Determination of the binding site size of hexaammineruthenium(iii) inside monolayers of DNA on gold.

Hexaammineruthenium(iii), RuHex3+, is a DNA-binding metal complex that is widely used as a redox marker for the indirect determination of DNA coverage at the electrode surface. The conversion of electrochemically quantifiable surface excess of RuHex3+ into DNA surface coverage requires the knowledge of the binding site size of RuHex3+ (s). Traditionally, s on surface-immobilized DNA has been assumed to be equivalent to that on solution-phase DNA, which was experimentally determined in previous studies. Nevertheless, the different local microenvironments existing inside DNA monolayers in comparison to that in bulk solutions cast doubt on the validity of this assumption. In this report, we used electrochemical techniques to investigate s on surface-immobilized DNA. The values of s inside the DNA monolayers were found to be significantly smaller than that reported on solution-phase DNA. Besides, s was found to depend on the DNA packing density and became larger by increasing the DNA surface coverage or hybridizing the surface-tethered DNAs with complementary strands. Our data indicate that the RuHex3+ method, in which an s value of 3 nucleotides is used for the conversion of RuHex3+ to DNA surface coverage, does not always give reliable results.

Targeted Detection of Single-Nucleotide Variations: Progress and Promise.

Advances in nucleic acid sequencing and genotyping technologies have facilitated the discovery of an increasing number of single-nucleotide variations (SNVs) associated with disease onset, progression, and response to therapy. The reliable detection of such disease-specific SNVs can ensure timely and effective therapeutic action, enabling precision medicine. This has driven extensive efforts in recent years to develop novel methods for the fast and cost-effective analysis of targeted SNVs. In this Review, we highlight the most recent and significant advances made toward the development of such methodologies.

Assessment of cytotoxicity of choline chloride-based natural deep eutectic solvents against human HEK-293 cells: A QSAR analysis.

Deep eutectic solvents (DESs) are a new generation of solvents. To consider them as green solvents, investigation of their toxicity is essential. In this work, the cytotoxicity of a number of natural deep eutectic solvents (NADESs) against HEK-293 human embryonic kidney cells was evaluated by MTT assay. The NADESs were prepared with choline chloride (ChCl) as hydrogen-bond acceptor (HBA) and different sugar alcohols as hydrogen-bond donor (HBD) constituents. They showed IC50 values in the range of 3.52-75.46 mM. These results were used to evaluate the effect of structural parameters on the cytotoxicity of the studied NADESs by using quantitative structure activity relationship (QSAR) analysis. A three-parameter linear model was obtained between - log(IC50) as a dependent variable and structural descriptors as independent variables. Rotatable bond number (RBN), mean atomic van der Waals volume (Mv) and the interaction of second power carbon numbers with the molar ratio of HBA to HBD in each NADES (C2 Ratio), were three major parameters. The statistical model covered about 76.4% and 69.8% variance of data in training and leave-one-out cross-validation, respectively. This work, as the first study on the QSAR analysis of DESs, can provide a good perspective for designing greener novel DESs.

Synthesis of highly stable and biocompatible gold nanoparticles for use as a new X-ray contrast agent.

This work reports a novel reduction procedure for the synthesis of Gum Arabic (GA) capped-gold nanoparticles (AuNPs) in glucosammonium formate as a new ionic liquid. The GA coated AuNPs show good stability in physiological media. The synthesized AuNPs were characterized by UV-Vis spectroscopy, transmission electron microscopy, dynamic light scattering and X-ray diffraction analysis. These stable AuNPs are introduced as a new contrast agent for X-ray Computed Tomography (X-ray CT). These nanoparticles have higher contrasting properties than the commercial contrast agent, Visipaque. The precursors used (Gum Arabic and glucose based-ionic liquid) for synthesis of AuNPs are biocompatible and non-toxic.

Nucleic acid-based electrochemical nanobiosensors.

The detection of biomarkers using sensitive and selective analytical devices is critically important for the early stage diagnosis and treatment of diseases. The synergy between the high specificity of nucleic acid recognition units and the great sensitivity of electrochemical signal transductions has already shown promise for the development of efficient biosensing platforms. Yet nucleic-acid based electrochemical biosensors often rely on target amplification strategies (e.g., polymerase chain reactions) to detect analytes at clinically relevant concentration ranges. The complexity and time-consuming nature of these amplification methods impede moving nucleic acid-based electrochemical biosensors from laboratory-based to point-of-care test settings. Fortunately, advancements in nanotechnology have provided growing evidence that the recruitment of nanoscaled materials and structures can enhance the biosensing performance (particularly in terms of sensitivity and response time) to the level suitable for use in point-of-care diagnostic tools. This Review highlights the significant progress in the field of nucleic acid-based electrochemical nanobiosensing with the focus on the works published during the last five years.

Blue-emitting copper nanoparticles as a fluorescent probe for detection of cyanide ions.

A simple and green method for the determination of cyanide ions (CN-) has been developed which is based on copper nanoparticles (CuNPs) acting as a fluorescent probe in aqueous solutions. In this study, fluorescent CuNPs have been synthesized in the presence of ascorbic acid which acts both as a reducing and protecting agent. The preparation of CuNPs by this method is very simple, low cost, high yield, and reproducible. The prepared CuNPs have the small average diameter of 10nm and show a blue emission at 440nm. However, upon the addition of CN- into the CuNPs sensing system, its fluorescence was quenched considerably as a result of the strong interaction between cyanide and copper. Under optimized conditions, a good relationship was observed between the fluorescence quenching of the system and the concentration of CN- in the range of 0.5-18µmolL-1 with a detection limit of 0.37µmolL-1. In addition, the developed sensor has a high selectivity and simple operations. Furthermore, as a cost-effective and selective fluorescent probe, the CuNPs sensor was successfully employed for the detection of CN- ions in water samples.

Chlorine triggered de-alloying of AuAg@Carbon nanodots: Towards fabrication of a dual signalling assay combining the plasmonic property of bimetallic alloy nanoparticles and photoluminescence of carbon nanodots.

Integration of Au-Ag alloy and fluorescent carbon nanodots (C-dots) into a single platform resulted in a new dual sensing assay for chlorine. Selective etching of Ag from AuAg@C-dots was transformed into: (i) colorimetric signal by surface plasmon resonance (SPR) tuning of the alloy and (ii) fluorimetric signal by perturbation of fluorescence energy transfer between C-dots and alloy nanoparticles. Fast oxidizing of silver atoms incorporated in the bimetallic structure induced by chlorine resulted in selective de-alloying of bimetallic hybrid nanoparticles and an intense visible change of the colloidal dispersion color. On the other hand, the systematic change in Au/Ag ratio strongly affected the emission intensity of C-dots in the hybrid structure leading to an enhancement in the fluorescence signal. Thus, the assay enables the detection of chlorine both under visible and UV lights with high sensitivity. The detection limit (DL) values were calculated as 6.2 × 10-7 M and 5.1 × 10-7 M through colorimetric and fluorimetric pathways, respectively. Most importantly, it was demonstrated to be selective over common cations, anions and some reactive oxygen species (ROS). This assay was successfully applied to the determination of chlorine concentration in bleach solution and tap water. It is robust and is suitable for cost effective chlorine measurement in environmental samples.

Simultaneous electrochemical determination of L-cysteine and L-cysteine disulfide at carbon ionic liquid electrode.

A linear sweep voltammetric method is used for direct simultaneous determination of L-cysteine and L-cysteine disulfide (cystine) based on carbon ionic liquid electrode. With carbon ionic liquid electrode as a high performance electrode, two oxidation peaks for L-cysteine (0.62 V) and L-cysteine disulfide (1.3 V) were observed with a significant separation of about 680 mV (vs. Ag/AgCl) in phosphate buffer solution (pH 6.0). The linear ranges were obtained as 1.0-450 and 5.0-700 µM and detection limits were estimated to be 0.298 and 4.258 µM for L-cysteine and L-cysteine disulfide, respectively. This composite electrode was applied for simultaneous determination of L-cysteine and L-cysteine disulfide in two real samples, artificial urine and nutrient broth. Satisfactory results were obtained which clearly indicate the applicability of the proposed electrode for simultaneous determination of these compounds in complex matrices.

Microwave-assisted synthesis of gold, silver, platinum and palladium nanostructures and their use in electrocatalytic applications.

Microwave-assisted ionic liquid method was used for synthesis of various noble metals, such as gold, silver, platinum and palladium nanomaterials. This route does not employ any template agent, surface capping agents or reducing agents. The process is fast, simple and of high yield. Different metal precursors in various ionic liquids media (1-butyl-3-methylimidazolium tetrafluoroborate, octyl pyridinium hexaflurophosphate and 1-octyl-3-methylimidazolium hexaflurophosphate) were applied to produce metal nanomaterials. Silver, platinium and palladium nanoparticles exhibit spherical morphology while nanosheets with high aspect ratio were obtained for gold. These metal nanostructures were incorporated into a carbon ionic liquid electrode to investigate their electrocatalytic properties. It was found that synthesis in different ionic liquids result in different activity. Excellent electrocatalytic effects toward adenine, hydrazine, formaldehyde and ethanol were observed for the modified electrodes with different nanoparticles synthesized in 1-butyl-3-methylimidazolium tetrafluoroborate. The high conductivity, large surface-to-volume ratio and active sites of nanosized metal particles are responsible for their electrocatalytic activity. In contrast, the carbon ionic liquid electrode modified with synthesized metal nanoparticles in octyl pyridinium hexaflurophosphate and 1-octyl-3-methylimidazolium hexaflurophosphate showed negligible activity for detection of these probes.

Synthesis of palladium nanoparticles on organically modified silica: application to design of a solid-state electrochemiluminescence sensor for highly sensitive determination of imipramine.

Organically modified silica substrate containing amine and vinyl functional groups were used for reduction and stabilization of palladium nanoparticles. Uniform spherical nanoparticles of palladium with average diameter of 10 nm were formed on silica substrate by direct contact of the substrate with an aqueous solution of palladium precursor, without the addition of any chemical reducer. Moreover, a sensitive and selective solid state electrochemiluminescence sensor was fabricated for the determination of imipramine, based on Ru(bpy)3(2+)-palladium nanoparticles doped carbon ionic liquid electrode. In this process, imipramine acts as a co-reactant for Ru(bpy)3(2+). It is believed that the enhancement of the electrochemiluminescence signal in the presence of palladium nanoparticles in the composite is due to palladium catalytic effect on electrochemical and also chemical process involved in formation of Ru(byp)3(2+)*. In addition, the results confirmed that, the rigid composite electrode shows the characteristic of microelectrode arrays. The proposed method was applied to the determination of imipramine in tablets and urine samples. The electrochemiluminescence intensity showed good linearity with the imipramine concentration from 1-100 pM, with a detection limit of 0.1 pM.

Chemometrics assisted resolving of net faradaic current contribution from total current in potential step and staircase cyclic voltammetry.

Total current in the electroanalytical data is assumed to be consisting of three main constituents: faradaic current, step charging current and induced charging current. Both charging currents can cause an interfering effect on precise determination of faradaic currents, and hence insert direct effects on sensitivity and detection limit of the electroanalytical techniques. Despite the widespread techniques introduced until now, the extraction of the net faradaic current from total current still remains a challenge. In this work, by using multivariate curve resolution-alternating least square (MCR-ALS) as a powerful curve resolution-based chemometrics method, a straightforward method has been introduced for resolving faradaic current from the two types of charging currents (step charging current and induced charging current) in single potential step and staircase cyclic voltammetric methods. By simultaneous analyses of the current data matrices for different electrochemical systems, the three sources of current were successfully identified and their contributions in the total signal were easily calculated. Also, in this manner, the cell time constant can be obtained easily. Contrary to the previously reported methods, the present method does not need any pre-determined mathematical method; particularly there is no need to know the cell time constant.

Synthesis of biologically stable gold nanoparticles using imidazolium-based amino acid ionic liquids.

A novel double-step reduction procedure for the synthesis of gold nanoparticles (AuNPs) using amino acid ionic liquids has been employed. 1-Dodecyl-3-methyl imidazolium tryptophan ([C(12)mim]Trp) and 1-ethyl-3-methyl imidazolium tryptophan ([C(2)mim]Trp) were used for this synthesis. The synthesized AuNPs were characterized by UV-vis spectroscopy, transmission electron microscopy and dynamic light scattering. The behavior of these AuNPs were also probed in a biological media. It was proven that AuNPs synthesized at [C(12)mim]Trp have more stability than AuNPs synthesized at [C(2)mim]Trp due to the longer alkyl chain of the imidazolium moiety. The solubility test shows that the resultant AuNPs have a hydrophilic nature. Finally, it was seen that due to the presence of a biomolecule, namely Trp, in the structure of AuNPs protecting shell, higher stability and biocompatibility was achieved in the biological media.

Highly efficient degradation of azo dyes by palladium/hydroxyapatite/Fe3O4 nanocatalyst.

Palladium/hydroxyapatite/Fe(3)O(4) (Pd/HAP/Fe(3)O(4)) nanocatalyst was synthesized and evaluated for its catalytic activity towards the degradation of azo dyes (methyl red, methyl orange and methyl yellow) selected as test dye species. The Pd/HAP/Fe(3)O(4) was employed as a novel catalyst that offers high catalytic activity, magnetic separateability and good stability. It was found that catalytic activity of this catalyst was significantly enhanced under acidic conditions. The degradation mechanism is proposed to be due to the reaction of Pd/HAP/Fe(3)O(4) with dissolved oxygen with the assistance of acid to form a Pd hydroperoxide, which oxidizes azo dyes under HAP catalysis. This in turn shows the clear importance of HAP as the support for the Pd nanocatalyst. The concentrations of dyes change exponentially with time and high rate constants were obtained for the degradation of these dyes. The pseudo-first-order equation was shown to fit degradation kinetics in most cases. Therefore, the Pd/HAP/Fe(3)O(4) nanostructures are considered as a highly efficient and promising catalyst in degradation systems and they can be effectively recovered after use.

Ion release from orthodontic brackets in 3 mouthwashes: an in-vitro study.

INTRODUCTION: Stainless steel orthodontic brackets can release metal ions into the saliva. Fluoridated mouthwashes are often recommended to orthodontic patients to reduce the risk of white-spot lesions around their brackets. However, little information is available regarding the effect of different mouthwashes in ion release of orthodontic brackets. The purpose of this study was to measure the amount of metal ion release from orthodontic brackets when kept in different mouthwashes. METHODS: One hundred sixty stainless steel brackets (0.022-in, 3M Unitek, Monrovia, Calif) were divided randomly into 4 equal groups and immersed in Oral B (Procter & Gamble, Weybridge, United Kingdom), chlorhexidine (Shahdaru Labratories, Tehran, Iran), and Persica (Poursina Pharmaceutical Laboratories, Tehran, Iran) mouthwashes and distilled deionized water and incubated at 37°C for 45 days. Nickel, chromium, iron, copper, and manganese released from the orthodontic brackets were measured with an inductively coupled plasma spectrometer. For statistical analysis, 1-way analysis of variance (ANOVA) and the Duncan multiple-range tests were used. RESULTS: The results showed that ion release in deionized water was significantly (P <0.05) higher than in the 3 mouthwashes. Higher ion release was found with chlorhexidine compared with the other 2 mouthwashes. There was no significant difference (P >0.05) in nickel, chromium, iron, and copper ion release in the Oral B and Persica mouthwashes. The level of manganese release was significantly different in all 4 groups. CONCLUSIONS: If ion release is a concern, Oral B and Persica mouthwashes might be better options than chlorhexidine for orthodontic patients with stainless steel brackets.

Metal paste nanocomposite electrodes as a new generation of metallic electrodes.

Fabrication of metal paste nanocomposite electrodes is introduced using metal nanostructures and ionic liquids. The combined application of unique properties of nanomaterials and ionic liquids in the design of these metal paste nanocomposites results in electrodes with interesting advantages compared to the conventional metal disk electrodes. In contrast to conventional metallic electrodes, which are usually prone to fouling effects and suffer from weak repeatability and reproducibility, these metal paste nanocomposite electrodes have very exciting advantages. Ease of electrode fabrication; cleaning and activating the electrode surface, together with high electrocatalytic activity; increased degree of active area and surface roughness; antifouling effect; good signal-to-noise ratio; low cost; and low weight are among the advantageous features of these electrodes. Compared to dropping mercury electrodes that have high toxicity, these metal paste nanocomposite electrodes have much less toxicity. Such abilities promote new opportunities for a wide range of electrochemical, sensing, and biosensing applications.

Construction of a carbon nanocomposite electrode based on amino acids functionalized gold nanoparticles for trace electrochemical detection of mercury.

A simple, highly sensitive and selective carbon nanocomposite electrode has been developed for the electrochemical trace determination of mercury. This mercury nanocomposite sensor was designed by incorporation of thiolated amino acids capped AuNps into the carbon ionic liquid electrode (CILE) which provides remarkably improved sensitivity and selectivity for the electrochemical stripping assay of Hg(II). Mercury ions are expected to interact with amino acids through cooperative metal-ligand interaction to form a stable complex which provides a sensitive approach for electrochemical detection of Hg(II) in the presence of other metal ions. The detection limit was found to be 2.3 nM (S/N = 3) that is lower than the permitted value of Hg(II) reported by the Environmental Protection Agency (EPA) limit of Hg(II) for drinkable water. The proposed nanocomposite electrode exhibits good applicability for monitoring Hg(II) in tap and waste water.

Electrodeposition of gold-platinum alloy nanoparticles on ionic liquid-chitosan composite film and its application in fabricating an amperometric cholesterol biosensor.

An electrodeposition method was applied to form gold-platinum (AuPt) alloy nanoparticles on the glassy carbon electrode (GCE) modified with a mixture of an ionic liquid (IL) and chitosan (Ch) (AuPt-Ch-IL/GCE). AuPt nanoparticles were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical methods. AuPt-Ch-IL/GCE electrocatalyzed the reduction of H(2)O(2) and thus was suitable for the preparation of biosensors. Cholesterol oxidase (ChOx) was then, immobilized on the surface of the electrode by cross-linking ChOx and chitosan through addition of glutaraldehyde (ChOx/AuPt-Ch-IL/GCE). The fabricated biosensor exhibited two wide linear ranges of responses to cholesterol in the concentration ranges of 0.05-6.2 mM and 6.2-11.2 mM. The sensitivity of the biosensor was 90.7 µA mM(-1) cm(-2) and the limit of detection was 10 µM of cholesterol. The response time was less than 7 s. The Michaelis-Menten constant (K(m)) was found as 0.24 mM. The effect of the addition of 1 mM ascorbic acid and glucose was tested on the amperometric response of 0.5 mM cholesterol and no change in response current of cholesterol was observed.

Single-walled carbon nanotubes as stationary phase in gas chromatographic separation and determination of argon, carbon dioxide and hydrogen.

A chromatographic technique is introduced based on single-walled carbon nanotubes (SWCNTs) as stationary phase for separation of Ar, CO(2) and H(2) at parts per million (ppm) levels. The efficiency of SWCNTs was compared with solid materials such as molecular sieve, charcoal, multi-walled carbon nanotubes and carbon nanofibers. The morphology of SWCNTs was optimized for maximum adsorption of H(2), CO(2) and Ar and minimum adsorption of gases such as N(2), O(2), CO and H(2)O vapour. To control temperature of the gas chromatography column, peltier cooler was used. Mixtures of Ar, CO(2) and H(2) were separated according to column temperature program. Relative standard deviation for nine replicate analyses of 0.2 mL H(2) containing 10 microL of each Ar or CO(2) was 2.5% for Ar, 2.8% for CO(2) and 3.6% for H(2). The interfering effects of CO, and O(2) were investigated. Working ranges were evaluated as 40-600 ppm for Ar, 30-850 ppm for CO(2) and 10-1200 ppm for H(2). Significant sensitivity, small relative standard deviation (RSD) and acceptable limit of detection (LOD) were obtained for each analyte, showing capability of SWCNTs for gas separation and determination processes. Finally, the method was used to evaluate the contents of CO(2) in air sample.

Development of a sensitive and selective Riboflavin sensor based on carbon ionic liquid electrode.

The electrochemical properties of Riboflavin adsorbed on carbon ionic liquid electrode (CILE) were studied by cyclic voltammetry. A film with a surface coverage of up to 3.3x10(-9) mol cm(-2) was formed after 10 min exposure time. Electron transfer coefficient and rate constant of electron transfer across the modified electrode were found to be 0.43 and 3.03 s(-1), respectively. Differential pulse voltammetry was used for the determination of Riboflavin. Two linear working ranges of 0.8-110 nM and 0.11-1.0 microM were obtained with correlation coefficients of 0.998 and 0.996, respectively. The experimental detection limit was obtained as 0.1 nM. The relative standard deviation for five replicate analyses was 4.7%. Other soluble vitamins had no significant interferences and the electrode was used for the determination of Riboflavin in pharmaceutical products, nutrition and beverages.

Hydrogen peroxide biosensor based on a myoglobin/hydrophilic room temperature ionic liquid film.

The composite film based on Nafion and hydrophilic room temperature ionic liquid (RTIL) 1-butyl-3-methyl-imidazolium chloride ([bmim]Cl) was used as an immobilization matrix to entrap myoglobin (Mb). The study of ionic liquid (IL)-Mb interaction by ultraviolet-visible (UV-vis) spectroscopy showed that Mb retains its native conformation in the presence of IL. The immobilized Mb displayed a pair of well-defined cyclic voltammetric peaks with a formal potential (E(o)(')) of -0.35 V in a 0.1 M phosphate buffer solution (PBS) of pH 7.0. The immobilized Mb exhibited excellent electrocatalytic response to the reduction of hydrogen peroxide, based on which a mediator-free amperometric biosensor for hydrogen peroxide was designed. The linear range for the determination of hydrogen peroxide was from 1.0 to 180 microM with a detection limit of 0.14 microM at a signal/noise ratio of 3. The apparent Michaelis constant (K(m)(app)) for the electrocatalytic reaction was 22.6 microM. The stability, repeatability, and selectivity of the sensor were evaluated. The proposed biosensor has a lower detection limit than many other IL-heme protein-based biosensors and is free from common interference in hydrogen peroxide biosensors.