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81.
Andrea Mazzanti Dr. Lodovico Lunazzi Prof. Renzo Ruzziconi Prof. Sara Spizzichino Manfred Schlosser Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(30):9186-9192
By making use of a novel diastereotopicity probe, namely C(CF3)2OH, it has been possible to measure by very low temperature 19F NMR spectroscopy the elusive aryl–aryl rotation barriers of biphenyls bearing an OH or F group in one ortho position. The experimental values (5.4 and 4.4 kcal mol?1, respectively) are matched by those from ab initio calculations (5.3 and 4.3 kcal mol?1, respectively). 相似文献
82.
Farré M Gajda-Schrantz K Kantiani L Barceló D 《Analytical and bioanalytical chemistry》2009,393(1):81-95
Nanotechnology is a major innovative scientific and economic growth area. However nanomaterial residues may have a detrimental
effect on human health and the environment. To date there is a lack of quantitative ecotoxicity data, and recently there has
been great scientific concern about the possible adverse effects that may be associated with manufactured nanomaterials. Nanomaterials
are in the 1- to 100-nm size range and can be composed of many different base materials (carbon, silicon and metals, such
as gold, cadmium and selenium) and they have different shapes. Particles in the nanometer size range do occur both in nature
and as a result of existing industrial processes. Nevertheless, new engineered nanomaterials and nanostructures are different
because they are being fabricated from the “bottom up”. Nanomaterial properties differ compared with those of the parent compounds
because about 40–50% of the atoms in nanoparticles (NPs) are on the surface, resulting in greater reactivity than bulk materials.
Therefore, it is expected that NPs will have different biological effects than parent compounds. In addition, release of manufactured
NPs into the aquatic environment is largely an unknown. The surface properties and the very small size of NPs and nanotubes
provide surfaces that may bind and transport toxic chemical pollutants, as well as possibly being toxic in their own right
by generating reactive radicals. This review addresses hazards associated and ecotoxicological data on nanomaterials in the
aquatic environment. Main weaknesses in ecotoxicological approaches, controversies and future needs are discussed. A brief
discussion on the scarce number of analytical methods available to determinate nanomaterials in environmental samples is included. 相似文献
83.
Rosini G Ayoub C Borzatta V Mazzanti A Marotta E Righi P 《Chemical communications (Cambridge, England)》2006,(41):4294-4296
The occurrence of p1,n1 salts can be exploited to sequester racemates; an application to technical mixtures of chrysanthemic acids (ChA) allowed the separation of trans- and cis-ChA and the recovery of the excess enantiomer of trans-ChA. 相似文献
84.
Reagentless and reversible maltose biosensors are demonstrated using ZnS coated CdSe (CdSe@ZnS) nanoparticle emission intensities. This method is based on electron transfer quenching of unimolecular protein-CdSe@ZnS nanoparticle assemblies, which is provided by a protein-attached Ru(II) complex. This Ru(II) complex is presumed to reduce a valence band hole of the CdSe@ZnS excited state by tunneling through the ZnS overcoating. The Ru(II) complex mediated quenching of CdSe@ZnS nanoparticle emission was only decreased 1.2-fold relative to the CdSe nanoparticle systems. While four different Ru(II) complex attachment sites provided different amounts of nanoparticle emission quenching (1.20 to 1.75-fold decrease), all of these attachment sites yielded maltose-dependent intensity changes (1.1 to 1.4-fold increase upon maltose addition). Maltose dissociation constants for these four biosensing systems range from 250 nM to 1.0 microM, which are similar to the maltose-maltose binding protein dissociation constant that these sensors are based on. The increased fluorescence intensity was found to only occur in the presence of maltose. Furthermore, the ability of these reagentless protein-nanoparticle assemblies to perform maltose biosensing reversibly is demonstrated with the addition of alpha-glucosidase. Three 50 microM maltose additions after alpha-glucosidase addition showed increases of 2.2 microM, 600 nM, and 150 nM maltose. This result demonstrates a fluorometric method for examining alpha-glucosidase activity. Using maltose binding protein to control Ru(II) complex interactions with CdSe@ZnS nanoparticle surfaces provide a novel class of highly fluorescent, photostable biosensors that are selective for maltose. 相似文献
85.
A series of terpolymers made of DMA, NAS and MAPS were synthesized by free radical copolymerization and used as functional coatings for the fabrication of glass slide DNA microarrays. The surface properties of coated glass slides were investigated through contact angle measurements, ellipsometry and atomic force microscopy. The terpolymer molecular weight showed a moderate effect on surface tension (gamma(s) = 56-62 mN x m(-1)), but no clear effect on polymeric layer thickness (5-8 nm) and roughness. Hybridization experiments with amine-functionalized oligonucleotides gave the best fluorescence intensity results for microarrays coated with intermediate-molecular-weight terpolymers. Finally, an accelerated ageing test of the microarray in a humidity chamber showed a nice relationship between decay curves of contact angle against water and fluorescence intensity. 相似文献
86.
Marta Llorca Marinella Farré Yolanda Picó Damià Barceló 《Analytical and bioanalytical chemistry》2010,398(3):1145-1159
The analytical suitabilities of three different liquid chromatography–tandem mass spectrometry (LC-MS/MS) systems, (1) triple quadrupole (QqQ), (2) conventional 3D ion trap (IT), and (3) quadrupole–linear IT (QqLIT), to determine trace levels of perfluorinated compounds (PFCs) in fish and shellfish were compared. Sample preparation was performed using alkaline extraction and solid-phase-extraction cleanup. This evaluation was focused on both quantitative (sensitivity, precision, and accuracy) and qualitative (identification capabilities) aspects. In the three instruments, the former facet was evaluated using selected reaction monitoring (SRM), which is the standard mode for quantitative LC-MS/MS analysis. Accuracy was similar in the three systems, with recoveries always over 70 %. Precision was better for the QqLIT and QqQ systems (7–15%) than for the IT system (10–17%). The QqLIT (working in SRM mode) and QqQ systems offered a linear dynamic range of at least 3 orders of magnitude, whereas that of the IT system was 2 orders of magnitude. The QqLIT system achieved at least 20-fold higher sensitivity than the QqQ system, and this was at least tenfold higher sensitivity than for the IT system. In the IT system, identification was based on sensitive full mass range acquisition and MS n fragmentation and in the QqLIT system, it was based on the use of an information-dependent-acquisition scan function, which allows the combination of an SRM or MS full scan acting as the survey scan and an enhanced product ion scan followed by MS3 as the dependent scan in the same analysis. Three instruments were applied to monitor the content in fish and shellfish (anchovies, swordfish, tuna, mussels, and oysters) obtained from Valencia and Barcelona markets (Spain). The eight target PFCs were detected at mean concentrations in the range from 10 ng ?kg-1 (perfluoro-7-methyloctanoic acid and perfluoro-1-decanesulfonate) to 4,200 ng ?kg-1 (perfluoropentanoic acid). Furthermore, perfluoroheptanoic and perfluoroundecanoic acids (not covered as target analytes) were identified in some samples. Figure
PFCs in the environment 相似文献
87.
Mira Petrovic Marinella Farré Miren Lopez de Alda Sandra Perez Cristina Postigo Marianne Köck Jelena Radjenovic Merixell Gros Damia Barcelo 《Journal of chromatography. A》2010,1217(25):4004-4017
An overview of liquid chromatography–mass spectrometry methods used for the determination of trace organic contaminants in environmental samples is presented. Among the organic contaminants the focus is given on five groups of emerging contaminants that raised most concern as environmental contaminants and therefore attracted attention of a research community: pharmaceuticals, drugs of abuse, polar pesticides, perfluorinated compounds and nanoparticles. Various aspects of current LC–MS methodology, using tandem and hybrid MS instruments, including sample preparation, are discussed. 相似文献
88.
89.
Depalo N Comparelli R Striccoli M Curri ML Fini P Giotta L Agostiano A 《The journal of physical chemistry. B》2006,110(35):17388-17399
Different types of cyclodextrins (CDs) have been tested as mediators for the water phase transfer of organic-capped CdS nanocrystals (NCs), and alphaCD has been demonstrated to be the most effective system. The formation of a complex based on alphaCDs and colloidal NCs has been considered to be responsible for the phase transfer process and extensively investigated by optical, structural, and calorimetric measurements, as a function of the experimental parameters (pH and NC and CD concentration). A mechanism for the complexation phenomena has been suggested. The fabrication of 2/3 D supramolecular architectures has been proposed according to two different strategies. First, a layer-by-layer procedure has been used to obtain multilayered structures where polyelectrolyte layers have been intercalated with negatively charged alphaCD-CdS NC complexes by exploiting electrostatic interaction between polyelectrolyte and cyclodextrin OH groups. Second, a monolayer of CdS NCs has been deposited onto a self-assembled monolayer of sulfated CDs, thus combining the use of an electrostatic-force-based approach and host-guest chemistry. The important role played by host-guest interactions has then been revealed. 相似文献
90.