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151.
Abstract: The synthesis of the indolo[2,3-a]carbazole ring is described starting from 3-chloromethylene-1,3-dihydro-indol-2-one 5 and 3-(cyano-ethoxycarbonyl-methyl)-indole-1-carboxylic acid ethyl ester 4. 相似文献
152.
Nicholas F. Chilton Russell P. Anderson Lincoln D. Turner Alessandro Soncini Keith S. Murray 《Journal of computational chemistry》2013,34(13):1164-1175
A new program, PHI, with the ability to calculate the magnetic properties of large spin systems and complex orbitally degenerate systems, such as clusters of d‐block and f‐block ions, is presented. The program can intuitively fit experimental data from multiple sources, such as magnetic and spectroscopic data, simultaneously. PHI is extensively parallelized and can operate under the symmetric multiprocessing, single process multiple data, or GPU paradigms using a threaded, MPI or GPU model, respectively. For a given problem PHI is been shown to be almost 12 times faster than the well‐known program MAGPACK, limited only by available hardware. © 2013 Wiley Periodicals, Inc. 相似文献
153.
Dr. Alessandro Barge Marina Caporaso Prof. Giancarlo Cravotto Dr. Katia Martina Dr. Paolo Tosco Prof. Silvio Aime Dr. Carla Carrera Dr. Eliana Gianolio Dr. Giorgio Pariani Dr. Davide Corpillo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(36):12086-12092
We report the synthesis and characterization of a water‐soluble, star‐shaped macromolecular platform consisting of eight β‐cyclodextrin (β‐CD) units anchored to the narrower rim of a γ‐CD core through bis(triazolyl)alkyl spacers. The efficient synthetic protocol is based on the microwave (MW)‐promoted Cu‐catalyzed 1,3‐dipolar cycloaddition of CD monoazides to CD monoacetylenes. The ligand‐hosting capability of the construct has been assessed by relaxometric titration and nuclear magnetic relaxation dispersion (NMRD) profiling, which showed it to be good, and this was supported by molecular dynamics simulations. To demonstrate the feasibility of obtaining supramolecular structures with high hosting ability, we designed a dimeric platform, formed by joining two nonamers through the γ‐CD cores through a bis(lithocholic acid) linker. With a view to the potential biological applications, cytotoxicity and extent of binding to human serum albumin were assessed. The properties of this dendrimeric multicarrier make it suitable for pharmaceutical and diagnostic purposes, ranging from targeted drug delivery to molecular imaging. 相似文献
154.
Ross S. Winter Dr. Jun Yan Dr. Christoph Busche Dr. Jennifer S. Mathieson Dr. Alessandro Prescimone Prof. Euan K. Brechin Dr. De‐Liang Long Prof. Leroy Cronin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(9):2976-2981
Two near isomeric clusters containing a novel {Mn8W4} Keggin cluster within a [W36Mn10Si4O136(OH)4(H2O)8]24? cluster are reported: K10Li14 [W36Si4O136MnII10(OH)4(H2O)8] ( 1 ) and K10Li13.5Mn0.25[W36Si4O136MnII10(OH)4(H2O)8] ( 1′ ). Bulk characterization of the clusters has been carried out by single crystal X‐ray structure analysis, ICP‐MS, TGA, ESI‐MS, CV and SQUID‐magnetometer analysis. X‐ray analysis revealed that 1′ has eight positions within the central Keggin core that were disordered W/Mn whereas 1 contained no such disorder. This subtle difference is due to a differences is how the two clusters assemble and recrystallize from the same mother liquor and represents a new type of isomerism. The rapid recrystallization process was captured via digital microscopy and this uncovered two “intermediate” types of crystal which formed temporarily and provided nucleation sites for the final clusters to assemble. The intermediates were investigated by single crystal X‐ray analysis and revealed to be novel clusters K4Li22[W36Si4Mn7O136(H2O)8]?56 H2O ( 2 ) and Mn2K8Li14[W36Si4Mn7O136(H2O)8]?45 H2O ( 3 ). The intermediate clusters contained different yet related building blocks to the final clusters which allowed for the postulation of a mechanism of assembly. This demonstrates a rare example where the use X‐ray crystallography directly facilitated understanding the means by which a POM assembled. 相似文献
155.
Núria Mas Alessandro Agostini Dr. Laura Mondragón Dr. Andrea Bernardos Dr. Félix Sancenón Dr. M. Dolores Marcos Prof. Ramón Martínez‐Máñez Prof. Ana M. Costero Prof. Salvador Gil Prof. Matilde Merino‐Sanjuán Prof. Pedro Amorós Dr. Mar Orzáez Prof. Enrique Pérez‐Payá 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(4):1346-1356
The preparation of a new capped silica mesoporous material, Rh‐Azo‐S , for on‐command delivery applications in the presence of target enzymes is described. The material consists of nanometric mesoporous MCM‐41‐like supports loaded with Rhodamine B and capped with an azopyridine derivative. The material was designed to show “zero delivery” and to display a cargo release in the presence of reductases and esterases, which are usually present in the colon, mainly due to intestinal microflora. The opening and cargo release of Rh‐Azo‐S in vitro studies were assessed and seen to occur in the presence of these enzymes, whereas no delivery was noted in the presence of pepsine. Moreover, Rh‐Azo‐S nanoparticles were used to study controlled Rhodamine B dye delivery in intracellular media. HeLa cells were employed for testing the “non”‐toxicity of nanoparticles. Moreover, delivery of the dye in these cells, through internalization and enzyme‐mediated gate opening, was confirmed by confocal microscopy. Furthermore, the nanoparticles capped with the Azo group and loaded with a cytotoxic camptothecin ( CPT ) were also prepared (solid CPT‐Azo‐S ) and used as delivery nanodevices in HeLa cells. When this solid was employed, the cell viability decreased significantly due to internalization of the nanoparticles and delivery of the cytotoxic agent. 相似文献
156.
Olga Bortolini Dr. Alberto Cavazzini Pier Paolo Giovannini Roberto Greco Nicola Marchetti Dr. Alessandro Massi Luisa Pasti 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(24):7802-7808
The heterogeneous proline‐catalyzed aldol reaction was investigated under continuous‐flow conditions by means of a packed‐bed microreactor. Reaction‐progress kinetic analysis (RPKA) was used in combination with nonlinear chromatography for the interpretation, under synthetically relevant conditions, of important mechanistic aspects of the heterogeneous catalytic process at a molecular level. The information gathered by RPKA and nonlinear chromatography proved to be highly complementary and allowed for the assessment of optimal operating variables. In particular, the determination of the rate‐determining step was pivotal for optimizing the feed composition. On the other hand, the competitive product inhibition was responsible for the unexpected decrease in the reaction yield following an apparently obvious variation in the feed composition. The study was facilitated by a suitable 2D instrumental arrangement for simultaneous flow reaction and online flow‐injection analysis. 相似文献
157.
Alessandro Marchetti Dr. Andrea Pizzi Dr. Greta Bergamaschi Dr. Nicola Demitri Dr. Ulrike Stollberg Prof. Ulf Diederichsen Dr. Claudia Pigliacelli Prof. Pierangelo Metrangolo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(14):e202104089
Iodination has long been employed as a successful labelling strategy to gain structural insights into proteins and other biomolecules via several techniques, including Small Angle X-ray Scattering, Inductively Coupled Plasma Mass Spectrometer (ICP-MS), and single-crystal crystallography. However, when dealing with smaller biomolecular systems, interactions driven by iodine may significantly alter their self-assembly behaviour. The engineering of amyloidogenic peptides for the development of ordered nanomaterials has greatly benefitted from this possibility. Still, to date, iodination has exclusively been applied to aromatic residues. In this work, an aliphatic bis-iodinated amino acid was synthesized and included into a custom pentapeptide, which showed enhanced fibrillogenic behaviour. Peptide single crystal X-ray structure and powder X-ray diffraction on its dried water solution demonstrated the key role of iodine atoms in promoting intermolecular interactions that drive the peptide self-assembly into amyloid fibrils. These findings enlarge the library of halogenated moieties available for directing and engineering the self-assembly of amyloidogenic peptides. 相似文献
158.
Galvagnini Francesco Dorigato Andrea Valentini Francesco Fiore Vincenzo La Gennusa Maria Pegoretti Alessandro 《Journal of Thermal Analysis and Calorimetry》2022,147(1):297-313
Journal of Thermal Analysis and Calorimetry - In this work, polyurethane (PU) insulating panels containing different amounts of a microencapsulated paraffin with a nominal melting temperature of... 相似文献
159.
Dr. Francesco Rigodanza Prof. Nadia Marino Dr. Alessandro Bonetto Prof. Antonio Marcomini Prof. Marcella Bonchio Prof. Mirco Natali Prof. Andrea Sartorel 《Chemphyschem》2021,22(12):1208-1218
The cobalt substituted polyoxotungstate [Co6(H2O)2(α-B-PW9O34)2(PW6O26)]17− ( Co6 ) displays fast electron transfer (ET) kinetics to photogenerated RuIII(bpy)33+, 4 to 5 orders of magnitude faster than the corresponding ET observed for cobalt oxide nanoparticles. Mechanistic evidence has been acquired indicating that: (i) the one-electron oxidation of Co6 involves Co(II) aquo or Co(II) hydroxo groups (abbreviated as Co6(II) −OH 2 and Co6(II) −OH, respectively, whose speciation in aqueous solution is associated to a pKa of 7.6), and generates a Co(III)−OH moiety ( Co6(III) −OH), as proven by transient absorption spectroscopy; (ii) at pH>pKa, the Co6(II) −OH→RuIII(bpy)33+ ET occurs via bimolecular kinetics, with a rate constant k close to the diffusion limit and dependent on the ionic strength of the medium, consistent with reaction between charged species; (iii) at pH <pKa, the process involves Co6(II) − OH2 → Co6(III)−OH transformation and proceeds via a multiple-site, concerted proton electron transfer (CPET) where water assists the transfer of the proton, as proven by the absence of effect of buffer base concentrations on the rate of the ET and by a H/D kinetic isotope in a range of 1.2–1.4. The reactivity of water is ascribed to its organization on the surface of the polyanionic scaffold through hydrogen bond networking involving the Co(II)−OH2 group. 相似文献
160.
Gaetano Isola Alessandro Polizzi Vincenzo Ronsivalle Angela Alibrandi Giuseppe Palazzo Antonino Lo Giudice 《Molecules (Basel, Switzerland)》2021,26(6)
Matrix metalloproteinase-9 (MMP-9) has been shown to play a key role in endothelial function and perhaps pivotal in the correlation between periodontal disease and cardiovascular disease (CVD). For the study, the impact of MMP-9 of periodontitis and CVD on serum and saliva concentrations was analyzed. For the study patients with periodontitis (n = 31), CVD (n = 31), periodontitis + CVD (n = 31), and healthy patients (n = 31) were enrolled. Clinical and demographic characteristics as well as serum and salivary MMP-9 were evaluated. MMP-9 concentrations in serum and saliva were statistically elevated in patients with CVD (p < 0.01) and in patients with periodontitis plus CVD (p < 0.001) compared to patients with periodontitis and healthy subjects. Multivariate regression analysis showed that c-reactive protein (hs-CRP) was the only significant predictor for MMP-9 serum (p < 0.001), whereas hs-CRP (p < 0.001) and total cholesterol (p = 0.029) were the statistically significant salivary MMP-9 predictors. This study evidenced that patients with CVD and periodontitis + CVD presented elevated MMP-9 concentrations in serum and saliva compared to patients with periodontitis and healthy subjects. Furthermore, hs-CRP was a negative predictor of serum and salivary MMP-9. 相似文献