19 research outputs found
A new class of silica-supported chromo-fluorogenic chemosensors for anion recognition based on a selenourea scaffold
[EN] The first example of a chemosensor (L) containing a selenourea moiety is described here. L is able to colorimetrically sense the presence of CN- and S2- in H2O: MeCN (75 : 25, v/v). Moreover, when L is loaded into functionalised mesoporous silica nanoparticles an increase in the selectivity towards S2- occurs via a selective fluorescence response.The authors thank the financial support from the Fondazione Banco di Sardegna, the Spanish Government, European FEDER funds (project MAT2015-64139-C4-1-R) and the Generalitat Valenciana (project PROMETEOII/2014/047). A. Llopis-Lorente is grateful to the "La Caixa'' Banking Foundation for his PhD fellowship. Dr Tiziana Pivetta is gratefully acknowledged for help with the interpretation of the mass spectra.Casula, A.; Llopis-Lorente, A.; Garau, A.; Isaia, F.; Kubicki, M.; Lippolis, V.; Sancenón Galarza, F.... (2017). A new class of silica-supported chromo-fluorogenic chemosensors for anion recognition based on a selenourea scaffold. Chemical Communications. 53(26):3729-3732. https://doi.org/10.1039/c7cc01214dS372937325326Lee, S., Yuen, K. K. Y., Jolliffe, K. A., & Yoon, J. (2015). Fluorescent and colorimetric chemosensors for pyrophosphate. Chemical Society Reviews, 44(7), 1749-1762. doi:10.1039/c4cs00353eZhang, J. F., Zhou, Y., Yoon, J., & Kim, J. S. (2011). Recent progress in fluorescent and colorimetric chemosensors for detection of precious metal ions (silver, gold and platinum ions). Chemical Society Reviews, 40(7), 3416. doi:10.1039/c1cs15028fZhou, X., Lee, S., Xu, Z., & Yoon, J. (2015). Recent Progress on the Development of Chemosensors for Gases. Chemical Reviews, 115(15), 7944-8000. doi:10.1021/cr500567rZhou, Y., & Yoon, J. (2012). Recent progress in fluorescent and colorimetric chemosensors for detection ofamino acids. Chem. Soc. Rev., 41(1), 52-67. doi:10.1039/c1cs15159bBusschaert, N., Caltagirone, C., Van Rossom, W., & Gale, P. A. (2015). Applications of Supramolecular Anion Recognition. Chemical Reviews, 115(15), 8038-8155. doi:10.1021/acs.chemrev.5b00099Gale, P. A., & Caltagirone, C. (2015). Anion sensing by small molecules and molecular ensembles. Chemical Society Reviews, 44(13), 4212-4227. doi:10.1039/c4cs00179fPanda, S., Panda, A., & Zade, S. S. (2015). Organoselenium compounds as fluorescent probes. Coordination Chemistry Reviews, 300, 86-100. doi:10.1016/j.ccr.2015.04.006Manjare, S. T., Kim, Y., & Churchill, D. G. (2014). Selenium- and Tellurium-Containing Fluorescent Molecular Probes for the Detection of Biologically Important Analytes. Accounts of Chemical Research, 47(10), 2985-2998. doi:10.1021/ar500187vWu, D., Chen, L., Kwon, N., & Yoon, J. (2016). Fluorescent Probes Containing Selenium as a Guest or Host. Chem, 1(5), 674-698. doi:10.1016/j.chempr.2016.10.005Mukherjee, A. J., Zade, S. S., Singh, H. B., & Sunoj, R. B. (2010). Organoselenium Chemistry: Role of Intramolecular Interactions†. Chemical Reviews, 110(7), 4357-4416. doi:10.1021/cr900352jManjare, S. T., Kim, S., Heo, W. D., & Churchill, D. G. (2013). Selective and Sensitive Superoxide Detection with a New Diselenide-Based Molecular Probe in Living Breast Cancer Cells. Organic Letters, 16(2), 410-412. doi:10.1021/ol4033013Kim, Y., Choi, M., Manjare, S. T., Jon, S., & Churchill, D. G. (2016). Diselenide-based probe for the selective imaging of hypochlorite in living cancer cells. RSC Advances, 6(38), 32013-32017. doi:10.1039/c6ra04257kYu, F., Li, P., Li, G., Zhao, G., Chu, T., & Han, K. (2011). A Near-IR Reversible Fluorescent Probe Modulated by Selenium for Monitoring Peroxynitrite and Imaging in Living Cells. Journal of the American Chemical Society, 133(29), 11030-11033. doi:10.1021/ja202582xSaravanan, C., Easwaramoorthi, S., Hsiow, C.-Y., Wang, K., Hayashi, M., & Wang, L. (2013). Benzoselenadiazole Fluorescent Probes – Near-IR Optical and Ratiometric Fluorescence Sensor for Fluoride Ion. Organic Letters, 16(2), 354-357. doi:10.1021/ol403082pGoswami, S., Hazra, A., Chakrabarty, R., & Fun, H.-K. (2009). Recognition of Carboxylate Anions and Carboxylic Acids by Selenium-Based New Chromogenic Fluorescent Sensor: A Remarkable Fluorescence Enhancement of Hindered Carboxylates. Organic Letters, 11(19), 4350-4353. doi:10.1021/ol901737sHussain, R. A., Badshah, A., & Shah, A. (2014). Synthesis and biological applications of selenoureas. Applied Organometallic Chemistry, 28(2), 61-73. doi:10.1002/aoc.3093Hussain, R. A., Badshah, A., Tahir, M. N., Hassan, T.-, & Bano, A. (2013). Synthesis, Chemical Characterization, DNA Binding, Antioxidant, Antibacterial, and Antifungal Activities of Ferrocence Incorporated Selenoureas. Journal of Biochemical and Molecular Toxicology, 28(2), 60-68. doi:10.1002/jbt.21536Hussain, R. A., Badshah, A., Tahir, M. N., Lal, B., & Khan, I. A. (2013). Synthesis, Chemical Characterisation, and DNA Binding Studies of Ferrocene-Incorporated Selenoureas. Australian Journal of Chemistry, 66(6), 626. doi:10.1071/ch12570Hussain, R. A., Badshash, A., Sohail, M., Lal, B., & Altaf, A. A. (2013). Synthesis, chemical characterization, DNA interaction and antioxidant studies of ortho, meta and para fluoro substituted ferrocene incorporated selenoureas. Inorganica Chimica Acta, 402, 133-139. doi:10.1016/j.ica.2013.04.003Takahashi, H., Nishina, A., Fukumoto, R., Kimura, H., Koketsu, M., & Ishihara, H. (2005). Selenoureas and thioureas are effective superoxide radical scavengers in vitro. Life Sciences, 76(19), 2185-2192. doi:10.1016/j.lfs.2004.08.037Caltagirone, C., Bazzicalupi, C., Bencini, A., Isaia, F., Garau, A., & Lippolis, V. (2012). Anion recognition properties of pyridine-2,6-dicarboxamide and isophthalamide derivatives containingl-tryptophan moieties. Supramolecular Chemistry, 24(2), 95-100. doi:10.1080/10610278.2011.628391Caltagirone, C., Bazzicalupi, C., Isaia, F., Light, M. E., Lippolis, V., Montis, R., … Picci, G. (2013). A new family of bis-ureidic receptors for pyrophosphate optical sensing. Organic & Biomolecular Chemistry, 11(15), 2445. doi:10.1039/c3ob27244cCasula, A., Bazzicalupi, C., Bettoschi, A., Cadoni, E., Coles, S. J., Horton, P. N., … Caltagirone, C. (2016). Fluorescent asymmetric bis-ureas for pyrophosphate recognition in pure water. Dalton Transactions, 45(7), 3078-3085. doi:10.1039/c5dt04497aOlivari, M., Montis, R., Karagiannidis, L. E., Horton, P. N., Mapp, L. K., Coles, S. J., … Caltagirone, C. (2015). Anion complexation, transport and structural studies of a series of bis-methylurea compounds. Dalton Transactions, 44(5), 2138-2149. doi:10.1039/c4dt02893gTetilla, M. A., Aragoni, M. C., Arca, M., Caltagirone, C., Bazzicalupi, C., Bencini, A., … Meli, V. (2011). Colorimetric response to anions by a «robust» copper(ii) complex of a [9]aneN3 pendant arm derivative: CN− and I− selective sensing. Chemical Communications, 47(13), 3805. doi:10.1039/c0cc04500dFernández-Bolaños, J. G., López, Ó., Ulgar, V., Maya, I., & Fuentes, J. (2004). Synthesis of O -unprotected glycosyl selenoureas. A new access to bicyclic sugar isoureas. Tetrahedron Letters, 45(21), 4081-4084. doi:10.1016/j.tetlet.2004.03.143GANS, P., SABATINI, A., & VACCA, A. (1996). Investigation of equilibria in solution. Determination of equilibrium constants with the HYPERQUAD suite of programs. Talanta, 43(10), 1739-1753. doi:10.1016/0039-9140(96)01958-3H. Deddek , Progress in NMR Spectroscopy, Pergamon, Oxford, 1995, vol. 27, pp. 1–323Bigoli, F., Demartin, F., Deplano, P., Devillanova, F. A., Isaia, F., Lippolis, V., … Trogu, E. F. (1996). Synthesis, Characterization, and Crystal Structures of New Dications Bearing the −Se−Se− Bridge. Inorganic Chemistry, 35(11), 3194-3201. doi:10.1021/ic9510019Isaia, F., Aragoni, M. C., Arca, M., Demartin, F., Devillanova, F. A., Floris, G., … Verani, G. (2008). Interaction of Methimazole with I2: X-ray Crystal Structure of the Charge Transfer Complex Methimazole−I2. Implications for the Mechanism of Action of Methimazole-Based Antithyroid Drugs. Journal of Medicinal Chemistry, 51(13), 4050-4053. doi:10.1021/jm8001857Roy, G., Bhabak, K. P., & Mugesh, G. (2011). Interactions of Antithyroid Drugs and Their Analogues with Halogens and their Biological Implications. Crystal Growth & Design, 11(6), 2279-2286. doi:10.1021/cg101688vCliment, E., Martínez-Máñez, R., Sancenón, F., Marcos, M. D., Soto, J., Maquieira, A., & Amorós, P. (2010). Controlled Delivery Using Oligonucleotide-Capped Mesoporous Silica Nanoparticles. Angewandte Chemie International Edition, 49(40), 7281-7283. doi:10.1002/anie.201001847Santos-Figueroa, L. E., Giménez, C., Agostini, A., Aznar, E., Marcos, M. D., Sancenón, F., … Amorós, P. (2013). Selective and Sensitive Chromofluorogenic Detection of the Sulfite Anion in Water Using Hydrophobic Hybrid Organic-Inorganic Silica Nanoparticles. Angewandte Chemie International Edition, 52(51), 13712-13716. doi:10.1002/anie.20130668
Getting Past the Language Gap: Innovations in Machine Translation
In this chapter, we will be reviewing state of the art machine translation systems, and will discuss innovative methods for machine translation, highlighting the most promising techniques and applications. Machine translation (MT) has benefited from a revitalization in the last 10 years or so, after a period of relatively slow activity. In 2005 the field received a jumpstart when a powerful complete experimental package for building MT systems from scratch became freely available as a result of the unified efforts of the MOSES international consortium. Around the same time, hierarchical methods had been introduced by Chinese researchers, which allowed the introduction and use of syntactic information in translation modeling. Furthermore, the advances in the related field of computational linguistics, making off-the-shelf taggers and parsers readily available, helped give MT an additional boost. Yet there is still more progress to be made. For example, MT will be enhanced greatly when both syntax and semantics are on board: this still presents a major challenge though many advanced research groups are currently pursuing ways to meet this challenge head-on. The next generation of MT will consist of a collection of hybrid systems. It also augurs well for the mobile environment, as we look forward to more advanced and improved technologies that enable the working of Speech-To-Speech machine translation on hand-held devices, i.e. speech recognition and speech synthesis. We review all of these developments and point out in the final section some of the most promising research avenues for the future of MT
Naphthalene-1-carbaldehyde oxime
The title compound, C11H9NO, crystallizes with two molecules, A and B, with similar conformations (r.m.s. overlay fit = 0.030 Å) in the asymmetric unit: the C—C=N...O torsion angles are −177.8 (3) and −179.1 (3)°. In the crystal, molecules are linked by alternating O—H...N (A → B) and O—H...O (B → A) hydrogen bonds to generate [100] chains. A weak C—H...O interaction is also observed
Mono- and Binuclear Copper(I) Complexes of Thionucleotide Analogues and Their Catalytic Activity on the Synthesis of Dihydrofurans
The
reaction of copper(I) halides with 2-thiouracil (TUC), 6-methyl-2-thiouacil
(MTUC), and 4-methyl-2-mercaptopyrimidine (MPMTH) in the presence
of triphenylphosphine (tpp) in a 1:1:2 molar ratio results in a mixed-ligand
copper(I) complex with the formulas [Cu<sub>2</sub>(tpp)<sub>4</sub>(TUC)Cl] (<b>1</b>), [Cu<sub>2</sub>(tpp)<sub>4</sub>(MTUC)Cl]
(<b>2</b>), [Cu(tpp)<sub>2</sub>(MPMTH)Cl]·<sup>1</sup>/<sub>2</sub>CH<sub>3</sub>OH (<b>3</b>), [Cu(tpp)<sub>2</sub>(MTUC)Br] (<b>4</b>), and [Cu(tpp)<sub>2</sub>(MTUC)I]·<sup>1</sup>/<sub>2</sub>CH<sub>3</sub>CN (<b>5</b>). The complexes
have been characterized by FT-IR, <sup>1</sup>H NMR, and UV–vis
spectroscopic techniques and single-crystal X-ray crystallography.
Complexes <b>1</b> and <b>2</b> are binuclear copper(I)
complexes. Two phosphorus atoms from tpp ligands are coordinated to
the copper(I) ions, forming two units that are linked to each other
by a deprotonated TUC or MTUC chelating ligand through a sulfur bridge.
A linear Cu–S–Cu moiety is formed. The tetrahedral geometry
around the metal centers is completed by the nitrogen-donor atom from
the TUC or MTUC ligand for the one unit, while for the other one,
it is completed by the chloride anion. Two phosphorus atoms from two
tpp ligands, one sulfur atom from MPMTH or MTUC ligand, and one halide
anion (Cl, Br, and I) form a tetrahedron around the copper ion in <b>3</b>–<b>5</b> and two polymorphic forms of <b>4</b> (<b>4a</b> and <b>4b</b>). In all of the complexes,
either mono- or binuclear intramolecular O–H···X
hydrogen bonds enhance the stability of the structures. On the other
hand, in almost all cases of mononuclear complexes (with the exception
of a symmetry-independent molecule in <b>4a</b>), intermolecular
NH···O hydrogen-bonding interactions lead to dimerization.
Complexes <b>1</b>–<b>5</b> were studied for their
catalytic activity for the intermolecular cycloaddition of iodonium
ylides toward dihydrofuran formation by HPLC, <sup>1</sup>H NMR, and
LC-HRMS spectroscopic techniques. The results show that the geometry
and halogen and ligand types have a strong effect on the catalytic
properties of the complexes. The highest yield of dihydrofurans was
obtained when “linear” complexes <b>1</b> and <b>2</b> were used as the catalysts. The activity of the metal complexes
on the copper(I)-catalyzed and uncatalyzed intramolecular cycloaddition
of iodonium ylide is rationalized through electronic structure calculation
methods, and the results are compared with the experimental ones
NGO Hybridisation as an Outcome of HIV Services Delivery in Global Fund-Supported Programmes in Ukraine
Ukraine has one of the world's fastest growing HIV rates and was one of the largest recipients of funding from the Global Fund to Fight AIDS, Tuberculosis and Malaria (GF). Doctoral research recently completed by the author investigates the conduct and practice of international and national nongovernmental organisations (NGOs) as Principal Recipients of GF grants in Ukraine from 2004 to 2012. The study aimed to understand how NGO-based services were implemented in the context of a state-owned health care system. An ethnographic enquiry including 50 participant interviews was conducted in three oblasts in Ukraine, and in its capital, Kyiv, between 2011 and 2013. The paper is based on a doctoral research and presents some of the findings that emerged from the analysis. The author argues that the accent on NGO-run services promoted by GF has rendered the original grass roots, community-based NGOs, to be undermined or replaced by 'quasi', hybrid NGOs created by health officials and AIDS centres head doctors. The outcome of such hybridization is a weakened civil society that is dependent on external funding and is unable to genuinely represent their communities. 2015 International Society for Third-Sector Research and The Johns Hopkins Universitysch_iihpub3992pu
Results of a Pilot Test of a Brief Computer-Assisted Tailored HIV Prevention Intervention for Use with a Range of Demographic and Risk Groups
There is a need for brief HIV prevention interventions that can be disseminated and implemented widely. This article reports the results of a small randomized field experiment that compared the relative effects of a brief 2-session counselor-delivered computer-tailored intervention and a control condition. The intervention is designed for use with African American, non-Hispanic white and Hispanic males and females who may be at risk of HIV through unprotected sex, selling sex, male to male sex, injecting drug use or use of stimulants. Participants (n=120) were recruited using a quota sampling approach and randomized using block randomization, which resulted in 10 male and 10 female participants of each racial/ethnic group (i.e. African-American, non-Hispanic white and Hispanic) being assigned to either the intervention or a control arm. In logistic regression analyses using a generalized estimating equations approach, at 3-month followup, participants in the intervention arm were more likely than participants in the control arm to report condom use at last sex (Odds ratio [OR] = 4.75; 95% Confidence interval [C.I.] = 1.70, 13.26; p = 0.003). The findings suggest that a brief tailored intervention may increase condom use. Larger studies with longer followups are needed to determine if these results can be replicated