politècnica de València is gratefully acknowledged for the electron microscopy measurements.Nowacka, AE.; Vismara, R.; Mercuri, G.; Moroni, M.; Palomino Roca, M.; Domasevitch, K.; Di Nicola, C.... (2020). Cobalt(II) Bipyrazolate Metal-Organic Frameworks as Heterogeneous Catalysts in Cumene Aerobic Oxidation: A Tag-Dependent Selectivity. Inorganic Chemistry. 59(12):8161-8172. https://doi.org/10.1021/acs.inorgchem.0c00481S816181725912Fortuin, J. P., & Waterman, H. I. (1953). Production of phenol from cumene. Chemical Engineering Science, 2(4), 182-192. doi:10.1016/0009-2509(53)80040-0Luyben, W. L. (2009). Design and Control of the Cumene Process. Industrial & Engineering Chemistry Research, 49(2), 719-734. doi:10.1021/ie9011535Matsui, S., & Fujita, T. (2001). New cumene-oxidation systems. 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T. (2016). Advancing Sustainable Manufacturing through a Heterogeneous Cobalt Catalyst for Selective C–H Oxidation. Industrial & Engineering Chemistry Research, 55(12), 3308-3312. doi:10.1021/acs.iecr.5b03674Scognamiglio, J., Jones, L., Letizia, C. S., & Api, A. M. (2012). Fragrance material review on 2-phenyl-2-propanol. Food and Chemical Toxicology, 50, S130-S133. doi:10.1016/j.fct.2011.10.011Rossin, A., Tuci, G., Luconi, L., & Giambastiani, G. (2017). Metal–Organic Frameworks as Heterogeneous Catalysts in Hydrogen Production from Lightweight Inorganic Hydrides. ACS Catalysis, 7(8), 5035-5045. doi:10.1021/acscatal.7b01495Chughtai, A. H., Ahmad, N., Younus, H. A., Laypkov, A., & Verpoort, F. (2015). Metal–organic frameworks: versatile heterogeneous catalysts for efficient catalytic organic transformations. Chemical Society Reviews, 44(19), 6804-6849. doi:10.1039/c4cs00395kLiu, J., Chen, L., Cui, H., Zhang, J., Zhang, L., & Su, C.-Y. (2014). Applications of metal–organic frameworks in heterogeneous supramolecular catalysis. Chem. Soc. Rev., 43(16), 6011-6061. doi:10.1039/c4cs00094cGascon, J., Corma, A., Kapteijn, F., & Llabrés i Xamena, F. X. (2013). Metal Organic Framework Catalysis: Quo vadis? ACS Catalysis, 4(2), 361-378. doi:10.1021/cs400959kLuo, S., Zeng, Z., Zeng, G., Liu, Z., Xiao, R., Chen, M., … Jiang, D. (2019). Metal Organic Frameworks as Robust Host of Palladium Nanoparticles in Heterogeneous Catalysis: Synthesis, Application, and Prospect. ACS Applied Materials & Interfaces, 11(36), 32579-32598. doi:10.1021/acsami.9b11990Deng, X., Li, Z., & García, H. (2017). Visible Light Induced Organic Transformations Using Metal-Organic-Frameworks (MOFs). Chemistry - A European Journal, 23(47), 11189-11209. doi:10.1002/chem.201701460Dhakshinamoorthy, A., Asiri, A. M., & Garcia, H. (2016). Metal-Organic Frameworks as Catalysts for Oxidation Reactions. Chemistry - A European Journal, 22(24), 8012-8024. doi:10.1002/chem.201505141Song, X., Hu, D., Yang, X., Zhang, H., Zhang, W., Li, J., … Yu, J. (2019). Polyoxomolybdic Cobalt Encapsulated within Zr-Based Metal–Organic Frameworks as Efficient Heterogeneous Catalysts for Olefins Epoxidation. ACS Sustainable Chemistry & Engineering, 7(3), 3624-3631. doi:10.1021/acssuschemeng.8b06736Zhang, T., Hu, Y.-Q., Han, T., Zhai, Y.-Q., & Zheng, Y.-Z. (2018). Redox-Active Cobalt(II/III) Metal–Organic Framework for Selective Oxidation of Cyclohexene. ACS Applied Materials & Interfaces, 10(18), 15786-15792. doi:10.1021/acsami.7b19323Ma, Y., Peng, H., Liu, J., Wang, Y., Hao, X., Feng, X., … Li, Y. (2018). Polyoxometalate-Based Metal–Organic Frameworks for Selective Oxidation of Aryl Alkenes to Aldehydes. Inorganic Chemistry, 57(7), 4109-4116. doi:10.1021/acs.inorgchem.8b00282Othong, J., Boonmak, J., Ha, J., Leelasubcharoen, S., & Youngme, S. (2017). Thermally Induced Single-Crystal-to-Single-Crystal Transformation and Heterogeneous Catalysts for Epoxidation Reaction of Co(II) Based Metal–Organic Frameworks Containing 1,4-Phenylenediacetic Acid. Crystal Growth & Design, 17(4), 1824-1835. doi:10.1021/acs.cgd.6b01788Wang, J.-C., Ding, F.-W., Ma, J.-P., Liu, Q.-K., Cheng, J.-Y., & Dong, Y.-B. (2015). Co(II)-MOF: A Highly Efficient Organic Oxidation Catalyst with Open Metal Sites. Inorganic Chemistry, 54(22), 10865-10872. doi:10.1021/acs.inorgchem.5b01938Tuci, G., Giambastiani, G., Kwon, S., Stair, P. C., Snurr, R. Q., & Rossin, A. (2014). Chiral Co(II) Metal–Organic Framework in the Heterogeneous Catalytic Oxidation of Alkenes under Aerobic and Anaerobic Conditions. ACS Catalysis, 4(3), 1032-1039. doi:10.1021/cs401003dHamidipour, L., & Farzaneh, F. (2013). Cobalt metal organic framework as an efficient heterogeneous catalyst for the oxidation of alkanes and alkenes. Reaction Kinetics, Mechanisms and Catalysis, 109(1), 67-75. doi:10.1007/s11144-012-0533-2Luz, I., León, A., Boronat, M., Llabrés i Xamena, F. X., & Corma, A. (2013). Selective aerobic oxidation of activated alkanes with MOFs and their use for epoxidation of olefins with oxygen in a tandem reaction. Catal. Sci. Technol., 3(2), 371-379. doi:10.1039/c2cy20449eSantiago-Portillo, A., Navalón, S., Cirujano, F. G., Xamena, F. X. L. i, Alvaro, M., & Garcia, H. (2015). MIL-101 as Reusable Solid Catalyst for Autoxidation of Benzylic Hydrocarbons in the Absence of Additional Oxidizing Reagents. ACS Catalysis, 5(6), 3216-3224. doi:10.1021/acscatal.5b00411Nowacka, A., Briantais, P., Prestipino, C., & Llabrés i Xamena, F. X. (2019). Selective Aerobic Oxidation of Cumene to Cumene Hydroperoxide over Mono- and Bimetallic Trimesate Metal–Organic Frameworks Prepared by a Facile «Green» Aqueous Synthesis. ACS Sustainable Chemistry & Engineering, 7(8), 7708-7715. doi:10.1021/acssuschemeng.8b06472Vismara, R., Tuci, G., Tombesi, A., Domasevitch, K. V., Di Nicola, C., Giambastiani, G., … Galli, S. (2019). Tuning Carbon Dioxide Adsorption Affinity of Zinc(II) MOFs by Mixing Bis(pyrazolate) Ligands with N-Containing Tags. ACS Applied Materials & Interfaces, 11(30), 26956-26969. doi:10.1021/acsami.9b08015Vismara, R., Tuci, G., Mosca, N., Domasevitch, K. V., Di Nicola, C., Pettinari, C., … Rossin, A. (2019). Amino-decorated bis(pyrazolate) metal–organic frameworks for carbon dioxide capture and green conversion into cyclic carbonates. Inorganic Chemistry Frontiers, 6(2), 533-545. doi:10.1039/c8qi00997jMosca, N., Vismara, R., Fernandes, J. A., Tuci, G., Di Nicola, C., Domasevitch, K. V., … Galli, S. (2018). Nitro-Functionalized Bis(pyrazolate) Metal-Organic Frameworks as Carbon Dioxide Capture Materials under Ambient Conditions. Chemistry - A European Journal, 24(50), 13170-13180. doi:10.1002/chem.201802240Pettinari, C., Tăbăcaru, A., & Galli, S. (2016). Coordination polymers and metal–organic frameworks based on poly(pyrazole)-containing ligands. Coordination Chemistry Reviews, 307, 1-31. doi:10.1016/j.ccr.2015.08.005Pettinari, C., Tăbăcaru, A., Boldog, I., Domasevitch, K. V., Galli, S., & Masciocchi, N. (2012). Novel Coordination Frameworks Incorporating the 4,4′-Bipyrazolyl Ditopic Ligand. Inorganic Chemistry, 51(9), 5235-5245. doi:10.1021/ic3001416Colombo, V., Montoro, C., Maspero, A., Palmisano, G., Masciocchi, N., Galli, S., … Navarro, J. A. R. (2012). Tuning the Adsorption Properties of Isoreticular Pyrazolate-Based Metal–Organic Frameworks through Ligand Modification. Journal of the American Chemical Society, 134(30), 12830-12843. doi:10.1021/ja305267mTăbăcaru, A., Pettinari, C., Masciocchi, N., Galli, S., Marchetti, F., & Angjellari, M. (2011). Pro-porous Coordination Polymers of the 1,4-Bis((3,5-dimethyl-1H-pyrazol-4-yl)-methyl)benzene Ligand with Late Transition Metals. Inorganic Chemistry, 50(22), 11506-11513. doi:10.1021/ic2013705Colombo, V., Galli, S., Choi, H. J., Han, G. D., Maspero, A., Palmisano, G., … Long, J. R. (2011). High thermal and chemical stability in pyrazolate-bridged metal–organic frameworks with exposed metal sites. Chemical Science, 2(7), 1311. doi:10.1039/c1sc00136aMasciocchi, N., Galli, S., Colombo, V., Maspero, A., Palmisano, G., Seyyedi, B., … Bordiga, S. (2010). Cubic Octanuclear Ni(II) Clusters in Highly Porous Polypyrazolyl-Based Materials. Journal of the American Chemical Society, 132(23), 7902-7904. doi:10.1021/ja102862jGalli, S., Masciocchi, N., Colombo, V., Maspero, A., Palmisano, G., López-Garzón, F. J., … Navarro, J. A. R. (2010). Adsorption of Harmful Organic Vapors by Flexible Hydrophobic Bis-pyrazolate Based MOFs. 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    Weighing the prognostic role of hyponatremia in hospitalized patients with metastatic solid tumors: the HYPNOSIS study

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    Previous works linked low sodium concentration with mortality risk in cancer. We aimed at weighing the prognostic impact of hyponatremia in all consecutive patients with metastatic solid tumors admitted in a two-years period at our medical oncology department. Patients were included in two cohorts based on serum sodium concentration on admission. A total of 1025 patients were included, of whom 279 (27.2%) were found to be hyponatremic. The highest prevalence of hyponatremia was observed in biliary tract (51%), prostate (45%) and small-cell lung cancer (38.9%). With a median follow-up of 26.9 months, median OS was 2 months and 13.2 months for the hyponatremia versus control cohort, respectively (HR, 2.65; P < 0.001). In the multivariable model, hyponatremia was independently associated with poorer OS (HR, 1.66; P < 0.001). According to the multivariable model, a nomogram system was developed and validated in an external set of patients. We weighed over time the influence of hyponatremia on survival of patients with metastatic solid tumors and pointed out the possibility to exploit serum sodium assessment to design integrated prognostic tools. Our study also highlights the need for a deeper characterization of the biological role of extracellular sodium levels in tumor development and progression

    Lung adenocarcinoma originates from retrovirus infection of proliferating type 2 pneumocytes during pulmonary post-natal development or tissue repair

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    Jaagsiekte sheep retrovirus (JSRV) is a unique oncogenic virus with distinctive biological properties. JSRV is the only virus causing a naturally occurring lung cancer (ovine pulmonary adenocarcinoma, OPA) and possessing a major structural protein that functions as a dominant oncoprotein. Lung cancer is the major cause of death among cancer patients. OPA can be an extremely useful animal model in order to identify the cells originating lung adenocarcinoma and to study the early events of pulmonary carcinogenesis. In this study, we demonstrated that lung adenocarcinoma in sheep originates from infection and transformation of proliferating type 2 pneumocytes (termed here lung alveolar proliferating cells, LAPCs). We excluded that OPA originates from a bronchioalveolar stem cell, or from mature post-mitotic type 2 pneumocytes or from either proliferating or non-proliferating Clara cells. We show that young animals possess abundant LAPCs and are highly susceptible to JSRV infection and transformation. On the contrary, healthy adult sheep, which are normally resistant to experimental OPA induction, exhibit a relatively low number of LAPCs and are resistant to JSRV infection of the respiratory epithelium. Importantly, induction of lung injury increased dramatically the number of LAPCs in adult sheep and rendered these animals fully susceptible to JSRV infection and transformation. Furthermore, we show that JSRV preferentially infects actively dividing cell in vitro. Overall, our study provides unique insights into pulmonary biology and carcinogenesis and suggests that JSRV and its host have reached an evolutionary equilibrium in which productive infection (and transformation) can occur only in cells that are scarce for most of the lifespan of the sheep. Our data also indicate that, at least in this model, inflammation can predispose to retroviral infection and cancer
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