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Review
. 2011 Aug 24;4(8):1483-1518.
doi: 10.3390/ma4081483.

Matrices for Sensors From Inorganic, Organic, and Biological Nanocomposites

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Free PMC article
Review

Matrices for Sensors From Inorganic, Organic, and Biological Nanocomposites

Claudio Nicolini et al. Materials (Basel). .
Free PMC article

Abstract

Matrices and sensors resulting from inorganic, organic and biological nanocomposites are presented in this overview. The term nanocomposite designates a solid combination of a matrix and of nanodimensional phases differing in properties from the matrix due to dissimilarities in structure and chemistry. The nanoocomposites chosen for a wide variety of health and environment sensors consist of Anodic Porous Allumina and P450scc, Carbon nanotubes and Conductive Polymers, Langmuir Blodgett Films of Lipases, Laccases, Cytochromes and Rhodopsins, Three-dimensional Nanoporous Materials and Nucleic Acid Programmable Protein Arrays.

Keywords: matrix; nanocomposite; sensors.

Figures

Figure 1
Figure 1
(A) SEM picture (top view) showing highly ordered anodic porous alumina on the surface of the microarray spot, resulting at the end of the photolithographic microstructuring technique and the two-step anodization process; (B) FIB (focused ion beam) system images of cross-sectional morphologies of the microarray spot, resulting at the end of the photolithographicmicrostructuring technique and the two-step anodization process. FIB-FEI® (www.fei.com) —measurements were made with gallium ions—37 pA—both for cutting and imaging; (C) Schematic diagram of anodic porous alumina (APA) microstructuring process; (D) APA functionalized rhodium–graphite s.p.e. working electrode. Schematic view illustrating the direct electron transfer between the cytochrome P450scc catalytic “core” and the APA modified working electrode. In the box is shown the specific interaction between the cytochrome P450scc negative surface (blue) and the positive charges of poly-l-lysine.
Figure 2
Figure 2
Cyclic voltammograms (CV), showing the I–V current-voltage curves of s.p.e. of APA–P450scc Electrode in presence of substrate LDL-cholesterol. The s.p.e. of APA–P450scc electrode was investigated, after a month, in a 10 mM K-phosphate buffer pH 7.4 in presence of LDL-cholesterol. (a) P450; (b) LDL 0.5 mg/mL; (c) LDL1.1 mg/mL; and (d) LDL1.6 mg/ml. Results are representative of one of three similar experiments.
Figure 3
Figure 3
Above: Scheme of the synthesis leading to the formation of a repeat unit starting from monomers. Based on the fraction of imine nitrogen groups per repeat unit, it is possible to obtain different reduced/oxidized polymer chains as follows: Fully reduced form (leucoemeraldine base) for y = 1; fully oxidized form (pernigraniline base) for y = 0; half oxidized form (emeraldine base) for y = 0.5. Below: UV-vis spectra of materials in the undoped form based on disubstituted conducting polymer (PDMA and PDOA): PDMA pure conducting polymer; PDMA-MWNTs nanocomposite material; PDMA-SWNTs nanocomposite material. PDOA pure conducting polymer; PDOA-MWNTs nanocomposite material; PDOA-SWNTs nanocomposite material.
Figure 3
Figure 3
Above: Scheme of the synthesis leading to the formation of a repeat unit starting from monomers. Based on the fraction of imine nitrogen groups per repeat unit, it is possible to obtain different reduced/oxidized polymer chains as follows: Fully reduced form (leucoemeraldine base) for y = 1; fully oxidized form (pernigraniline base) for y = 0; half oxidized form (emeraldine base) for y = 0.5. Below: UV-vis spectra of materials in the undoped form based on disubstituted conducting polymer (PDMA and PDOA): PDMA pure conducting polymer; PDMA-MWNTs nanocomposite material; PDMA-SWNTs nanocomposite material. PDOA pure conducting polymer; PDOA-MWNTs nanocomposite material; PDOA-SWNTs nanocomposite material.
Figure 4
Figure 4
Left: Representation of nanocomposite materials based on wrapped up polymer chains around CNTs without the formation of strong interactions. Right: Scheme of the protonated pernigraniline chains growing process by addition of anilinium cations in para position. Their stability is strictly ruled by the possible delocalization of the positive charges along the polymer backbone, which is increased by the best reachable alignment (“in a plane” zigzag configuration) of the benzene/quinoid-like rings.
Figure 5
Figure 5
LB-based protein crystals preparation and characterization.
Figure 6
Figure 6
Above: AFM 2D images of immobilized lipase: (a) 1 layers; (b) 5 layers; (c) 10 layers of lipase. 50 µL of lipase at a concentration of 10 mg/mL was dispersed onto the air/water interface and immediately compressed. Monolayers were sequentially deposited at 20 nN/m onto a silicon slide for analysis. Center: Lineweaver–Burke plots of olive oil activity of the free (upper plot) and LB film-contained (lower plot) lipase. One LB monolayer of lipase was used for the immobilized enzyme corresponding to 10−4 mg of free enzyme. Below: MALDI TOF MS spectrum of recombinant Laccase from Rigidoporus lignosus. The spectrum was acquired in linear mode and the matrix utilized was sinapinic acid. The spectrum was calibrated externally by Protein standard solution II (Bruker). The peak at m/z = 56516 ± 94 has been assigned as a Laccase one; the other peaks at m/z = 28520 ± 83, m/z = 27549 ± 44 and m/z = 18374 ± 22 have been interpreted as different domains of Laccase erroneously expressed by the clone.
Figure 6
Figure 6
Above: AFM 2D images of immobilized lipase: (a) 1 layers; (b) 5 layers; (c) 10 layers of lipase. 50 µL of lipase at a concentration of 10 mg/mL was dispersed onto the air/water interface and immediately compressed. Monolayers were sequentially deposited at 20 nN/m onto a silicon slide for analysis. Center: Lineweaver–Burke plots of olive oil activity of the free (upper plot) and LB film-contained (lower plot) lipase. One LB monolayer of lipase was used for the immobilized enzyme corresponding to 10−4 mg of free enzyme. Below: MALDI TOF MS spectrum of recombinant Laccase from Rigidoporus lignosus. The spectrum was acquired in linear mode and the matrix utilized was sinapinic acid. The spectrum was calibrated externally by Protein standard solution II (Bruker). The peak at m/z = 56516 ± 94 has been assigned as a Laccase one; the other peaks at m/z = 28520 ± 83, m/z = 27549 ± 44 and m/z = 18374 ± 22 have been interpreted as different domains of Laccase erroneously expressed by the clone.
Figure 7
Figure 7
Above: Stereo view of the superimposed retinal-binding pocket for 11-cis (left) and all-trans (right) retinal. The retinal is colored in magenta and cyan respectively; backbone atoms in yellow and blue, respectively, and sidechain atoms according to the CPK scheme. Below: SDS-Page of rhodopsin protein after purification step: rhodopsin concentrated samples were run on lanes 1, 2, 3, 4 and molecular weight markers were run on lane M. Molecular weight of rhodopsin thus determined was ~33 KDa.
Figure 7
Figure 7
Above: Stereo view of the superimposed retinal-binding pocket for 11-cis (left) and all-trans (right) retinal. The retinal is colored in magenta and cyan respectively; backbone atoms in yellow and blue, respectively, and sidechain atoms according to the CPK scheme. Below: SDS-Page of rhodopsin protein after purification step: rhodopsin concentrated samples were run on lanes 1, 2, 3, 4 and molecular weight markers were run on lane M. Molecular weight of rhodopsin thus determined was ~33 KDa.
Figure 8
Figure 8
Above: Stereo view of homology model of Cytochrome P450scc, based on Cytochrome 450 2B4. Acidic amino residues are labeled. Secondary structure elements are colored. Heme is shown as sticks. Center: The impedance characteristic for an Au–P450scc electrode in 100 mM phosphate buffer, 50 mM KCl, pH 7.4. The lines show the best fit to the experimental data. The insets present the equivalent circuits fitting the impedance data. RS is the uncompensated solution resistance; ZC is the double layer capacitance; RAu and CAu are the ohmic and capacitive contributions respectively of the gold nanoparticles on the electrode to the impedance, while RP450 and CP450 are the same contributions respectively to the impedance due to presence of cytochrome P450scc on the electrode. Both plots represent the phase (□) and the modulus (■) vs. frequency. Below: The amperometric response of screen-printed rhodium–graphite Au–P450scc electrode to increasing cholesterol concentration. About 100 µM stock solution in 0.3% sodium cholate, measured when fractions of 10 µM of cholesterol has been repeatedly added. The total volume of electrolyte was 60 µL. The current was measured at the potential−400 mV (vs. Ag/AgCl).
Figure 9
Figure 9
Above: NAPPA technology [103]. Below left: NAPPA region image with human kinase proteins acquired by the DNASER device. Below right: Multi-nanogravimetry quartz crystals for biosensor will consist of four gold coated quartz crystals 8 mm wide on which will be spotted NAPPA genes in the geometry previously adopted, i.e., 16 spots (4 × 4)—each of 300 microns of diameter—spaced of 750 microns, center to center.

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