Paloma Martínez-Ruiz

Molecularly imprinted polymers for on-line preconcentration by solid phase extraction of pirimicarb in water samples

The synthesis and performance of a molecularly imprinted polymers (MIPs) as a selective solid phase extraction sorbent for the preconcentration of the carbamate pirimicarb from water samples is described. The MIP was prepared using pirimicarb as the template, methacrylic acid as the functional monomer and ethylene glycol dimethacrylate as the cross-linking monomer, and using chloroform as the solvent. The detection of pirimicarb was carried out by differential pulse voltammetry (DPV) at a hanging mercury drop electrode (HMDE) in 0.1 mol l −1 HCl. Solvents of different polarities were checked for the polymer synthesis, and different experimental variables (sample pH, selection of the eluent used, eluent volume, analyte and eluent flow rates and sample volume) associated with the rebinding/extraction process were optimised. For a 25 ml sample, the process took about 13 min and resulted in a nominal enrichment factor of 50 (eluent MeOH:H2O:HAc, 7:2:1; 0.5 ml) for pirimicarb. A limit of detection of 4.1 gl −1 was obtained, and a good reproducibility of the measurements using different MIP microcolumns was found. Furthermore, the MIP selectivity was evaluated by checking several substances with similar and different molecular structures to that of pirimicarb. As an application, pirimicarb was determined in water samples of diverse origin which were spiked at a concentration level of 71.5 gl −1 .

Bridgehead-norbornane-derived β-amino alcohol catalysts: structural factors influencing the chirality transfer

Abstract Five new optically active bridgehead-norbornane-derived β-amino alcohols with different substitution patterns have been obtained using a straightforward procedure from commercial (+)-camphor or (−)-fenchone, and tested as chiral catalysts in the enantioselective diethylzinc-addition to benzaldehyde. The obtained results show that chirality transfer is mainly governed by the hydroxyl group and, therefore, by the surroundings of the CO stereocenter. On the other hand, the N- alkyl substitution play an important role by modulating the degree of enantioselectivity.

Decorating graphene oxide/nanogold with dextran-based polymer brushes for the construction of ultrasensitive electrochemical enzyme biosensors

A novel strategy was employed to prepare a water-soluble graphene derivative by using dextran-based polymer brushes as solubilizing agents. Graphene oxide was grafted with (3-mercaptopropyl) trimethoxysilane and further decorated with Au nanoparticles. This hybrid nanomaterial was then reduced and anchored with polysaccharide-based polymer brushes by chemisorption of an end-group thiolated dextran derivative on the Au nanoparticles. The resulting hybrid nonmaterial allowed highly stable aqueous dispersions to be obtained, which were used to coat glassy carbon electrodes for the preparation of a model tyrosinase electrochemical biosensor for catechol. The enzyme electrode showed excellent electroanalytical performance with fast response in about 5 s, a linear range of 100 pM-120 nM, a very high sensitivity of 45.9 A M-1 and a very low detection limit of 40 pM for catechol.

Crumpled reduced graphene oxide–polyamidoamine dendrimer hybrid nanoparticles for the preparation of an electrochemical biosensor

Reduced graphene nanoparticles were prepared from graphene oxide through a two-step covalent modification approach. Graphene oxide was first enriched with reactive epoxy groups by anchoring (3-glycidyloxypropyl)trimethoxysilane at the hydroxyl groups located on the nanocarbon basal plane. Modified graphene oxide was further cross-linked and partially reduced by treatment with the fourth-generation ethylenediamine core polyamidoamine G-4 dendrimer producing graphene nanoparticles with crumpled paper-like morphology. This graphene derivative was employed as a coating material for glassy carbon electrodes and the nanostructured electrode was tested for the preparation of electrochemical biosensors by immobilizing the enzyme tyrosinase through cross-linking with glutaraldehyde. This bioelectrode showed excellent electroanalytical behavior for catechol with a fast response in about 6 s, linear range of 10 nM to 22 μM, sensitivity of 424 mA M-1, and low detection limit of 6 nM. The enzyme biosensor also showed high stability when stored at 4 °C under dry and wet conditions.

The role of the substitution pattern on the catalytic activity of chiral bridgehead norbornane-derived β-amino alcohols

The enantioselective addition of diethylzinc to benzaldehyde has been used as standard procedure to test a series of new chiral catalysts derived from norbornane framework. The new ligands are β-amino alcohols possessing both heteroatomic substituents attached to the C(1) and C(2)-endo positions (novel non-coplanar disposition) of a 3,3-dimethylsubstituted norbornane. The results obtained, compared with other previously reported on the related C(2)-exo-7,7-dimethyl series, demonstrate that the relative disposition of the amino, hydroxy and gem-dimethyl groups, as well as the N-alkyl substituents, play an important role on the catalytic activity. Interesting transition-state models have been also proposed in order to explain the observed experimental results.

Integrated Amperometric Affinity Biosensors Using Co2+–Tetradentate Nitrilotriacetic Acid Modified Disposable Carbon Electrodes: Application to the Determination of β-Lactam Antibiotics

A novel strategy for the construction of disposable amperometric affinity biosensors is described in this work. The approach uses a recombinant bacterial penicillin binding protein (PBP) tagged by an N-terminal hexahistidine tail which was immobilized onto Co(2+)-tetradentate nitrilotriacetic acid (NTA)-modified screen-printed carbon electrodes (SPCEs). The biosensor was employed for the specific detection and quantification of β-lactam antibiotics residues in milk, which was accomplished by means of a direct competitive assay using a tracer with horseradish peroxidase (HRP) for the enzymatic labeling. The amperometric response measured at -0.20 V versus the Ag pseudoreference electrode of the SPCE upon the addition of H2O2 in the presence of hydroquinone (HQ) as redox mediator was used as the transduction signal. The developed affinity sensor allowed limits of detection to be obtained in the low part-per-billion level for the antibiotics tested in untreated milk samples. Moreover, the biosensor exhibited a good selectivity against other antibiotics residues frequently detected in milk and dairy products. The analysis time was of approximately 30 min.

Density functional theory study of self-association of N-methylformamide and its effect on intramolecular and intermolecular geometrical parameters and the cis/trans population

The single-point total energy (E) of several acyclic and cyclic oligomers of N-methylformamide (NMF) was computed by the first time without any geometrical restriction, using the B3LYP6-31G* method of the density functional theory in order to determine the effect of self-association on intramolecular geometrical parameters of cis- and trans-NMF, the intermolecular distances of the hydrogen-bonding chains formed by NMF as well as intermolecular association energies including counterpoise corrections. It is concluded that liquid NMF exists mainly as polymers formed by self-association of trans-NMF units, whereas the cis-NMF isomer occurs as isolated units inserted along the chains. These computational results are in accordance with the experimentally determined predominance (ca. 90%) of trans-NMF population by means of (1)H- NMR and other spectroscopic techniques, but in severe contradiction with a recent interpretation of x-ray diffraction data on liquid NMF, postulating a cyclic trimer of cis-NMF (c-C(3)) as the predominating species. The counterpoise-corrected values of the association energy, DeltaE(CP), calculated for cyclic oligomers, increase with the polymerization degree (n) revealing a high grade of cooperative effect for amidic hydrogen-bonded chains. Noteworthy, the difference between the DeltaE(CP) values of the cyclic cis- and trans-homooligomers of NMF is positive for n=2 and 3 but negative for n > or =4.

Neoglycoenzyme-Gated Mesoporous Silica Nanoparticles: Toward the Design of Nanodevices for Pulsatile Programmed Sequential Delivery

We report herein the design of a stimulus-programmed pulsatile delivery system for sequential cargo release based on the use of a lactose-modified esterase as a capping agent in phenylboronic acid functionalized mesoporous silica nanoparticles. The dual-release mechanism was based on the distinct stability of the cyclic boronic acid esters formed with lactose residues and the long naturally occurring glycosylation chains in the modified neoglycoenzyme. Cargo delivery in succession was achieved using glucose and ethyl butyrate as triggers.

Seed-mediated growth of jack-shaped gold nanoparticles from cyclodextrin-coated gold nanospheres

Branched gold nanoparticles were prepared by a seed-mediated approach using per-6-thio-6-deoxy-β-cyclodextrin capped gold nanospheres as seeds and a growth medium similar to those commonly employed to prepare gold nanorods, containing AgNO3, ascorbic acid and cetyltrimethylammonium bromide. Novel jack-shaped gold nanoparticles (102-105 nm) were obtained at a specific range of Ag(+) ion concentrations (62-102 μM). The crystalline structure of these nanoparticles was confirmed by high-resolution transmission electron microscopy. The influence of the perthiolated β-cyclodextrin on the successful preparation of gold nanojacks was demonstrated. The jack-shaped gold nanoparticles showed strong absorption in the near infrared region and excellent catalytic activity for the electrochemical oxidation of H2O2.

Gold nanoparticles/silver-bipyridine hybrid nanobelts with tuned peroxidase-like activity

Gold nanoparticles-decorated silver-bipyridine coordination polymers with intrinsic peroxidase-like activity are reported. Both morphology and mimetic enzyme activity can be tuned by rational manipulation of the nanohybrid composition. The nanomaterial was used for the electrochemical determination of H2O2 and glucose.