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101.
Distributions from high- HERA event data analyzed in a general search for new physics at H1 have been incorporated into QUAERO, an algorithm designed
to automate tests of specific hypo-theses with high energy collider data. The use of QUAERO@H1 to search for leptoquarks,
R-parity violating supersymmetry, and excited quarks provides examples to develop intuition for the algorithm’s performance. 相似文献
102.
Stefano Federico Tuhina Khan Nicola Relitti Giulia Chemi Margherita Brindisi Simone Brogi Ettore Novellino Daniela M. Zisterer Giuseppe Campiani Sandra Gemma Stefania Butini 《Tetrahedron letters》2018,59(51):4466-4470
We developed a Jocic-type protocol for the construction of the pyrrolonaphthoxazepine (PNOX) core. After an initial investigation based on the isolation of a trichloromethyl carbinol derivative, we shifted our attention towards a multicomponent single-step protocol. Screening of a variety of bases and solvents led to the identification of the optimum conditions for the preparation of the key α-aryloxy carboxylic acids to undergo intramolecular cyclization. The novel chemical route significantly improved overall yields for the preparation of PNOX-based compounds and was successfully extended to the preparation of 1,4-benzoxazinone-based templates. 相似文献
103.
Giulia Marsico Barbara A. Pignataro Marco Masi Antonio Evidente Francesca Casella Maria Chiara Zonno Jun-Hyung Tak Jeffrey R. Bloomquist Stefano Superchi Patrizia Scafato 《Tetrahedron》2018,74(28):3912-3923
The first asymmetric total synthesis of both enantiomers of the natural products colletorin A and colletochlorin A is presented. The proposed methodology is based on the coupling reaction between highly substituted aromatic Gilman cuprates and optically active allyl bromides, in turn obtained by Sharpless asymmetric dihydroxylation. The latter ensured a high degree of regio- and stereocontrol in the enantioselective step of the synthesis. The same synthetic strategy has been also applied for the preparation of differently halogenated synthetic analogues of colletochlorin A in high enantiomeric purity. The enantioselective synthesis of colletorin A and colletochlorin A allows to reliably assign their absolute configuration. Preliminary assessment of their herbicidal and insecticidal properties evidence the possibility to modulate the bioactivity of these compounds, highlighting its dependence on both the absolute stereochemistry and the halogen nature. 相似文献
104.
105.
Federico Begato Roberto Penasa Klaus Wurst Prof. Giulia Licini Prof. Cristiano Zonta 《Angewandte Chemie (International ed. in English)》2023,62(30):e202304490
Dynamic covalent chemistry (DCC) has, in recent years, provided valuable tools to synthesize molecular architectures of increasing complexity. We have also taken advantage of imine DCC chemistry to prepare TPMA -based supramolecular cages for molecular recognition applications. However, the versatility of this approach has as a major drawback the intrinsic hydrolytic lability of imines, which hampers some applications. We present herein a synthetic strategy that combines the advantages of a thermodynamic-driven formation of a supramolecular structure using imine chemistry, together with the possibility to synthetize chiral hydrolytically stable structures through a [3,3]-sigmatropic rearrangement. A preliminary mechanistic analysis of this one-pot synthesis and the scope of the reaction are also discussed. 相似文献
106.
Hardouin J Guénin E Malosse C Caron M Lecouvey M 《Rapid communications in mass spectrometry : RCM》2008,22(15):2287-2300
1-hydroxymethylene-1,1-bisphosphonic acids (HMBPs) are important drugs for the treatment of a variety of bone diseases. Since these compounds have no chromophore, their detection is challenging and mass spectrometry (MS) appears to be an appropriate sensitive tool. Our work deals with the analysis by electrospray ionization tandem mass spectrometry (ESI-MSn) of the well-known nitrogen-containing HMBP alendronate and of three analogues, considered as potential prodrugs. These four molecules share a common structure with different protecting groups on the phosphonic acid and on the amine functions. We describe the dissociation mechanisms of nitrogen-containing HMBPs in positive ion mode and we compare, in negative ion mode, our results with literature data. In both modes, the dissociations are essentially losses of ROH, and of phosphorus-containing species (HPO2, ROP(OH)2 and ROPO(OH)2), where R=H, C6H5, or CH3OC6H5. These fingerprints will be of great value for differentiating alendronate from its potential prodrugs in complex biological mixtures. 相似文献
107.
Nardello-Rataj V Caron L Borde C Aubry JM 《Journal of the American Chemical Society》2008,130(45):14914-14915
A series of "Balanced Catalytic Surfactants" (BCS) [(Cn)2N(C1)2]2MoO4 (n = 8, 9, 10, 12) based on amphiphilic double-tailed quaternary ammonium with molybdate as a counterion has been developed for the dark singlet [4 + 2] cyclooxygenation of organic substrates in three-liquid-phase microemulsion systems. These cationic surfactants form three-liquid-phase microemulsion systems at room temperature in the presence of an appropriate organic solvent and water without addition of any cosurfactant or electrolyte. Comparative peroxidation of rubrene points out the specific advantages of these three-phase media over phase transfer catalysis in two phase systems and on conventional one-phase microemulsions based on sodium molybdate: (i) only three constituents, (ii) low amounts of surfactants, (iii) insensitivity to water dilution, (iv) fast separation of the three phases, (v) straightforward recovery of the product and the surfactant from the oil and microemulsion phases, respectively. The preparative peroxidation of alpha-terpinene and 1,4,5-trimethylnaphtalene was performed in the ternary systems [(C8)2N(C1)2]2MoO4/water/tert-butyl acetate or benzene. The reusability of the catalyst, the catalytic nature of the BCS, and the ability of the systems to oxidize poorly reactive substrates were demonstrated showing the broadness of the applicability of such systems. 相似文献
108.
Structure and dynamics of a partially folded protein are decoupled from its mechanism of aggregation
Calloni G Lendel C Campioni S Giannini S Gliozzi A Relini A Vendruscolo M Dobson CM Salvatella X Chiti F 《Journal of the American Chemical Society》2008,130(39):13040-13050
A common strategy to study the mechanism of amyloid formation is the characterization of the structure and dynamics of the precursor state, which is in most cases a partially folded protein. Here we investigated the highly dynamic conformational state formed by the protein domain HypF-N at low pH, before aggregation, using fluorescence, circular dichroism, and NMR spectroscopies. The NMR analysis allowed us, in particular, to identify the regions of the sequence that form hydrophobic interactions and adopt an alpha-helical secondary structure in the pH-denatured ensemble. To understand the role that this residual structure plays in the aggregation of this protein, we probed the mechanism of aggregation using protein engineering experiments and thus identified the regions of the sequence of HypF-N that play a critical role in the conversion of this dynamic state into thioflavin T-binding and beta-sheet containing protofibrils. The combination of these two complementary approaches revealed that the aggregation of pH-denatured HypF-N is not structure-dependent, meaning that it is not driven by the regions of the protein that are either less or more protected in the initial partially folded state. It is, by contrast, promoted by discrete protein regions that have the highest intrinsic propensity to aggregate because of their physicochemical properties. 相似文献
109.
From evidence-based policy making to policy analytics 总被引:1,自引:0,他引:1
This paper aims at addressing the problem of what characterises decision-aiding for public policy making problem situations. Under such a perspective it analyses concepts like “public policy”, “deliberation”, “legitimation”, “accountability” and shows the need to expand the concept of rationality which is expected to support the acceptability of a public policy. We then analyse the more recent attempt to construct a rational support for policy making, the “evidence-based policy making” approach. Despite the innovation introduced with this approach, we show that it basically fails to address the deep reasons why supporting the design, implementation and assessment of public policies is such a hard problem. We finally show that we need to move one step ahead, specialising decision-aiding to meet the policy cycle requirements: a need for policy analytics. 相似文献
110.
[reaction: see text] The Ti(IV) complex 2c bearing a C3-symmetric triphenolate amine ligand is an air and moisture tolerant complex that efficiently catalyzes sulfoxidation reactions at room temperature without previous activation (catalyst loading down to 0.01%, TONs up to 8000, TOFs up to 1700 h-1, quantitative yields). Reactions were performed with aqueous hydrogen peroxide as oxidant, which adds value to the methodology from the environmental viewpoint. 相似文献