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11.
Gema?M.?Durán Carlos?Abellán Ana?M.?Contento ángel?RíosEmail author 《Mikrochimica acta》2017,184(3):815-824
The authors describe a method for the differentiation of penicillamine (PA) enantiomers by using CdSe/ZnS quantum dots (QDs) modified with β-cylodextrin (β-CD-CdSe/ZnS QDs). Selective enantiorecognition of L-PA and D-PA was accomplished by virtue of selective host-guest interaction between the PAs and the β-CD pockets on the QDs. The fluorescence intensity of the modified QDs decreases in the presence of L-PA. On the contrary, it increases in the presence of D-PA. These findings form the basis for a new method for recognition of PA enantiomers. Under optimized conditions, a linear relationship exists between fluorescence intensity and D-PA concentration in the 0.1 to 5.0 mg L?1 range, and between 0.8 and 5.0 mg L?1 for L-PA. Detection limits are 0.06 mg L?1 for D-PA, and 0.2 mg L?1 for L-PA. The potential of this method has been demonstrated by the determination of D-PA in pharmaceutical formulations and L-PA in (spiked) environmental samples. 相似文献
12.
Natalia Campillo Pilar ViñasNerea Aguinaga Gema FérezManuel Hernández-Córdoba 《Journal of chromatography. A》2010,1217(27):4529-4534
A stir bar microextraction (SBSE) procedure for the determination of seven strobilurin fungicides in fruit samples using liquid chromatography (LC) and diode array detection (DAD) has been developed. The samples were sonicated in the presence of ethanol before submitting the extracts to SBSE. The incorporation of drazoxolon as an internal standard before SBSE allowed calibration without the need to use the standard additions method. Under the optimized conditions, detection limits were in the 0.3–2 ng g−1 range, corresponding to trifloxystrobin and metominostrobin, respectively. The SBSE–LC–DAD procedure showed good repeatability (RSD below 11% in all cases) and provided recoveries of 80–105% from spiked samples. The method was applied to fifteen fruit samples, and low levels of pyraclostrobin and trifloxystrobin were found in two of them. 相似文献
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Alexandra Muñoz‐Bonilla Gema Marcelo Cintia Casado Francisco J. Teran Marta Fernández‐García 《Journal of polymer science. Part A, Polymer chemistry》2012,50(24):5087-5096
In this article, magnetite nanoparticles (MNPs) coated with glycopolymer bearing glucose moieties were designed with optimal structural, colloidal, and magnetic properties for biomedical applications. MNPs with an average size of 17 ± 2 nm were synthesized by thermal decomposition process and then their surfaces were modified with active vinyl groups. Two different monomers were immobilized onto the surfaces: dopamine methacrylamide, a monomer with properties inspired on mussels adhesive capacity, or unprotected glycomonomer, 2‐{[(D ‐glucosamin‐2N‐yl)carbonyl]‐oxy}ethyl methacrylate. Afterward, the glycomonomer were polymerized at the interface of both vinyl functionalized MNPs by conventional radical polymerization. The resultant hybrid NPs were water dispersible presenting good stability in aqueous solution for long time periods. Moreover, the high density of carbohydrates at the surface of the magnetic NPs could confer targeting properties to the system as demonstrated by studies of their binding interactions with lectins, where the binding activity is higher as the glycopolymer content augments. The magnetic and magneto‐thermal properties of the synthesized hybrid NPs were evaluated. The magnetization curves reveal superparamagnetic features at 300 K, with high values of saturation magnetization. Furthermore, the hybrid glycoparticles show suitable heat dissipation power when exposed to alternating magnetic field conditions. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
14.
The [2+2+2] cycloaddition is an elegant, atom-efficient and group tolerant process for the synthesis of carbo- and heterocycles, mostly aromatic, involving the formation of several C-C bonds in a single step. Cyclotrimerisation is catalyzed by a variety of organometallic complexes, including more than 15 different metals. The aim of this tutorial review is to point out the most recent advances in this field and to encourage the use of this reaction enroute to complex molecules. After summarizing the most common catalysts and reaction conditions generally used, we survey the mechanistic features currently accepted for this reaction. Section 4 covers the scope of the different [2+2+2] cycloaddition versions starting with the cyclotrimerisation of three triple bonds, including nitriles, with especial emphasis on asymmetric reactions that create central, axial or planar chirality. Then, reactions that use double bonds are addressed. Finally, the most outstanding examples of natural products synthesis using [2+2+2] cycloadditions as a key step reported recently are shown. 相似文献
15.
Ignatyev I Montejo M Ortega PG González JJ 《Physical chemistry chemical physics : PCCP》2011,13(41):18507-18515
Activation barrier heights for the dehydration reaction of geminal carbinols and silanediols R'R″X(OH)(2) (X = C, Si) were estimated at the B3LYP and MP2 levels of theory employing Dunning's correlation-consistent triple-zeta basis sets. It was shown that the barrier height for carbon derivatives steadily decreases upon substitution by R groups, usually termed as electron-donating, such as alkyl and amino groups. Substitution by electron-withdrawing groups leads, however, only to small changes in barrier heights compared to that of methanediol. A similar tendency was also found for silicon derivatives, but high activation barriers of this reaction remain even for amino group substituted silanediols. Introduction of additional water molecules into the reactive space of carbinol dehydration drastically reduces barrier heights and brings the transition state energy for methanediol close to the experimental value. The difference between dehydration barrier heights for both methanediol and carbinols with electron-rich substituents becomes well-defined for dimeric species. The higher acidity of the hydroxyl group protons in molecules containing halogens and C==O groups brings about a noticeable growth in the dehydration barrier heights of these compounds. This difference in barrier heights for oligomeric species may be the reason for the stability of carbinols with electron-rich substituents. 相似文献
16.
Campos-Martin JM Blanco-Brieva G Fierro JL 《Angewandte Chemie (International ed. in English)》2006,45(42):6962-6984
Hydrogen peroxide (H2O2) is widely used in almost all industrial areas, particularly in the chemical industry and environmental protection. The only degradation product of its use is water, and thus it has played a large role in environmentally friendly methods in the chemical industry. Hydrogen peroxide is produced on an industrial scale by the anthraquinone oxidation (AO) process. However, this process can hardly be considered a green method. It involves the sequential hydrogenation and oxidation of an alkylanthraquinone precursor dissolved in a mixture of organic solvents followed by liquid-liquid extraction to recover H2O2. The AO process is a multistep method that requires significant energy input and generates waste, which has a negative effect on its sustainability and production costs. The transport, storage, and handling of bulk H2O2 involve hazards and escalating expenses. Thus, novel, cleaner methods for the production of H2O2 are being explored. The direct synthesis of H2O2 from O2 and H2 using a variety of catalysts, and the factors influencing the formation and decomposition of H2O2 are examined in detail in this Review. 相似文献
17.
The reactions in benzene of 9-alkyl-3-aminocarbazoles with ethyl-3-oxobutanoate yielded ethyl-3-[(9-alkyl-9H-carbazol-3-yl)amino]but-2-enoate condensation products or N-(9-ethyl-9H-carbazol-3-yl)-3-oxobutanamide acylation products. The condensation products were cyclized to the corresponding 4,7-dihydro-pyrido[2,3-c]-carbazol-1-ones upon heating in mineral oil at 240-250 degrees C. The structures of the synthesized compounds were investigated by IR, mass spectrometry, (1)H- and (13)C-NMR spectroscopy and MM2 molecular mechanics and AM1 semi-empirical quantum mechanical methods. 相似文献
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Gema Vivo-Llorca Vicente Candela-Noguera Dr. María Alfonso Dr. Alba García-Fernández Prof. Mar Orzáez Dr. Félix Sancenón Prof. Ramón Martínez-Máñez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(69):16318-16327
Triple-negative breast cancer (TNBC) is the most aggressive breast cancer subtype. In the last years, navitoclax has emerged as a possible treatment for TNBC. Nevertheless, rapid navitoclax resistance onset has been observed thorough Mcl-1 overexpression. As a strategy to overcome Mcl-1-mediated resistance, herein we present a controlled drug co-delivery system based on mesoporous silica nanoparticles (MSNs) targeted to TNBC cells. The nanocarrier is loaded with navitoclax and the Mcl-1 inhibitor S63845 and capped with a MUC1-targeting aptamer ( apMUC1-MSNs(Nav/S63845) ). The apMUC1-capped nanoparticles effectively target TNBC cell lines and successfully induce apoptosis, overcoming navitoclax resistance. Moreover, navitoclax encapsulation protects platelets against apoptosis. These results point apMUC1-gated MSNs as suitable BH3 mimetics nanocarriers in the targeted treatment of MUC1-expressing TNBC. 相似文献
20.
Alcaide B Almendros P Cabrero G Ruiz MP 《Chemical communications (Cambridge, England)》2008,(5):615-617
Molecular iodine (10 mol%) efficiently catalyzes the ring expansion of 4-oxoazetidine-2-carbaldehydes in the presence of tert-butyldimethyl cyanide to afford protected 5-cyano-3,4-dihydroxypyrrolidin-2-ones with good yield and high diastereoselectivity, through a novel C3-C4 bond cleavage of the beta-lactam nucleus. 相似文献