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981.
Vitamin C: an experimental and theoretical study on the gas‐phase structure and ion energetics of protonated ascorbic acid 下载免费PDF全文
Andreina Ricci Federico Pepi Paola Cimino Anna Troiani Stefania Garzoli Chiara Salvitti Brunella Di Rienzo Vincenzo Barone 《Journal of mass spectrometry : JMS》2016,51(12):1146-1151
In order to investigate the gas‐phase mechanisms of the acid catalyzed degradation of ascorbic acid (AA) to furan, we undertook a mass spectrometric (ESI/TQ/MS) and theoretical investigation at the B3LYP/6‐31 + G(d,p) level of theory. The gaseous reactant species, the protonated AA, [C6H8O6]H+, were generated by electrospray ionization of a 10?3 M H2O/CH3OH (1 : 1) AA solution. In order to structurally characterize the gaseous [C6H8O6]H+ ionic reactants, we estimated the proton affinity and the gas‐phase basicity of AA by the extended Cooks's kinetic method and by computational methods at the B3LYP/6‐31 + G(d,p) level of theory. As expected, computational results identify the carbonyl oxygen atom (O2) of AA as the preferred protonation site. From the experimental proton affinity of 875.0 ± 12 kJ mol?1 and protonation entropy ΔSp 108.9 ± 2 J mol?1 K?1, a gas‐phase basicity value of AA of 842.5 ± 12 kJ mol?1 at 298 K was obtained, which is in agreement with the value issuing from quantum mechanical computations. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
982.
Maria Chiara Brambilla 《Journal of Pure and Applied Algebra》2008,212(5):1229-1251
The Alexander-Hirschowitz theorem says that a general collection of k double points in imposes independent conditions on homogeneous polynomials of degree d with a well-known list of exceptions. Alexander and Hirschowitz completed its proof in 1995, solving a long standing classical problem, connected with the Waring problem for polynomials. We expose a self-contained proof based mainly on the previous works by Terracini, Hirschowitz, Alexander and Chandler, with a few simplifications. We claim originality only in the case d=3, where our proof is shorter. We end with an account of the history of the work on this problem. 相似文献
983.
We prove the following formula
for 1 < p < + ∞, and related more general results. The equality above easily follows by integrating by parts for p ≥ 2. The case 1
< p < 2 is more involved because of the presence of the singularity of |u|
p-2 near the zeroes of u and a sectional characterization of Sobolev spaces is required.
相似文献
984.
Dr. Anna Dall'Anese Dr. Massimo Tosolini Chiara Alberoni Dr. Gabriele Balducci Dr. Maurizio Polentarutti Prof. Dr. Claudio Pellecchia Prof. Dr. Paolo Tecilla Prof. Dr. Barbara Milani 《欧洲无机化学杂志》2023,26(1):e202200481
The last two decades have witnessed the development of homogeneous catalysts for ethylene homo- and co-polymerization reactions based on late transition metals. When Pd(II) is the metal of choice, the best ligand-metal combination deals with either bidentate nitrogen-donor molecules or phosphinobenzene sulfonate derivatives. In this contribution we have investigated the coordination chemistry to Pd(II) of a bidentate phosphorus ligand, namely 4,5-bis(diphenylphosphino)acenaphthene ( 1 ). Starting from the neutral complex, [Pd( 1 )(CH3)Cl], we obtained the cationic derivatives [Pd( 1 )(CH3)(L)][SbF6], with L being either CH3CN or 3,5-lutidine. Using in situ NMR spectroscopy we investigated the reaction of [Pd( 1 )(CH3)(NCCH3)][SbF6] with ethylene, at room temperature, and ambient ethylene pressure. We discovered that [Pd( 1 )(CH3)(NCCH3)][SbF6] acts as a catalyst for butenes and hexenes synthesis with the relevant Pd-ethyl intermediate as the catalyst resting state. At the same time the color of the solution turned from pale yellow to light red due to the formation of the dinuclear species [Pd(μ-η2−C6H5)PPh)−PPh2]2[SbF6]2. Both the neutral Pd(II) complex, activated in situ by NaSbF6, and the monocationic acetonitrile derivative were tested in the ethylene homopolymerization reaction at high pressure, leading to low molecular weight, branched, polyethylene. 相似文献
985.
Donatella Ferrara Marco Beccaria Chiara E. Cordero Giorgia Purcaro 《Journal of separation science》2023,46(20):2300390
Microwave-assisted extraction (MAE) is an important technique in analytical chemistry. It offers several advantages over traditional extraction methods, such as improved extraction efficiency, shorter extraction times, reduced solvent consumption, and enhanced analyte recovery. Using microwaves, heat is directly applied to the sample, leading to rapid and efficient extraction of target compounds by enhancing the solubility and diffusion of the target compounds, thus requiring lower solvent volume. Therefore, MAE can be considered a more environmentally friendly and cost-effective option facilitating the transition toward greener and more sustainable analytical chemistry workflows. This contribution systematically reviews the application of MAE to a selection of target compounds/compounds classes of relevance for food quality and safety assessment. As inclusion criteria, MAE active temperature control and molecularly-resolved characterization of the extracts were considered. Contents include a brief introduction of the principles of operation, available systems characteristics, and key parameters influencing extraction efficiency and selectivity. The application section covers functional food components (e.g., phenols, diterpenes, and carotenoids), lipids, contaminants (e.g., polycyclic aromatic hydrocarbons and mineral oil hydrocarbons), pesticides, veterinary drug residues, and a selection of process contaminants and xenobiotics of relevance for food safety. 相似文献
986.
Eleonora Rollo Dante Catellani Chiara Dall'Asta Michele Suman 《Journal of mass spectrometry : JMS》2023,58(10):e4969
Within the last decades, in the EU, there has been an increasing interest in toxic plant alkaloids as food contaminants, especially after the continuous and growing consumption of plant-based foods compared with food of animal origin. In this regard, the once neglected presence of these tropane alkaloids (TAs) and pyrrolizidine alkaloids (PAs) has recently been reconsidered by the European Food Safety Authority, highlighting the lack of data and the need to develop risk assessment strategies. For this reason, the emphasis has been placed on detecting their occurrence in food through the development of accurate and sensitive analytical methods to achieve the determination of these compounds. The present study aims to elaborate and validate an analytical method based on QuEChERS sample preparation approach, exploiting the UHPLC coupled to the HRMS to simultaneously identify and quantify 21 PAs and two TAs in cereals and spices. For TAs, the obtained limit of detection (LOD) is 0.1 μg·kg−1 and the limit of quantification (LOQ) is 0.4 μg·kg−1, while for PAs, the LODs values ranging between 0.2 to 0.3 μg·kg−1 and the LOQ, between 0.4 and 0.8 μg·kg−1, ensuring compliance with the recently established European Regulations. Several commercial samples were analysed to further verify the applicability of this comprehensive analytical approach. 相似文献
987.
Dr. Isaac J. Gresham Seamus G. Lilley Dr. Andrew R. J. Nelson Dr. Kaloian Koynov Prof. Chiara Neto 《Angewandte Chemie (International ed. in English)》2023,62(41):e202308008
Slippery covalently-attached liquid surfaces (SCALS) with low contact angle hysteresis (CAH, <5°) and nanoscale thickness display impressive anti-adhesive properties, similar to lubricant-infused surfaces. Their efficacy is generally attributed to the liquid-like mobility of the constituent tethered chains. However, the precise physico-chemical properties that facilitate this mobility are unknown, hindering rational design. This work quantifies the chain length, grafting density, and microviscosity of a range of polydimethylsiloxane (PDMS) SCALS, elucidating the nanostructure responsible for their properties. Three prominent methods are used to produce SCALS, with characterization carried out via single-molecule force measurements, neutron reflectometry, and fluorescence correlation spectroscopy. CO2 snow-jet cleaning was also shown to reduce the CAH of SCALS via a modification of their grafting density. SCALS behavior can be predicted by reduced grafting density, Σ, with the lowest water CAH achieved at Σ≈2. This study provides the first direct examination of SCALS grafting density, chain length, and microviscosity and supports the hypothesis that SCALS properties stem from a balance of layer uniformity and mobility. 相似文献
988.
Perrino C Lee S Choi SW Maruyama A Spencer ND 《Langmuir : the ACS journal of surfaces and colloids》2008,24(16):8850-8856
Poly( L-lysine)- graft-dextran (PLL- g-dex), graft copolymers with dextran side chains grafted onto a poly( L-lysine) backbone, previously shown to be effective as stabilizers of DNA triple helices and as carriers of functional genes to target cells or tissues, were employed in this work to prevent nonspecific adsorption of proteins, as determined by means of optical waveguide lightmode spectroscopy. PLL- g-dex copolymers readily adsorb from aqueous solution onto negatively charged oxide surfaces and significantly reduce nonspecific protein adsorption onto bare silica-titania surfaces. While effective and equivalent surface adsorption and antifouling properties were observed for PLL- g-dex copolymers in a variety of architectures, nanotribological analysis by atomic force microscopy was able to distinguish between the different brush densities produced. 相似文献
989.
Melegari M Suman M Pirondini L Moiani D Massera C Ugozzoli F Kalenius E Vainiotalo P Mulatier JC Dutasta JP Dalcanale E 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(19):5772-5779
Phosphonate cavitands are an emerging class of synthetic receptors for supramolecular sensing. The molecular recognition properties of the third-generation tetraphosphonate cavitands toward alcohols and water at the gas-solid interface have been evaluated by means of three complementary techniques and compared to those of the parent mono- and diphosphonate cavitands. The combined use of ESI-MS and X-ray crystallography defined precisely the host-guest association at the interface in terms of type, number, strength, and geometry of interactions. Quartz crystal microbalance (QCM) measurements then validated the predictive value of such information for sensing applications. The importance of energetically equivalent multiple interactions on sensor selectivity and sensitivity has been demonstrated by comparing the molecular recognition properties of tetraphosphonate cavitands with those of their mono- and diphosphonate counterparts. 相似文献
990.
Cavaliere C Foglia P Gubbiotti R Sacchetti P Samperi R Laganà A 《Rapid communications in mass spectrometry : RCM》2008,22(20):3089-3099
A rapid-resolution liquid chromatography/mass spectrometric (RRLC/MS) method for detection and quantitation of polyphenols in grape berry skins and seeds has been developed. Pulp-free berry skins were treated with liquid nitrogen and ground; seeds were also ground. Then, 3 g of samples were extracted with 30 mL of a mixture of methanol/water/formic acid 70:30:1 (v/v/v) under sonication and 1 microL of the final extract was injected into two 100 x 2.1 mm i.d., 1.8 microm Zorbax Eclipse plus C18 columns connected in series. Compounds were fractionated using a gradient elution of acidified acetonitrile/methanol 50:50 (v/v)/water. Columns were thermostatted at 70 degrees C. MS was carried out on an Agilent 6410 QqQ instrument equipped with an electrospray ionization source. Positive and negative MS/MS product ion scans were used for compound identification, whereas positive full scan MS in the m/z range 200-1400 was used for quantitation. By means of mass spectra comparison, various flavonols, flavan-3-ols, anthocyanins and stilbenes were identified. Quantitation was performed by external calibration, and concentration values were corrected for matrix effect that was evaluated in separate experiments. Semi-quantitative estimation was performed for compounds for which standards were not commercially available. Recoveries ranged from 90-102% with relative standard deviation (RSD) <5%, whereas the between samples RSD was in the range 4-12%. Two surrogate standards were used for quality control. The developed method was applied to analyze the polyphenol content of three Vitis vinifera table cultivars at physiological maturity and after proper preservation for 6 weeks. Results demonstrated that during preservation about half of the polyphenol content was lost. 相似文献