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Carbon nanoparticles were prepared from glycerol by a thermal process in the presence of H3PO4. These particles were spherical with an average diameter of 66 nm and consisted of a carbon core with carboxylic acid and alcohol functional groups on the surface. The particles were characterized using Fourier-transform infrared, electron microscopy, X-ray diffraction, light scattering, ultraviolet–visible, fluorescence, and X-ray photoelectron spectroscopy techniques. Glassy carbon electrodes were modified, by drop casting, with the carbon nanoparticles and used for heavy metal detection with square wave anodic stripping voltammetry. Parameters such as accumulation (pre-concentration) time, amount of carbon nanoparticles casted, reduction time and reduction potential were optimized. Potential application of these glassy carbon electrodes modified with carbon nanoparticles for electrochemical analysis was demonstrated by the detection of heavy metal ions in tap water. The average recoveries of Pb2+ and Cu2+ in spiked tap water samples were 98.2% and 96.7% with a relative standard deviations of 7.4% and 8.5%, respectively.

Herein, we demonstrate the use of lysozyme (Lys) as a model to fabricate a protein carrier system based on gold nanoparticles (AuNPs) via the Layer-by-Layer (LbL) technology. Poly(ethyleneimine) (PEI) and poly(sodium 4-styrenesulfonate) (PSS) were used as cationic and anionic polymers respectively to grow oppositely charged layers. Mild aqueous conditions were utilized to avoid protein denaturation and activity instead of organic solvents that have been used in other encapsulation systems. Two different strategies were used: (A) lysozyme acting as a reducing and stabilizing agent in the formation of AuNPs at a temperature of 45 ± 2 °C followed by only two subsequent polymeric layers deposited by LbL, and (B) citrate acting as a reducing agent prior to stabilization of the AuNPs by mercaptoundecanoic acid. Dynamic light scattering, UV-vis spectroscopy, IR spectroscopy and transmission electron microscopy were used to characterize the nanoconjugates. Furthermore, the enzymatic activity of the resulting protein/nanoparticle conjugates was evaluated using the bacteria Micrococcus lysodeikticus as a substrate.

Core-shell nanospheres with tailorable magnetic properties and strong luminescence promise versatile and efficient biomedical and electronic applications. We report a low-cost sonochemical synthesis of ZnO/iron oxide core-shell nanostructures with tunable magnetic properties. The high-resolution transmission electron microscopy (HRTEM) illustrates the distinguished dispersity of the oxide nanoparticles, whereas elemental profiling using line scan data confirm the formation of the distinguished core and shell phases. Annealing in N2–H2 and Ar–H2 ambient alters the magnetic properties such as coercive field, saturation magnetization, and remnant magnetization within the inverse spinel iron oxide with space group Fd3m. Subtle structural changes between maghemite (γ-Fe2O3) and its reduced form, magnetite (Fe3O4), have been identified in the thin (0.5–3 nm) shell region of atomic dimensions. Structural composition including phase transitions and defect states are investigated using XRD, XPS, and Raman measurements. Coexistence of ferromagnetism (from the shell and characterized by magnetic measurements) and strong luminescence (from ZnO core and obtained from photoluminescence spectroscopy) at room temperature indicates exotic magneto-optical coupling, which is supported by the blue-shifted luminescence spectra. Our approach combining nanotechnology and solid-state chemistry opens a new frontier to the building of innovative nanomaterials for integration, especially multifunctional core-shell oxide nanomaterials.

Label-free bioaffinity sensors directly detect changes in the inherent property of the analyte, receptor or the molecular aggregates formed upon binding. This chapter introduces a label-free biosensor that utilizes a two-dimensional planar thin-film as the gate of a field effect transistor (FET). The direct label-free detection of biomolecules by the FET is based on the change of conductance due to the depletion or accumulation of carriers within the transistor structures when the charged biomolecules bind to the gate. The selectivity and sensitivity of the FET can be improved by modifying the gate of the FET with bioreceptors molecules such as antibodies, antigens, and oligonucleotides. Performance and sensitivity are further improved by fabricating the FETs from 1D nanostructured materials (e.g. conducting polymer nanowires). Improvements using 1D conducting nanowires include large conductance changes, real-time monitoring because the binding between the receptor and the target is reversible, direct conversion of chemical information into an electronic signal, and the development of high-density arrays due to the very small size of the nanostructures.

Biomedical applications for metal and metal oxide nanoparticles are rapidly increasing. Here their functional impact on two well-characterized model enzymes, Luciferase (Luc) or β-galactosidase (β-Gal) was quantitatively compared. Nickel oxide nanoparticle (NiO-NP) activated β-Gal (400% control) and boron carbide nanoparticle (B4C-NP) inhibited Luc(10% control), whereas zinc oxide (ZnO-NP) and cobalt oxide (Co3O4-NP) activated β-Gal to a lesser extent and magnesium oxide (MgO) moderately inhibited both enzymes. Melanoma specific killing was in the order; ZnOB4C ≥ CuMgOCo3O4Fe2O3NiO, ZnO-NP inhibiting B16F10 and A375 cells as well as ERK enzyme (90%) and several other cancer-associated kinases (AKT, CREB, p70S6K). ZnO-NP or nanobelt (NB) serve as photoluminescence (PL) cell labels and inhibit 3-D multi-cellular tumor spheroid (MCTS) growth and were tested in a mouse melanoma model. These results demonstrate nanoparticle and enzyme specific biochemical activity and suggest their utility as new tools to explore the important model metastatic foci 3-D environment and their chemotherapeutic potential.

Electrochemical detection of glucose was performed on carbon nanofibers containing an osmium based redox polymer and using glucose oxidase enzyme. Redox polymer assembled on the nanofibers provided a more stable support that preserved enzyme activity and promoted the electrical communication to the glassy carbon electrode. The morphologies, structures, and electrochemical behavior of the redox polymer modified nanofibers were characterized by scanning electron microscope, energy dispersive spectrometer and voltammetry. The glucose oxidase showed excellent communication with redox polymer as observed with the increased activity toward glucose. Both cyclic voltammetry and amperometry showed a linear response with glucose concentration. The linear range for glucose determination was from 1 to 12 mM with a relatively high sensitivity of 0.20±0.01 μA mM−1 for glucose oxidase in carbon nanofibers and 0.10±0.01 μA mM−1 without carbon nanofibers. The apparent Michaelis–Menten constant (Km) for glucose oxidase with carbon nanofibers was 0.99 mM. On the other hand, the Km value for the glucose oxidase without the nanofibers was 4.90 mM.

The growing use of carbon nanotubes (CNTs) in industrial and consumer products raises important questions about their environmental fate and impact on prokaryotes. In the environment, CNTs are exposed to a variety of conditions (e.g., UV light) that could lead to decomposition and changes in their chemical properties. Therefore, the potential cytotoxic effect of both pristine and artificially aged carboxyl functionalized CNTRENE®C100LM CNTmaterial at neutral and acidic conditions onEscherichia coliK12 was analyzed using a minimal inhibitory concentration (MIC) assay, which also allowed monitoring of non-lethal growth effects. However, there were no observable MIC or significant changes in growth behavior inE. coliK12 when exposed to pristine or aged CNTs. Exposure to pristine CNTRENE®C100LM CNT material did not appear to influence cell morphology or damage the cells when examined by electron microscopy. In addition, RNA sequencing revealed no observable regulatory changes in typical stress response pathways. This is surprising considering that previous studies have claimed high cytotoxicity of CNTs, including carboxyl functionalized single-walled CNTs, and suggest that other factors such as trace heavy metals or other impurities are likely responsible for many of the previously reported cytotoxicity inE. coliand possibly other microorganisms.

With the advent of nanobiotechnology, there will be an increase in the interaction between engineered nanomaterials and biomolecules. Nanoconjugates with cells, organelles, and intracellular structures containing DNA, RNA, and proteins establish sequences of nano–bio boundaries that depend on several intricate complex biophysicochemical reactions. Given the complexity of these interactions, and their import in governing life at the molecular level, it is extremely important to begin to understand such nanoparticle–biomaterial association. Here we report a unique method of probing the kinematics between an energy biomolecule, adenosine triphosphate (ATP), and hydrothermally synthesized ZnO nanostructures using micro Raman spectroscopy, X-ray diffraction, and electron microscopy experiments. For the first time we have shown by Raman spectroscopy analysis that the ZnO nanostructures interact strongly with the nitrogen (N7) atom in the adenine ring of the ATP biomolecule. Raman spectroscopy also confirms the importance of nucleotide base NH2 group hydrogen bonding with water molecules and phosphate group ionization and their pH dependence. Calculation of molecular bond force constants from Raman spectroscopy reinforces our experimental data. These data present convincing evidence of pH-dependent interactions between ATP and zinc oxide nanomaterials. Significantly, Raman spectroscopy is able to probe such difficult to study and subtle nano–bio interactions and may be applied to elegantly elucidate the nano–bio interface more generally.

Graphene decorated with zinc oxide nanoparticles were synthesized in a single step. Through this process zinc oxide nanoparticles weredepositedontographenenanosheets.Thenano-compositeswerecharacterizedusingX-rayDiffraction(XRD),ScanningElectron Microscope (SEM), energy dispersive spectroscopy (EDX), cyclic voltammetry and electrochemical impedance spectroscopy. The nanocomposite material displayed excellent catalytic properties toward Cholesterol in combination with cholesterol oxidase (ChOx). The cholesterol detection limit was found to be 5.0 μmol L −1 and a sensitivity 1.3 μA/μ Mc m 2 with linear correlation coefficient R 2 = 0.980. The Cholesterol oxidation also followed the Michaelis-Menten kinetics with apparent Km of 46.5 μM

We demonstrate the use of cysteine-modified polymer nanofibers for the rapid and efficient removal of Cr(III) from real tannery waste water samples. Various parameters such as pH, load of nanofibers and time of exposure were optimized to achieve maximum removal. The optimum parameters were found to be 0.1 mg of nanofibers per mL of tannery waste water with a pH of 5.5 and an exposure time of 45 min. Almost 99% Cr(III) was removed at these ideal conditions thus demonstrating the efficacy of our material. The maximum removal capacity at these ideal conditions was estimated to be approximately 1.75 g of chromium/gram of polymeric material. This is probably due to a variety of factors including the apparent high surface to volume ratio exhibited by these nanofibers and also due to the availability of numerous cysteine groups that are known to have high binding affinities with heavy metal ions. These nanoscale polymeric materials show great potential towards the removal of heavy metal cations from waste waters.

We describe a versatile method for students to fabricate carbon nanotube-based enzyme-modified biosensor electrodes using a layer-by-layer electrostatic self-assembly procedure. Amperometric experiments employing a simple three-electrode cell enabled sensitive and selective determination of glucose in various commercially produced beverages familiar to students. The method was optimized with respect to various parameters, and the results compared very well with standard methods used for glucose determination. The procedure is versatile, robust, and relatively inexpensive. It can be performed by undergraduate students as was demonstrated by the good results obtained by the upper-level instrumental analysis class. The experiment can easily be integrated into laboratory classes for analytical chemistry, biotechnology, or biochemistry students to demonstrate important principles and techniques of nanoscale science, materials science, biochemistry, electrochemistry, and sensor technology.

We describe the synthesis of zinc oxide (ZnO) nanoparticles and demonstrate their attachment to multiwalled carbon tubes, resulting in a composite with a unique synergistic effect. Morphology and size of ZnO nanostructures were controlled using hydrothermal synthesis, varying the hydrothermal treatment temperature, prior to attachment to carboxylic acid functionalized multi-walled carbon nanotubes for sensing applications. A strong dependence of electrocatalytic activity on nanosized ZnO shape was shown. High activity for H 2 O 2 reduction was achieved when nanocomposite precursors with a roughly semi-spherical morphology (no needle-like particles present) formed at 90 °C. A 2.4-fold increase in cyclic voltammetry current accompanied by decrease in overpotential from the composites made from the nanosized, needle-like-free ZnO shapes was observed as compared to those composites produced from needle-like shaped ZnO. Electrocatalytic activity varied with pH, maximizing at pH 7.4. A stable, linear response for H 2 O 2 concentrations was observed in the 1–20 mM concentration range.

Since the first generation of DNA vaccines was introduced in 1988, remarkable improvements have been made to improve their efficacy and immunogenicity. Although human clinical trials have shown that delivery of DNA vaccines is well tolerated and safe, the potency of these vaccines in humans is somewhat less than optimal. The development of a gene-based vaccine that was effective enough to be approved for clinical use in humans would be one of, if not the most important, advance in vaccines to date. This paper highlights the literature relating to gene-based vaccines, specifically DNA vaccines, and suggests possible approaches to boost their performance. In addition, we explore the idea that combining RNA and nanomaterials may hold the key to successful gene-based vaccines for prevention and treatment of disease.

This principle goal of this research was to examine the effects of various nanomaterials on the activity and behavior of the firefly enzyme luciferase. Nanomaterials have been found to stabilize, and in some instances, shown to increase the activity of enzymes. In this study gold, manganese oxide (MnO), and zinc oxide (ZnO) nanomaterials were utilized in order to test their effects on enzyme activity. Luciferase was used because its activity is easy to analyze, as it typically produces a large amount of bioluminescence easily detected by a Microtiter plate reader. Following incubation with the various nanomaterials, luciferase was subjected to degradation by several protein denaturing agents, such as heat, SDS, urea, ethanol, protease, hydrogen peroxide, and pH changes. Results indicated that luciferase activity is indeed affected when combined with nanomaterials, accompanied by both increases and decreases in enzyme activity depending on the type of nanomaterial and denaturing agent used. In most of the experiments, when incubated with ZnO nanomaterials, luciferase depicted significant increases in activity and bioluminescence. Additional experiments, in which human A375 cells were treated with luciferase-nanomaterial mixtures, also depicted increased enzyme activity and bioluminescence for luciferase incubated with ZnO nanomaterials. Ultimately, our findings indicated that when luciferase was subjected to multiple types of denaturation, zinc oxide nanomaterials dramatically preserved and increased enzyme activity and bioluminescence.

We report the development of a novel, sim- ple, and highly effective polymeric material with nano- scale dimensions for use in removal of heavy metal ions from aqueous media. The nanomaterial was � 200 nm in diameter and several microns long and was fabricated in the form of nanowires via template-directed electrochemi- cal polymerization. The nanowires were covalently modi- fied by cysteine, a nonessential amino acid with very high binding constants for selected toxic heavy metal ions, such as, As 3þ ,C d 2þ ,P b 2þ , and Cu 2þ . We demonstrated rapid and efficient removal of As 3þ ,C d 2þ ,P b 2þ , and Cu 2þ ions from natural water samples. The arsenic removal capacity was found to be � 160 mg As 3þ per gram of the material, a substantially greater removal capacity than other materi- als reported to date. The removal capacity of other heavy metals ions was also rapid and effective, their concentra- tions becoming undetectable in a matter of minutes after treatment with the nanowires. These nanowires have dem- onstrated potential that could lead to a low cost, novel, and highly effective technique for use in treatment of drinking water and for other environmental remediation purposes. V C 2009 Wiley Periodicals, Inc. J Appl Polym Sci 116: 308-313, 2010

Zinc and manganese nanomaterials may have potential for biomedical nanotechnology. Here first generation Zn and Mn oxide nanomaterials were prepared as determined by XRD. Transmission electron microscopy confirmed their nanoscale in two dimensions and revealed a rod or belt-like morphology for MnO or ZnO respectively. Association of MnO and ZnO to three model biomedically important proteins (albumin, protamine and thrombin) has been characterized by ultra-violet and dynamic laser light spectroscopy, UVS and DLLS respectively. UVS demonstrated a concentration-dependent loss of protein from the supernatant upon sedimentation of MnO or ZnO. Shifts in the surface charge of the MnO or ZnO by DLLS confirmed the protein's adsorption to the surface. MnO and ZnO were incubated with live human cells in culture (HeLa, A375 or 1321N1). A marked difference was observed for the two nanomaterials behavior in cell culture where the MnO could be discerned associating at the cell surface whereas the ZnO caused the cells to exhibit a rounded up morphology. Trypan blue dye exclusion studies demonstrated cytotoxicity of the ZnO at high concentrations 62.5-31.5 microg/mL whereas surprisingly the MnO demonstrated no cytotoxicity at any of the concentrations tested.

A sensitive electrochemical detection method was developed involving multiwalled carbon nanotubes (MWCNTs) covalently modified with osmium-based redox polymer. The polycationic redox polymer, poly[4-vinylpyridine Os(bipyridine) 2 Cl]-co-ethylamine (POs-EA), was first synthesized and covalently attached to MWCNTs. The redox polymer modified MWCNTs were then trapped in a hydrogel formed from polyethyleneglycol diacrylate (PEG-DA) using 1-phenyl-2-hydroxy-2-methyl-1-propanone as a photoinitiator. Upon exposure to aqueous media, the gel swelled to allow movement of analytes in and out of the gel without having any effect on the redox polymer modified nanotube signal. Cyclic voltammetry showed reversible pairs of oxidation–reduction peaks at 0.35 V ( vs Ag/AgCl) corresponding to the Os II /Os III . This assembly was able to catalytically oxidize both acetaminophen and ascorbic acid (AA). Amperometric data showed a linearity between 0 and 100 μM ( R 2 of 0.999, n = 10) 0.5 mV vs Ag/AgCl (sensitivity 0.003 μA/μM) for ascorbic acid, while for acetaminophen the linearity was between 0 and 1.5 μM ( R 2 of 0.9999, n = 8) with a sensitivity of 65 μA/μM. This sensing system was found to exhibit remarkable stability over several weeks with excellent reproducibility.

A sensitive voltammetric method for detection of trace heavy metal ions using chemically modified carbon nanotubes (CNTs) electrode surfaces is described. The CNTs were covalently modified with cysteine prior to casting on electrode surfaces. Cysteine is an amino acid with high affinities towards some heavy metals. In this assay, heavy metals ions accumulated on the cysteine-modified CNT electrode surfaces prior to being subjected to differential pulse anodic stripping voltammetry analysis. The resulting peak currents were linearly related to the concentrations of the metal ions. The method was optimized with respect to accumulation time, reduction time and reduction potential. The detection limits were found to be 1 ppb and 15 ppb for Pb2+ and Cu2+ respectively. The technique was used for the detection of Pb2+ and Cu2+ in spiked lake water. The average recoveries of Pb2+ and Cu2+ were 96.2% and 94.5% with relative standard deviations of 8.43% and 7.53% respectively. The potential for simultaneous detection of heavy metal ions by the modified CNTs was also demonstrated.

Layer by layer films of protein and redox polymer were constructed and used to simultaneously analyze ascorbic acid and hydrogen peroxide. The films were made using hemoglobin and poly[4-vinylpyridine Os(bipyridine)(2)Cl]-co-ethylamine (Pos-Ea). The film growth was monitored using cyclic voltammetry, quartz crystal microbalance (QCM) and atomic force microscopy (AFM). Reversible pairs of oxidation-reduction peaks were observed using cyclic voltammetry corresponding to the Os(II)/Os(III) from redox polymer and HbFe(III)/HbFe(II) redox couples at 0.35 and -0.25 V vs. Ag/AgCl, respectively. The two redox centers were independent of each other. This enabled the simultaneous and independent determination of ascorbic acid and hydrogen. Peak currents were linearly related to concentration for both analytes in a mixture. The linear range of ascorbic acid was 0-1 mM (R(2) = 0.9996, n = 5) at scan rate of 50 mV s(-1) (sensitivity 3.5 microA/mM) while hydrogen peroxide linear range was 1.0-10.0 microM (R(2) = 0.991, n = 6) with sensitivity of 1.85 microA/microM.

Field-effect transistors based on single nanowires of conducting polymers (i.e., polyaniline and polypyrrole) were fabricated and characterized. The 100-nm-wide and 2.5-μm-long conducting polymer nanowire field-effect transistors were turned “on” and “off” by electrical or chemical signals. A large modulation in the electrical conductivity of up to 3 orders of magnitude was demonstrated as a result of varying the electrochemical gate potential of these nanowires. Single nanowire conducting polymer field-effect transistors show higher electrical performance than field-effect transistors based on conducting polymer nanowire electrode junctions and thin films in terms of their transconductance (gm) and on/off current (Ion/Ioff) ratio. Furthermore, the performance of single nanowires conducting polymer field-effect transistors was found to be comparable to the silicon nanowire field-effect transistors. These results imply that it is possible to tune the sensitivities of these conducting polymer nanowires by s...

We report the electropolymerization and characterization of polypyrrole films doped with poly(m-aminobenzene sulfonic acid (PABS) functionalized single-walled nanotubes (SWNT) (PPy/SWNT-PABS). The negatively charged water-soluble SWNT-PABS served as anionic dopant during the electropolymerization to synthesize PPy/SWNTPABS composite films. The synthetic, morphological and electrical properties of PPy/SWNT-PABS films and chloride doped polypyrrole (PPy/Cl) films were compared. Characterization was performed by cyclic voltammetry, atomic force microscopy (AFM), scanning electron microscopy (SEM) and Raman spectroscopy. SEM and AFM images revealed that the incorporation of SWNT-PABS significantly altered the morphology of the PPy. Cyclic voltammetry showed improved electrochemical properties of PPy/SWNT-PABS films as compared to PPy/Cl films. Raman Spectroscopy confirmed the presence of SWNT-PABS within composite films. Field effect transistor (FET) and electrical characterization studies show that the incorporation of the SWNT-PABS increased the electronic performance of PPy/SWNT-PABS films when compared to PPy/Cl films. Finally, we fabricated PPy/SWNT-PABS nanotubes which may lead to potential applications to sensors and other electronic devices.

Advances in conducting electroactive polymers (CEPs) have driven the design of novel chemical and biochemical sensors. The redox properties of CEPs have been intensely studied for more than two decades with emphasis on their synthesis and characterization. Little attention has been paid to the importance of mechanism in sensor designs. However, in order to design robust and stable sensors, it is important to understand how the polymer structure, morphology, adhesion properties and microenvironment affect sensor performance. This work describes how chemical and biological sensors have been designed, fabricated, characterized and tested based on the fundamental understanding in CEPs. The use of photopolymerized conducting polymers in sensor designs is described. Four focus areas are presented in which the electronic properties of CEPs have enabled the design of novel sensors for organics, nucleic acids, biological molecules, vapors and metal ions.

An electrochemical method for the determination of lead has been developed using overoxidized polypyrrole (OPPy) electrode doped with 2(2-pyridylazo)chromotropic acid anion (PACh 2� ). The PACh 2� acts both as a chelating agent and a counter anion within the polypyrrole matrix. In a typical assay, Pb 2� is accumulated on a solid electrode via the formation of a lead � /PACh complex at open circuit. The electrode containing the Pb 2� PACh 2� is then transferred to a 0.1 M acetate buffer where it is subjected to differential pulse anodic stripping voltammetry. The resulting stripping peak current was linearly related to the concentration of lead. The method has been optimized with respect to pH, concentration of chelating agent, accumulation time, reduction potential and time. The detection limit was found to be 10 ng ml � 1 with a linear range of 0 � /200 ng ml � 1 . The method has been validated for the determination of lead using spiked potable water at 25 ng ml � 1 . The average recovery was 93.4% with a relative standard deviation of 8.54%. # 2002 Elsevier Science B.V. All rights reserved.

Two-dimensional fluorescence difference spectroscopy (2-D FDS) was used to determine the unique spectral signatures of zinc oxide (ZnO), magnesium oxide (MgO), and 5% magnesium zinc oxide nanocomposite (5% Mg/ZnO) and was then used to demonstrate the change in spectral signature that occurs when physiologically important proteins, such as angiotensin-converting enzyme (ACE) and ribonuclease A (RNase A), interact with ZnO nanoparticles (NPs). When RNase A is bound to 5% Mg/ZnO, the intensity is quenched, while the intensity is magnified and a significant shift is seen when torula yeast RNA (TYRNA) is bound to RNase A and 5% Mg/ZnO. The intensity of 5% Mg/ZnO is quenched also when thrombin and thrombin aptamer are bound to the nanocomposite. These data indicate that RNA–protein interaction can occur unimpeded on the surface of NPs, which was confirmed by gel electrophoresis, and importantly that the change in fluorescence excitation, emission, and intensity shown by 2-D FDS may indicate specificity of biomolecular interactions.

We demonstrate an extremely facile, rapid, specific and selective method for detecting proteins using aptamerconjugated gold nanoparticles coupled with dynamic light scattering (DLS) at ambient conditions. Addition of proteins to aptamer-conjugated gold nanoparticles (GNPs) induced the formation of protein-aptamer-gold nanoparticle conjugate complexes. The average hydrodynamic diameter of the nanoconjugate complexes as measured by DLS, increased with the corresponding increase in protein concentration. This correlation formed the analytical basis of the assay. The nanoparticles and nanoconjugate complexes were characterized by transmission electron microscopy, ultra-violet visible spectroscopy and DLS. Various parameters affecting the assay were optimized. Using thrombin as the model analyte, we demonstrated the detection of as low as 1.41 nM (0.05 μg/mL) of the protein. A linear dynamic range of up to 300 nM (11 μg/mL) was realized. The presence of other interfering proteins such as BSA showed no effect on the assay response.The presence of other interfering proteins such as bovine serum albumin (BSA) showed no significant effect on the assay response.

The sections in this article are Introduction Fabrication of Conducting Polymer Nanowires Surface Modification of Conducting Polymer Nanowires Assembly/Alignment of Conducting Polymer Nanowires Biomedical Applications of Conducting Polymer Nanowires Sensing and Detection Proteins and Disease Markers Detection of Bacteria Detection of Small Molecules Detection of Heavy-Metal Ions and Pesticides Drug Delivery and DNA Carriers Summary and Future Perspectives Keywords: conducting polymers; nanowires; nanotubes; biomedical; nanostructured materials; nanotechnology; biosensors; drug delivery

In this study, manganese oxide (MnO) nanorods and its association with polyamidoamine dendrimer (PAMAM) and macromolecular RNA were analyzed. Because manganese is found naturally in cells and tissues and binds proteins and nucleic acids, nanomaterials derived from manganese, such as first generation MnO, may have potential as a biocompatible delivery agent for therapeutic or diagnostic biomedical applications. Nucleic acids have a powerful influence over cell processes, such as gene transcription and RNA processing; however, macromolecular RNA is particularly difficult to stabilize as a nanoparticle and to transport across cell membranes while maintaining structure and function. PAMAM is a cationic, branching dendrimer known to form strong complexes with nucleic acids and to protect them from degradation, and is also considered to be a cell penetrating material. There is currently much interest in polyinosinic:polycytidylic RNA (poly I:C) because of its potent and specific immunogenic properties and as a solo or combination therapy. In order to address this potential, here, as a first step, we used PAMAM to attach poly I:C onto MnO nanorods. Morphology of the MnO nanorods was examined by field emission scanning electron microscopy (FESEM) and their composition by energy dispersive X-ray microanalysis (EDX). Evidence was generated for RNA : PAMAM : MnO nanorod binding by a gel shift assay using gel electrophoresis, a sedimentation assay using UV spectroscopy, and zeta potential shifts using dynamic laser light scattering. The data suggest that RNA was successfully attached to the MnO nanorods using PAMAM, and this suggestion was supported by direct visualization of the ternary complexes with FESEM characterizations. In order to confirm that the associations were biocompatible and taken up by cells, MTT assays were carried out to assess the metabolic activity of HeLa cells after incubation with the complexes and appropriate controls. Subsequently, we performed transfection assays using PAMAM:MnO complexes with pDNA encoding a green fluorescent protein reporter gene instead of RNA. The results suggest that the complexes had minimal impact on metabolic activity, were readily taken up by cells, and the fluorescent protein was expressed. From the evidence, we conclude that complexes of PAMAM:MnO interact with nucleic acids to form associations that are well-tolerated and readily taken up by cells.

Using X-Ray Diffraction, Scanning Electron Microscopy, and Superconducting Quantum Interference Device magnetometer, detailed structural, morphological, and magnetic properties are reported on undoped and cobalt doped ZnO Dilute Magnetic Semiconductors, which were prepared by the hydrothermal method. Synthesis of undoped ZnO and cobalt-doped ZnO nanorods was carried out using aqueous solutions of Zn(NO3)2⋅6H2O, Co(C2H3OO)2⋅4H2O, and NH4OH as hydrolytic catalyst. Samples of different sizes and shapes were synthesized by varying process parameters such as solution molarity (0.05M, 0.15M, 0.3M, 0.5M), pH of the precursors in the range 8-11, growth temperature (100°-130°C), growth time (3-6 hrs), and annealing time. Optimum synthesis parameters to grow ZnO and cobalt-doped ZnO nanorods have been obtained. These nanorods show paramagnetic-like behavior. Our results do not indicate ferromagnetism behavior, unlike reported in thin films and nanocrystalline samples. The differences are likely due to the possible ...

DNA and RNA micro- and nanoparticles are increasingly being used for gene and siRNA drug delivery and a variety of other applications in bionanotechnology. On the nanoscale, these entities represent unique challenges from a physicochemical characterization perspective. Here, nucleic acid conjugates with protamine and gold nanoparticles (GNP) were characterized comparatively in the nanorange of concentration by UV/Vis NanoDrop spectroscopy, fluorimetry, and gel electrophoresis. Given the intense interest in splice-site switching oligomers (SSOs), we utilized a human tumor cell culture system (HeLa pLuc-705), in which SSO-directed splicing repair upregulates luciferase expression, in order to investigate bioactivity of the bionanoconjugates. Process parameters important for bioactivity were investigated, and the bimolecular nanoconjugates were confirmed by shifts in the dynamic laser light scatter (DLLS), UV/Vis spectrum, gel electrophoresis, or sedimentation pattern. The data presented herein may be useful in the future development of pharmaceutical and biotechnology formulations, processes, and analyses concerning protein, DNA, or RNA bionanoconjugates.

We report the electrochemical deposition of poly(pyrrolepropylic acid) nanowires, their covalent modification with antibodies and their conversion into potential functional sensor devices. The nanowires and the devices were characterised by optical microscopy, fluorescence microscopy, electron microscopy and electrical measurements. Fluorescence images, current–voltage (I–V) profiles and real-time sensing measurements demonstrated a rapid and highly sensitive and selective detection of human serum albumin (HSA), a substance that has been used to diagnose incipient renal disease. The detection is based on the selective binding of HSA onto anti-HSA that is covalently attached to the nanowires. The binding changes the electrical properties of the nanowires thus enabling the real-time detection. Whilst the utility of the research was demonstrated for protein binding/detection, the technology could easily be designed for the detection of other analytes by the modification of polymer nanowires with other analyte-specific molecules/biomolecules. Therefore, the technology has the potential to positively impact broad analytical applications in the biomedical, environmental and other sectors.

Environmental security is one of the fundamental requirements of our well being. However, it still remains a major global challenge. Therefore, in addition to reducing and/or eliminating the amounts of toxic discharges into the environment, there is need to develop techniques that can detect and monitor these environmental pollutants in a sensitive and selective manner to enable effective remediation. Because of their integrated nature, biosensors are ideal for environmental monitoring and detection as they can be portable and provide selective and sensitive rapid responses in real time. In this review we discuss the main concepts behind the development of biosensors that have most relevant applications in the field of environmental monitoring and detection. We also review and document recent trends and challenges in biosensor research and development particularly in the detection of species of environmental significance such as organophosphate nerve agents, heavy metals, organic contaminants, pathogenic microorganisms and their toxins. Special focus will be given to the trends that have the most promising applications in environmental security. We conclude by highlighting the directions towards which future biosensors research in environmental security sector might proceed.

This chapter addresses the applications of conducting polymer nanowires (CP NWs) in chemical and biological sensing. In the first section, we introduce CP NWs as new members of the one-dimensional (1D) nanostructured materials family. We discuss the advantages associated with the use of 1D nanostructure materials in general and CP NWs in particular. In the second section, various methods that are used to synthesize and fabricate CP NWs are discussed including their strengths and limitations. The third section outlines the functionalization of these nanostructures to tailor them to respond only to desired target analytes while the fourth section involves the assembly/alignment of these CP NWs to form functional devices. We demonstrate some sensing applications based on CP NWs in the fifth section and conclude with a brief summary and outlook on the future of CP NWs in sensing applications and some of the limitations that have to be overcome to make them competitive sensing materials. Keywords: conducting polymer nanowires; field effect transistors; functionalization; assembly; applications

This paper describes a new approach for the preparation of polyamic acid (PAA) composites containing Ag and Au nanoparticles. The composite film of PAA and metal particles were obtained upon electrodeposition of a PAA solution containing gold or silver salts with subsequent thermal treatment, while imidization to polyimide is prevented. The structural characterization of the films is provided by 1H NMR and Fourier transform infrared spectroscopy (FTIR), while the presence of metallic nanoparticles within the polymeric matrix was confirmed by scanning electron microscopy (SEM), cyclic voltammetry (CV), energy-dispersive X-ray analysis (EDX), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). This approach utilizes the unique reactivity of PAA by preventing the cyclization of the reactive soluble intermediate into polyimides at low temperature to design polymer-assisted nanostructured materials. The ability to prevent the cyclization process should enable the design of a new class of electrode materials by use of thermal reduction and/or electrodeposition.

Due to the increased threats of chemical and biological agents of injury by terrorist organizations, a significant effort is underway to develop tools that can be used to detect and effectively combat chemical and biochemical toxins. In addition to the right mix of policies and training of medical personnel on how to recognize symptoms of biochemical warfare agents, the major success in combating terrorism still lies in the prevention, early detection and the efficient and timely response using reliable analytical technologies and powerful therapies for minimizing the effects in the event of an attack. The public and regulatory agencies expect reliable methodologies and devices for public security. Today's systems are too bulky or slow to meet the “detect-to-warn” needs for first responders such as soldiers and medical personnel. This paper presents the challenges in monitoring technologies for warfare agents and other toxins. It provides an overview of how advances in environmental analytical methodologies could be adapted to design reliable sensors for public safety and environmental surveillance. The paths to designing sensors that meet the needs of today's measurement challenges are analyzed using examples of novel sensors, autonomous cell-based toxicity monitoring, ‘Lab-on-a-Chip’ devices and conventional environmental analytical techniques. Finally, in order to ensure that the public and legal authorities are provided with quality data to make informed decisions, guidelines are provided for assessing data quality and quality assurance using the United States Environmental Protection Agency (US-EPA) methodologies.

This paper extends the classification approaches described in reference [1] in the following way: (1.) developing and evaluating a new method for evolving organophosphate nerve agent Support Vector Machine (SVM) classifiers using Evolutionary Programming, (2.) conducting research experiments using a larger database of organophosphate nerve agents, and (3.) upgrading the architecture to an object-based grid system for evaluating the classification of EP derived SVMs. Due to the increased threats of chemical and biological weapons of mass destruction (WMD) by international terrorist organizations, a significant effort is underway to develop tools that can be used to detect and effectively combat biochemical warfare. This paper reports the integration of multi-array sensors with Support Vector Machines (SVMs) for the detection of organophosphates nerve agents using a grid computing system called Legion. Grid computing is the use of large collections of heterogeneous, distributed resources (including machines, databases, devices, and users) to support large-scale computations and wide-area data access. Finally, preliminary results using EP derived support vector machines designed to operate on distributed systems have provided accurate classification results. In addition, distributed training time architectures are 50 times faster when compared to standard iterative training time methods.

The need for rapid and accurate detection systems is expanding and the utilization of cross-reactive sensor arrays to detect chemical warfare agents in conjunction with novel computational techniques may prove to be a potential solution to this challenge. We have investigated the detection, prediction, and classification of various organophosphate (OP) nerve agent simulants using sensor arrays with a novel learning scheme known as support vector machines (SVMs). The OPs tested include parathion, malathion, dichlorvos, trichlorfon, paraoxon, and diazinon. A new data reduction software program was written in MATLAB V. 6.1 to extract steady-state and kinetic data from the sensor arrays. The program also creates training sets by mixing and randomly sorting any combination of data categories into both positive and negative cases. The resulting signals were fed into SVM software for "pairwise" and "one" vs all classification. Experimental results for this new paradigm show a significant increase in classification accuracy when compared to artificial neural networks (ANNs). Three kernels, the S2000, the polynomial, and the Gaussian radial basis function (RBF), were tested and compared to the ANN. The following measures of performance were considered in the pairwise classification: receiver operating curve (ROC) Az indices, specificities, and positive predictive values (PPVs). The ROC Az) values, specifities, and PPVs increases ranged from 5% to 25%, 108% to 204%, and 13% to 54%, respectively, in all OP pairs studied when compared to the ANN baseline. Dichlorvos, trichlorfon, and paraoxon were perfectly predicted. Positive prediction for malathion was 95%.

Due to the increased threats of chemical and biological weapons of mass destruction (WMD) by international terrorist organizations, a significant effort is underway to develop tools that can be used to detect and effectively combat biochemical warfare. Furthermore, recent events have highlighted awareness that chemical and biological agents (CBAs) may become the preferred, cheap alternative WMD, because these agents can effectively attack large populations while leaving infrastructures intact. Despite the availability of numerous sensing devices, intelligent hybrid sensors that can detect and degrade CBAs are virtually nonexistent. This paper reports the integration of multi-array sensors with Support Vector Machines (SVMs) for the detection of organophosphates nerve agents using parathion and dichlorvos as model stimulants compounds. SVMs were used for the design and evaluation of new and more accurate data extraction, preprocessing and classification. Experimental results for the paradigms developed using Structural Risk Minimization, show a significant increase in classification accuracy when compared to the existing AromaScan baseline system. Specifically, the results of this research has demonstrated that, for the Parathion versus Dichlorvos pair, when compared to the AromaScan baseline system: (1) a 23% improvement in the overall ROC Az index using the S2000 kernel, with similar improvements with the Gaussian and polynomial (of degree 2) kernels, (2) a significant 173% improvement in specificity with the S2000 kernel. This means that the number of false negative errors were reduced by 173%, while making no false positive errors, when compared to the AromaScan base line performance. (3) The Gaussian and polynomial kernels demonstrated similar specificity at 100% sensitivity. All SVM classifiers provided essentially perfect classification performance for the Dichlorvos versus Trichlorfon pair. For the most difficult classification task, the Parathion versus Paraoxon pair, the following results were achieved (using the three SVM kernels: (1) ROC Az indices from approximately 93% to greater than 99%, (2) partial Az values from ≈79% to 93%, (3) specificities from 76% to ≈84% at 100 and 98% sensitivity, and (4) PPVs from 73% to ≈84% at 100% and 98% sensitivities. These are excellent results, considering only one atom differentiates these nerve agents.

This article reviews applications of nanoscale carbon-based materials in heavy metal sensing and detection. These materials, including single-walled carbon nanotubes, multi-walled carbon nanotubes and carbon nanofibers among others, have unique and tunable properties enabling applications in various fields spanning from health, electronics and the environment sector. Specifically, we highlight the unique properties of these materials that enable their applications in the sorption and preconcentration of heavy metals ions prior to detection by spectroscopic, chromatographic and electrochemical techniques. We also discuss their distinct properties that enable them to be used as novel electrode materials in sensing and detection. The fabrication and modification of these electrodes is discussed in detail and their applications in various electrochemical techniques such as voltammetric stripping analysis, potentiometric stripping analysis, field effect transistor-based devices and electrical impedance are critically reviewed. Perspectives and futures trends in the use of these materials in heavy metal sensing and detection will also be highlighted.

Nanotechnology has virtually exploded in the last few years with seemingly limitless opportunity across all segments of our society. If gene and RNA therapy are to ever realize their full potential, there is a great need for nanomaterials that can bind, stabilize, and deliver these macromolecular nucleic acids into human cells and tissues. Many researchers have turned to gold nanomaterials, as gold is thought to be relatively well tolerated in humans and provides an inert material upon which nucleic acids can attach. Here, we review the various strategies for associating macromolecular nucleic acids to the surface of gold nanoparticles (GNPs), the characterization chemistries involved, and the potential advantages of GNPs in terms of stabilization and delivery.

This article describes a laboratory procedure designed for a junior-level instrumental analysis course using a pressure-assisted chelating extraction (PACE) technique to digest heavy metals from solid matrices. PACE can achieve the digestion of metals through direct contact between solids and chelates under controlled temperature and pressure. After digestion, the metals can be analyzed using flame atomic absorption spectroscopy (FAAS). The exercise requires two three-hour laboratory periods. In one lab period, students use a wet acid-digestion technique to remove heavy metals from sediment samples and analyze them using FAAS. In the second lab period, students digest the samples using PACE and similarly analyze the sediment samples by FAAS. The PACE results are then compared with the results from wet acid-digestion. In the experiments performed by the students, mean lead recoveries were 95% with an RSD of 10% with PACE, and 111% with an RSD of 37% with the acid-digestion technique. The PACE approach allo...