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71.
Cocrystal Formation through Mechanochemistry: from Neat and Liquid‐Assisted Grinding to Polymer‐Assisted Grinding 下载免费PDF全文
Dr. Dritan Hasa Gabriela Schneider Rauber Prof. Dario Voinovich Prof. William Jones 《Angewandte Chemie (International ed. in English)》2015,54(25):7371-7375
Mechanochemistry is an effective method for the preparation of multicomponent crystal systems. In the present work, we propose an alternative to the established liquid‐assisted grinding (LAG) approach. Polymer‐assisted grinding (POLAG) is demonstrated to provide a new class of catalysts for improving reaction rate and increasing product diversity during mechanochemical cocrystallization reactions. We demonstrate that POLAG provides advantages comparable to the conventional liquid‐assisted process, whilst eliminating the risk of unwanted solvate formation as well as enabling control of resulting particle size. It represents a new approach for the development of functional materials through mechanochemistry, and possibly opens new routes toward the understanding of the mechanisms and pathways of mechanochemical cocrystal formation. 相似文献
72.
Identification of Structure–Activity Relationships from Screening a Structurally Compact DNA‐Encoded Chemical Library 下载免费PDF全文
Dr. Raphael M. Franzini Dr. Torun Ekblad Dr. Nan Zhong Moreno Wichert Willy Decurtins Angela Nauer Mauro Zimmermann Dr. Florent Samain Dr. Jörg Scheuermann Dr. Peter J. Brown Prof. Dr. Jonathan Hall Dr. Susanne Gräslund Prof. Dr. Herwig Schüler Prof. Dr. Dario Neri 《Angewandte Chemie (International ed. in English)》2015,54(13):3927-3931
Methods for the rapid and inexpensive discovery of hit compounds are essential for pharmaceutical research and DNA‐encoded chemical libraries represent promising tools for this purpose. We here report on the design and synthesis of DAL‐100K, a DNA‐encoded chemical library containing 103 200 structurally compact compounds. Affinity screening experiments and DNA‐sequencing analysis provided ligands with nanomolar affinities to several proteins, including prostate‐specific membrane antigen and tankyrase 1. Correlations of sequence counts with binding affinities and potencies of enzyme inhibition were observed and enabled the identification of structural features critical for activity. These results indicate that libraries of this type represent a useful source of small‐molecule binders for target proteins of pharmaceutical interest and information on structural features important for binding. 相似文献
73.
Seven new microcystin variants discovered from a native Microcystis aeruginosa strain – unambiguous assignment of product ions by tandem mass spectrometry 下载免费PDF全文
74.
Vollet DR Awano CM de Vicente FS Ruiz AI Donatti DA 《Langmuir : the ACS journal of surfaces and colloids》2011,27(17):10986-10992
The structure and formation kinetics of organic/silica hybrid species prepared from acid hydrolysis of vinyltriethoxisilane has been studied in situ by small-angle X-ray scattering (SAXS) at 298, 318, and 333 K in a strongly basic step of the process. The evolution of the SAXS intensity is compatible with the formation of linear chains which grow, coil, and branch to form polymeric macromolecules in solution. The SAXS data were analyzed by the scattering from a persistent chain model for polymeric macromolecules in solution using a modified branching Sharp and Bloomfield global function, which incorporates a branching probability typical of randomly and nonrandomly branched polycondensates, and in a particular case, it is also valid for polydisperse coils of linear chains. Growth of linear chains and coiling dominate the process up to the formation of likely monodisperse Gaussian coils or polydisperse coils of linear chains. The link probability to form a branching point is increased with time to form nonrandomly branched polycondensates in solution. The kinetics of the process is accelerated with temperature, but all the curves formed by the time evolution of the structural parameters in all temperatures can correspondingly be matched on a unique curve by using an appropriate time scaling factor. The activation energy of the process was evaluated as ΔE = 21 ± 1 kJ/mol. The characteristics of the kinetics are in favor of a complex overall mechanism controlled by both condensation reactions and dynamical forces driven by interfacial energy up to the final structure development of the hybrids. 相似文献
75.
Sonia Fiorilli Dario Caldarola Hao Ma Barbara Onida 《Journal of Sol-Gel Science and Technology》2011,60(3):260-265
Silica spheres with uniform size of 230–250 nm were functionalized with sulfonic groups and bi-functionalized with carboxylic and sulfonic groups via a co-condensation route, by adding the organosilanes (3-(triethoxysilyl)mercaptopropyl and 4-(triethoxysilyl)butyronitrile) to a pre-hydrolized TEOS solution. The conversion of mercapto and cyano groups to, respectively, sulfonic and carboxylic groups was carried out by treating both the samples with nitric acid solution. The presence of alkyl-SO3H and alkyl-COOH species at the silica surface in an approximate molar ratio of 1:1 was assessed by TG and NMR. FT-IR spectroscopy showed that both Brønsted acidic groups are accessible and give proton-transfer reaction to ammonia with the formation of ammonium ion. Sulfonic groups react irreversibly with ammonia at room temperature at variance with carboxylic groups which give a reversible proton-transfer, in agreement with the stronger Brønsted acidity of the former. 相似文献
76.
Narcisi V Mascini M Perez G Del Carlo M Tiscar PG Yamanaka H Compagnone D 《Talanta》2011,85(4):1927-1932
A post-PCR nucleic acid work by comparing experimental data, from electrochemical genosensors, and bioinformatics data, derived from the simulation of the secondary structure folding and prediction of hybridisation reaction, was carried out in order to rationalize the selection of ssDNA probes for the detection of two Bonamia species, B. exitiosa and B. ostreae, parasites of Ostrea edulis.Six ssDNA probes (from 11 to 25 bases in length, 2 thiolated and 4 biotinylated) were selected within different regions of B. ostreae and B. exitiosa PCR amplicons (300 and 304 bases, respectively) with the aim to discriminate between these parasite species. ssDNA amplicons and probes were analyzed separately using the “Mfold Web Server” simulating the secondary structure folding behaviour. The hybridisation of amplicon-probe was predicted by means of “Dinamelt Web Server”. The results were evaluated considering the number of hydrogen bonds broken and formed in the simulated folding and hybridisation process, variance in gaps for each sequence and number of available bases. In the experimental part, thermally denatured PCR products were captured at the sensor interface via sandwich hybridisation with surface-tethered probes (thiolated probes) and biotinylated signalling probes. A convergence between analytical signals and simulated results was observed, indicating the possibility to use bioinformatic data for ssDNA probes selection to be incorporated in genosensors. 相似文献
77.
78.
Hydrochlorothiazide is a common diuretic antihypertensive drug of the thiazide family. Its poor aqueous solubility is one of the reasons for its limited bioavailability after oral administration. This work aimed at the development of a hydrochlorothiazide:β-cyclodextrin (HTZ:β-CD) pharmaceutical composition in order to improve water solubility and bioavailability of the drug. The HTZ:β-CD complexes were prepared by three different methods: spray-drying, freeze-drying and fluid bed. Complexes were characterized by thermal analysis, Fourier transform-infrared (FTIR) spectroscopy, powder X-ray diffractometry, NMR (2D-ROESY), scanning electron microscopy (SEM), particle analysis and intrinsic dissolution. The findings reveal that three binary systems prepared presented better solubility results in comparison with free HTZ. Increased diuretic effect was observed to HTZ:β-CD obtained by fluid bed in comparison to free drug in rats. Results taken together suggest that pharmacological effect of HTZ in complex was increased by solubility improvement promoted by cyclodextrin. 相似文献
79.
[2.2]Paracyclophanes, incorporating functional groups in the aliphatic bridges, suitable for elimination to give [2.2]paracyclophanedienes, are synthesized through a novel approach. It relies on a double Pummerer rearrangement on dithiacyclophane precursors, followed by ring contraction through a photochemical sulfur extrusion, and it is compatible with aryl moieties possessing very different electronic properties. 相似文献
80.
The synthesis of versatile fluorine compounds and monomers for conducting polymer research and cyclopolymerizations is presented. Semiprotected 2,3,5,6-tetrafluoroterephthaldehyde 1 could be elaborated through Wittig olefination chemistry, deprotection and reduction to the previously unknown 4-vinyl-2,3,5,6-tetrafluorobenzylalcohol 8 in good yields. Compound 8 can be reacted to form the malonate ester, and then alkylation on the malonate moiety in mild conditions affords difunctional monomer 3. Through sequential esterifications on the malonate moiety, and subsequent alkylation, compound 4, a difunctional monomer for cyclopolymerization bearing one styrene and one perfluoroaryl styrene moiety, has been obtained. Preliminary experiments show that it is possible to cyclopolymerize 4 under free radical conditions. 相似文献