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71.
Cordaro M Di Donna L Grassi G Maiuolo L Mazzotti F Perri E Sindona G Tagarelli A 《European journal of mass spectrometry (Chichester, England)》2004,10(5):691-697
An evaluation of the gas-phase ion chemistry of rotenone (1) by electrospray ionisation (ESI) mass spectrometry (MS) and tandem mass spectrometry (MS2) is presented, aiming at providing tools for its determination in natural and biological matrices. The behaviour of its cycloadducts with benzonitrile-N-oxide (2) and 2,4,6-trimethylbenzonitrile-N-oxide (3) was also evaluated and the MS data thus obtained have provided evidence into the mechanism of formation of the key product ion at m/z 192 which can be considered a marker in the MS and MS2 spectra of rotenone and its derivatives. 相似文献
72.
Caterina Fraschetti Matthias C. Letzel Marlene Paletta Jochen Mattay Maurizio Speranza Antonello Filippi Massimiliano Aschi Alexander B. Rozhenko 《Journal of mass spectrometry : JMS》2012,47(1):72-78
The effect of cyclochirality of rccc‐2,8,14,20‐tetra‐n‐decyl‐4,10,16,22‐tetra‐O‐methylresorcin[4]arene (C) on the enantiodiscrimination of a number of chiral bidentate and tridentate aromatic and aliphatic biomolecules (G) has been investigated by nano‐electrospray ionization (nano‐ESI)‐Fourier transform ion cyclotron resonance mass spectrometry. The experimental approach is based on the formation of diastereomeric proton‐bound [C·H·G]+ complexes by nano‐ESI of solutions containing an equimolar amount of quasi‐enantiomers (C) together with the chiral guest (G) and the subsequent measurement of the rate of the G substitution by the attack of several achiral and chiral amines. In general, the heterochiral complexes react faster than the homochiral ones, except when G is an aminoalcoholic neurotransmitter whose complexes, beyond that, exhibit the highest enantioselectivity. The kinetic results were further supported by both collision‐induced dissociation experiments on some of the relevant [C2·H·G]+ three‐body species and Density functional theory (DFT) calculations performed on the most selective systems. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
73.
74.
Volonterio A Bellosta S Bravin F Bellucci MC Bruché L Colombo G Malpezzi L Mazzini S Meille SV Meli M Ramírez De Arellano C Zanda M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(18):4510-4522
Partially modified retro- (PMR) and retro-inverso (PMRI) psi[NHCH(CF(3))]Gly peptides, a conceptually new class of peptidomimetics, have been synthesized in wide structural diversity and variable length by aza-Michael reaction of enantiomerically pure alpha-amino esters and peptides with enantiomerically and geometrically pure N-4,4,4-trifluorocrotonoyl-oxazolidin-2-ones. The factors underlying the observed moderate to good diastereocontrol have been investigated. The conformations of model PMR-psi[NHCH(CF(3))]Gly tripeptides have been studied in solution by (1)H NMR spectroscopy supported by MD calculations, as well as in the solid-state by X-ray diffraction. Remarkable stability of turn-like conformations, comparable to that of parent malonyl-based retropeptides, was evidenced, as a likely consequence of two main factors: 1) severe torsional restrictions about sp(3) bonds in the [CO-CH(2)-CH(CF(3))-NH-CH(R)-CO] module, which is biased by the stereoelectronically demanding CF(3) group and the R side chain; 2) formation of nine-membered intramolecularly hydrogen-bonded rings, which have been clearly detected both in CHCl(3) solution and in some crystal structures. The former factor seems to be more important, as turn-like conformations were found in the solid-state even in the absence of intramolecular hydrogen bonding. The relative configuration of the -C*H(CF(3))NHC*H(R)- stereogenic centers has a major effect on the stability of the turn-like conformation, which seems to require a syn stereochemistry. X-ray diffraction and ab initio computational studies showed that the [-CH(CF(3))NH-] group can be seen as a sort of hybrid between a peptide bond mimic and a proteolytic transition state analogue, as it combines some of the properties of a peptidyl -CONH- group (low NH basicity, CH(CF(3))-NH-CH backbone angle close to 120 degrees, C-CF(3) bond substantially isopolar with the C=O) with some others of the tetrahedral intermediate [-C(OX)(O(-))NH-] involved in the protease-mediated hydrolysis reaction of a peptide bond (high electron density on the CF(3) group, tetrahedral backbone carbon). 相似文献
75.
Sala Vila A Castellote-Bargalló AI Rodríguez-Palmero-Seuma M López-Sabater MC 《Journal of chromatography. A》2003,1008(1):73-80
We developed and validated a new high-performance liquid chromatographic method for the separation of phospholipid classes in human milk, infant formulas and phospholipidic sources of long-chain polyunsaturated fatty acids (LC-PUFAs) used in paediatric nutrition. Phosphatidylcholine, phosphatidylethanolamine, phosphatidylinositol, phosphatidylserine and sphingomyelin were separated in less than 25 min using an Extrasil silica column (150 x 4.0 mm I.D., 3-microm particle size) by isocratic elution with a mixture of isopropanol-hexane-water. Phospholipids were determined by an evaporative light-scattering detector. Several chromatographic conditions were assayed to optimise the method, whose suitability is shown by the detection limits, linearity ranges and precision rates obtained. The main advantages of the proposed method are its speed and the direct determination of the main phospholipids present in human milk, infant formulas and the phospholipid sources of LC-PUFAs used in paediatric nutrition. 相似文献
76.
Craig J. Richmond Roc Matheu Dr. Albert Poater Dr. Laura Falivene Dr. Jordi Benet‐Buchholz Dr. Xavier Sala Prof. Luigi Cavallo Prof. Antoni Llobet 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(52):17282-17286
Extremely slow and extremely fast new water oxidation catalysts based on the Ru–bda (bda=2,2′‐bipyridine‐6,6′‐dicarboxylate) systems are reported with turnover frequencies in the range of 1 and 900 cycles s?1, respectively. Detailed analyses of the main factors involved in the water oxidation reaction have been carried out and are based on a combination of reactivity tests, electrochemical experiments, and DFT calculations. These analyses give a convergent interpretation that generates a solid understanding of the main factors involved in the water oxidation reaction, which in turn allows the design of catalysts with very low energy barriers in all the steps involved in the water oxidation catalytic cycle. We show that for this type of system π‐stacking interactions are the key factors that influence reactivity and by adequately controlling them we can generate exceptionally fast water oxidation catalysts. 相似文献
77.
Dividing a complex reaction involving a hypervalent iodine reagent into three limiting mechanisms by ab initio molecular dynamics 下载免费PDF全文
Oliver Sala Hans Peter Lüthi Antonio Togni Marcella Iannuzzi Jürg Hutter 《Journal of computational chemistry》2015,36(11):785-794
The electrophilic N‐trifluoromethylation of MeCN with a hypervalent iodine reagent to form a nitrilium ion, that is rapidly trapped by an azole nucleophile, is thought to occur via reductive elimination (RE). A recent study showed that, depending on the solvent representation, the SN2 is favoured to a different extent over the RE. However, there is a discriminative solvent effect present, which calls for a statistical mechanics approach to fully account for the entropic contributions. In this study, we perform metadynamic simulations for two trifluoromethylation reactions (with N‐ and S‐nucleophiles), showing that the RE mechanism is always favoured in MeCN solution. These computations also indicate that a radical mechanism (single electron transfer) may play an important role. The computational protocol based on accelerated molecular dynamics for the exploration of the free energy surface is transferable and will be applied to similar reactions to investigate other electrophiles on the reagent. Based on the activation parameters determined, this approach also gives insight into the mechanistic details of the trifluoromethylation and shows that these commonly known mechanisms mark the limits within which the reaction proceeds. © 2015 Wiley Periodicals, Inc. 相似文献
78.
Direct On‐Surface Patterning of a Crystalline Laminar Covalent Organic Framework Synthesized at Room Temperature 下载免费PDF全文
Alejandro de la Peña Ruigómez David Rodríguez‐San‐Miguel Dr. Kyriakos C. Stylianou Dr. Massimiliano Cavallini Dr. Denis Gentili Dr. Fabiola Liscio Prof. Silvia Milita Dr. Otello Maria Roscioni Dr. Maria Luisa Ruiz‐González Carlos Carbonell Prof. Daniel Maspoch Dr. Rubén Mas‐Ballesté Dr. José Luis Segura Dr. Félix Zamora 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(30):10666-10670
We report herein an efficient, fast, and simple synthesis of an imine‐based covalent organic framework (COF) at room temperature (hereafter, RT‐COF‐1 ). RT‐COF‐1 shows a layered hexagonal structure exhibiting channels, is robust, and is porous to N2 and CO2. The room‐temperature synthesis has enabled us to fabricate and position low‐cost micro‐ and submicropatterns of RT‐COF‐1 on several surfaces, including solid SiO2 substrates and flexible acetate paper, by using lithographically controlled wetting and conventional ink‐jet printing. 相似文献
79.
Stabilization of Titanium Dioxide Nanoparticles at the Surface of Carbon Nanomaterials Promoted by Microwave Heating 下载免费PDF全文
Rui Zhang Prof. Dr. Saveria Santangelo Dr. Enza Fazio Prof. Dr. Fortunato Neri Dr. Massimiliano D'Arienzo Prof. Dr. Franca Morazzoni Prof. Dr. Yihe Zhang Prof. Dr. Nicola Pinna Dr. Patrícia A. Russo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(42):14901-14910
TiO2 is frequently combined with carbon materials, such as reduced graphene oxide (RGO), to produce composites with improved properties, for example for photocatalytic applications. It is shown that heating conditions significantly affect the interface and photocatalytic properties of TiO2@C, and that microwave irradiation can be advantageous for the synthesis of carbon‐based materials. Composites of TiO2 with RGO or amorphous carbon were prepared from reaction of titanium isopropoxide with benzyl alcohol. During the synthesis of the TiO2 nanoparticles, the carbon is involved in reactions that lead to the covalent attachment of the oxide, the extent of which depends on the carbon characteristics, heating rate, and mechanism. TiO2 is more efficiently stabilized at the surface of RGO than amorphous carbon. Rapid heating of the reaction mixture results in a stronger coupling between the nanoparticles and carbon, more uniform coatings, and smaller particles with narrower size distributions. The more efficient attachment of the oxide leads to better photocatalytic performance. 相似文献