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81.
Vazquez-Roig P Andreu V Onghena M Blasco C Picó Y 《Analytical and bioanalytical chemistry》2011,400(5):1287-1301
The distribution of 17 pharmaceuticals between water and the solid phase (sediments and soils) was studied by utilizing solid-phase extraction (SPE) and liquid chromatography?Ctandem mass spectrometry (LC-MS/MS). Two extraction procedures for soils and sediments, prior to the SPE, one based on pressurized liquid extraction (PLE) with hot water and the other on methanol/water ultrasonic extraction, were compared. Absolute recoveries were 71.2?C99.3% [relative standard deviation (RSD) <21.4%)] for water, and the method detection limits (MDLs) ranged from 0.3 to 10?ng?L?1. Recoveries were 35.4?C105.3% (RSDs <19.1%) and 42.1?C97.8% (RSDs <14%) for soil and sediment samples, respectively, using PLE and 20.2?C86.5% (RSDs <25.1%) and 30.3?C97.4% (RSDs <19.1%) using ultrasonic extraction. Fifteen of the 17 pharmaceuticals were present in the L??Albufera water at concentrations up to 17???g?L?1. Oxytetracycline and tetracycline were not detected. In sediments, only tetracycline, norfloxacin and diclofenac were not found. The other studied pharmaceuticals were present in the range from less than the method quantification limit (MQL) to 35.83?ng?g?1. Among the 17 target compounds, ofloxacin, ciprofloxacin, norfloxacin, trimethoprim, clofibric acid and diclofenac were not detected in soil samples. The average concentrations ranged from less than the MQL for ibuprofen to 34.91?ng?g?1 for tetracycline. These results indicate that pharmaceuticals could survive the wastewater treatment processes, which could lead to their dissemination in water environments. 相似文献
82.
Li W Shavel A Guzman R Rubio-Garcia J Flox C Fan J Cadavid D Ibáñez M Arbiol J Morante JR Cabot A 《Chemical communications (Cambridge, England)》2011,47(37):10332-10334
An oriented attachment and growth mechanism allows an accurate control of the size and morphology of Cu(2-x)S nanocrystals, from spheres and disks to tetradecahedrons and dodecahedrons. The synthesis conditions and the growth mechanism are detailed here. 相似文献
83.
Andreu I Neshchadin D Rico E Griesser M Samadi A Morera IM Gescheidt G Miranda MA 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(36):10089-10096
A thorough mechanistic study has been performed on the reaction between benzophenone (BZP) and a series of 1,4-dienes, including 1,4-cyclohexadiene (CHD), 1,4-dihydro-2-methylbenzoic acid (MBA), 1,4-dihydro-1,2-dimethylbenzoic acid (DMBA) and linoleic acid (LA). A combination of steady-state photolysis, laser flash photolysis (LFP), and photochemically induced dynamic nuclear polarization (photo-CIDNP) have been used. Irradiation of BZP and CHD led to a cross-coupled sensitizer-diene product, together with 6, 7, and 8. With MBA and DMBA as hydrogen donors, photoproducts arising from cross-coupling of sensitizer and diene radicals were found; compound 7 was also obtained, but 6 and o-toluic acid were only isolated in the irradiation of BZP with MBA. Triplet lifetimes were determined in the absence and in the presence of several diene concentrations. All three model compounds showed similar reactivity (k(q) ≈10(8) M(-1) s(-1)) towards triplet excited BZP. Partly reversible hydrogen abstraction of the allylic hydrogen atoms of CHD, MBA, and DMBA was also detected by photo-CIDNP on different timescales. Polarizations of the diamagnetic products were in full agreement with the results derived from LFP. Finally, LA also underwent partly reversible hydrogen abstraction during photoreaction with BZP. Subsequent hydrogen transfer between primary radicals led to conjugated derivatives of LA. The unpaired electron spin population in linoleyl radical (LA(.)) was predominantly found on H(1-5) protons. To date, LA-related radicals were only reported upon hydrogen transfer from highly substituted model compounds by steady-state EPR spectroscopy. Herein, we have experimentally established the formation of LA(.) and shown that it converts into two dominating conjugated isomers on the millisecond timescale. Such processes are at the basis of alterations of membrane structures caused by oxidative stress. 相似文献
84.
Cuquerella MC Andreu I Soldevila S Bosca F 《The journal of physical chemistry. A》2012,116(21):5030-5038
Generation of triplet eximers of 6-fluoro-7-piperazinyl-quinolone-3-carboxylic acids (FQs) have been detected in aqueous media using laser flash photolysis (LFP). These transient species (SS) are generated by self-quenching reactions of FQ triplet excited states such as pefloxacin (PFX), norfloxacin (NFX), the N-acetylated form of NFX (ANFX), and its methyl ester (EANFX) with their ground states. In this context, self-quenching rate constants in the range of (1-7) × 10(8) M(-1) s(-1) were determined. The triplet excimers show transient absorption spectra with λ(max) ca. 710 nm for SS(NFX), 740 nm for SS(PFX), and 620 nm for SS(ANFX) and E(ANFX), which are red-shifted with respect to their predecessors triplet excited states. These excimers can be also observed in the presence of phosphate buffer (PB). Experiments performed with NFX and ANFX at different PB concentrations showed that deprotonation processes are not involved in the generation of SS. The triplet multiplicity of the FQ excimers was confirmed by energy transfer reactions with naproxen. The correlation between fluorescence, intersystem crossing, excimer and photodegradation quantum yields of (A)NFX indicated that FQ self-quenching reactions are mainly a deactivation pathway. On the other hand, generation of FQ radical anions absorbing at λ(max) ca. 620 nm has been observed by an efficient electron transfer reaction from Trp to NFX, PFX, and ANFX (rate constants ca. 1 × 10(9) M(-1) s(-1)). 相似文献
85.
Multimeric presentation, a rather effective way of enhancing peptide immunogenicity, is best exemplified by MAP (multiple antigenic peptide) dendrimers consisting of a branched Lys core on which several copies of the peptide epitope are displayed. While accessible by solid-phase synthesis, MAPs can also be conveniently made in solution, e.g., by linking the epitope (N-acetylated and with a C-terminal Cys) through a thioether bond onto the α and ε (haloacetyl-activated) positions of the Lys core. We now report the reverse version of this approach, whereby a chloroacetyl-derivatised epitope is tethered to a thiol-functionalised form of a Lys dendron core. This convergent approach can be carried out either in solution or in the solid phase and is advantageous because (i) in situ tris(2-carboxyethyl)phosphine (TCEP)-mediated reduction of disulfide bonds maintains the thiol platform reactive throughout the ligation process; (ii) the low amounts of TCEP used pose minimal risk to chloroacetyl groups in the peptide, resulting in (iii) significantly reduced byproduct formation, hence cleaner products. For the solid phase version of the method, an optimised procedure has been devised to convert the Lys core into a tetrathiol dendron. 相似文献
86.
87.
88.
Raquel Andreu Javier Garín María Jesús Modrego Raquel Alicante Magali Allain 《Tetrahedron letters》2009,50(24):2920-1669
Dipolar, V-shaped compounds derived from 4H-pyranylidene-linked acceptors have been synthesized, and their linear and nonlinear optical properties (displaying μβ values up to 3000 × 10−48 esu) have been compared to those of analogous one-dimensional derivatives. The pyranylidene ring behaves strictly as a spacer, and not as a donor group. 相似文献
89.
F. Andreu J. M. Mazón J. D. Rossi J. Toledo 《Calculus of Variations and Partial Differential Equations》2009,35(3):279-316
In this paper, we study the nonlocal ∞-Laplacian type diffusion equation obtained as the limit as p → ∞ to the nonlocal analogous to the p-Laplacian evolution,
We prove exist ence and uniqueness of a limit solution that verifies an equation governed by the subdifferential of a convex
energy functional associated to the indicator function of the set . We also find some explicit examples of solutions to the limit equation. If the kernel J is rescaled in an appropriate way, we show that the solutions to the corresponding nonlocal problems converge strongly in
L
∞(0, T; L
2 (Ω)) to the limit solution of the local evolutions of the p-Laplacian, v
t
= Δ
p
v. This last limit problem has been proposed as a model to describe the formation of a sandpile. Moreover, we also analyze
the collapse of the initial condition when it does not belong to K by means of a suitable rescale of the solution that describes the initial layer that appears for p large. Finally, we give an interpretation of the limit problem in terms of Monge–Kantorovich mass transport theory.
F. Andreu, J. M. Mazón and J. Toledo were supported by the Spanish MEC and FEDER, project MTM2005-00620, and by the project
ACOMP2007/112 from Generalitat Valenciana. J. D. Rossi was partially supported by Generalitat Valenciana under AINV2007/03
and ANPCyT PICT 5009, UBA X066 and CONICET (Argentina). 相似文献
90.
Rodrigo Caas-Arranz Patricia de Len Sira Defaus Elisa Torres Mar Forner María J. Bustos David Andreu Esther Blanco Francisco Sobrino 《Molecules (Basel, Switzerland)》2021,26(16)
An approach based on a dendrimer display of B- and T-cell epitopes relevant for antibody induction has been shown to be effective as a foot-and-mouth disease (FMD) vaccine. B2T dendrimers combining two copies of the major FMD virus (FMDV) type O B-cell epitope (capsid proteinVP1 (140–158)) covalently linked to a heterotypic T-cell epitope from non-structural protein 3A (21–35), henceforth B2T-3A, has previously been shown to elicit high neutralizing antibody (nAb) titers and IFN-γ-producing cells in both mice and pigs. Here, we provide evidence that the B- and T-cell epitopes need to be tethered to a single molecular platform for successful T-cell help, leading to efficient nAb induction in mice. In addition, mice immunized with a non-covalent mixture of B2T-3A dendrimers containing the B-cell epitopes of FMDV types O and C induced similarly high nAb levels against both serotypes, opening the way for a multivalent vaccine platform against a variety of serologically different FMDVs. These findings are relevant for the design of vaccine strategies based on B- and T-cell epitope combinations. 相似文献