Visual colorimetric sensor for nitroguanidine detection based on hydrogen bonding-induced aggregation of uric acid-functionalized gold nanoparticles.

A colorimetric assay is proposed for the quantification of nitroguanidine (NQ), based on triggering the aggregation of uric acid-modified gold nanoparticles (AuNPs@UA) by intermolecular hydrogen bonding interaction between uric acid (UA) and NQ. The red-to-purplish blue (lavender) color change of AuNPs@UA with increasing NQ concentrations could be perceived with the naked eye or detected by UV-vis spectrophotometry. The absorbance versus concentration correlation gave a linear calibration curve in the range of 0.6-3.2 mg L-1 NQ, with a correlation coefficient of 0.9995. The detection limit of the developed method was 0.063 mg L-1, lower than those of noble metal aggregation methods in the literature. The synthesized and modified AuNPs were characterized using UV-vis spectrophotometry, scanning transmission electron microscopy (STEM), dynamic light scattering (DLS), and Fourier transform infrared spectroscopy (FTIR). Some critical parameters such as modification conditions of AuNPs, UA concentration, solvent environment, pH, and reaction time were optimized for the proposed method. The non-interference of common explosives (i.e., nitroaromatic, nitramine, nitrate ester, insensitive and inorganic explosives), common soil and groundwater ions (Na+, K+, Ca2+, Mg2+, Cu2+, Fe2+, Fe3+, Cl-, NO3-, SO42-, CO32-, PO43-) and possible interfering compounds (used as camouflage agents for explosives; D-(+)-glucose, sweeteners, acetylsalicylic acid (aspirin), household powder detergents, and paracetamol) on the proposed method was demonstrated, proving that the procedure was fairly selective for NQ, due to special hydrogen bonding interactions between UA-functionalized AuNPs and NQ. Finally, the proposed spectrophotometric method was applied to NQ-contaminated soil, and the obtained results were statistically compared with those of the liquid chromatography-tandem mass spectrometric (LC-MS/MS) method in the literature.

Determination of ketamine using melamine-modified gold nanoparticles.

Ketamine is used in medicine because of its anaesthetic and antidepressant effects at low doses. Unfortunately, due to its narcotic effect when used at high doses, its abuse among young people is increasing. It is also one of the most common drugs used in rape. Therefore, there is a need for fast and inexpensive tests that can be performed on-site. With the advancement of nanotechnology, nanoparticle-based approaches have found their place in selective analyses as in many fields. In the developed method, firstly gold nanoparticles were modified with melamine (AuNPs@Mel). Under optimized conditions, hydrogen bonds formed between ketamine and AuNPs@Mel cause the red colour of AuNPs@Mel to shift to blue-purple (i.e. aggregation-induced surface plasmon absorption shift). The association between absorbance and concentration produced a calibration line (curve) having a linearity correlation coefficient of 0.9981 for ketamine concentrations ranging from 4.76 to 47.6 mg L-1. The detection limit of the proposed method was 1.5 mg L-1 and the RSD (relative standard deviation) values of concentrations were changed ranging from 5.2% to 8.2%. The intra-assay and inter-assay measurements using the suggested method resulted in coefficients of variation (CVs) of 5.7% and 8.5%, respectively. Scan transmission electron microscopy (STEM), UV-vis spectrophotometry and FTIR spectroscopy were used to characterize the synthesized and modified AuNPs. Additionally, the procedure was successfully carried out with some interference materials and a real sample of fetal bovine serum. Lastly, using the Student t-test and F tests, the suggested technique was compared to and confirmed against an LC-MS/MS procedure previously published.

Detection of nitric oxide radical and determination of its scavenging activity by antioxidants using spectrophotometric and spectrofluorometric methods.

Although reactive nitrogen species (RNS) may attack biomacromolecules and cause tissue damage when unbalanced by natural antioxidant defenses of the organism, they can also take part in cell signaling under different physiological states and defend against certain pathogens. Since there is a scarcity of analytical methods to detect radicalic NO and its scavengers, a functionalized gold nanoparticle-based spectrophotometric method and a spectrofluorometric method have been separately developed to test antioxidant activity toward scavenging of NO produced from sodium nitroprusside (SNP). The spectrophotometric method involves conversion of NO to nitrite, followed by the formation of an azo dye with 4-aminothiophenol (4-ATP)-modified gold nanoparticles (AuNPs) and N-(1-naphthyl)-ethylene diamine dichloride (NED) and its absorbance measurement at 565 nm. Calibration equations were established by taking the absorbance difference in the presence and absence of antioxidants. In the spectrofluorometric method, the excess of NO radicals, after being scavenged by thiol type antioxidants, caused a decrease in resorcinol fluorescence. The developed spectrophotometric method was applied to orange juice and its trolox equivalent (TE) antioxidant activity was found. By further applying the developed methods to real samples such as bovine serum albumin (BSA), fetal bovine serum (FBS), saliva and certain biomolecules, it is envisaged that these novel methods improving the selectivity of previous methods can be useful in human health and disease research associated with nitric oxide. The developed methods were compared and validated against the conventional Griess assay with Student t-test and F tests.

Determination of formaldehyde in textile dye and auxiliary chemicals with headspace gas chromatography-flame ionization detector.

Formaldehyde is a chemical used in many different industrial sectors and is classified as a carcinogen as well as causing allergic reactions. Due to the health effects of formaldehyde, which is widely used in textile dyes and auxiliary chemicals, its analysis in this type of matrices becomes important. In this study, in order to meet these requirements, formaldehyde was converted to oxime derivative by derivatization with o-(2,3,4,5,6-Pentafluorobenzyl)hydroxylamine hydrochloride. This derivative was successfully sampled with the headspace technique and analyzed with a gas chromatography-flame ionization detector (GC-FID). For the developed method, derivatization and salt effect parameters were investigated. For the method, the limit of detection (LOD) was found as 0.05 mg L-1 and real sample analyzes were made for different types of dyes used in the textile industry, and sodium naphthalene sulfoxylate formaldehyde. In addition, the developed method was validated with sodium naphthalene sulfoxylate formaldehyde against ISO 14184-1 method by applying student t-, F-tests and no difference was found in terms of accuracy and precision. Thus, the applicability of the developed method to dyes and auxiliary chemicals used in the textile industry was successfully demonstrated. This allows all quality control processes to be handled using only one method.

Colorimetric sensors and nanoprobes for characterizing antioxidant and energetic substances.

The development of analytical techniques for antioxidant compounds is important, because antioxidants that can inactivate reactive species and radicals are health-beneficial compounds, also used in the preservation of food and protection of almost every kind of organic substance from oxidation. Energetic substances include explosives, pyrotechnics, propellants and fuels, and their determination at bulk/trace levels is important for the safety and well-being of modern societies exposed to various security threats. Most of the time, in field/on site detection of these important analytes necessitates the use of colorimetric sensors and probes enabling naked-eye detection, or low-cost and easy-to-use fluorometric sensors. The use of nanosensors brings important advantages to this field of analytical chemistry due to their various physico-chemical advantages of increased surface area, surface plasmon resonance absorption of noble metal nanoparticles, and superior enzyme-mimic catalytic properties. Thus, this critical review focuses on the design strategies for colorimetric sensors and nanoprobes in characterizing antioxidant and energetic substances. In this regard, the main themes and properties in optical sensor design are defined and classified. Nanomaterial-based optical sensors/probes are discussed with respect to their mechanisms of operation, namely formation and growth of noble metal nanoparticles, their aggregation and disaggregation, displacement of active constituents by complexation or electrostatic interaction, miscellaneous mechanisms, and the choice of metallic oxide nanoparticles taking part in such formulations.

Magnetite nanoparticles-based hydroxyl radical scavenging activity assay of antioxidants using N, N-dimethyl-p-phenylenediamine probe.

Excessive amounts of reactive oxygen species (ROS), unless counterbalanced by antioxidants, can cause cellular damage under oxidative stress conditions; therefore, antioxidative defenses against ROS must be measured. With the development of nanotechnology, nanoparticles have found numerous applications in science, health, and industries. Magnetite nanoparticles (Fe 3 O 4 :MNPs) have attracted attention because of their peroxidase-like activity. In this study, hydroxyl radicals (•OH) generated by MNPs-catalyzed degradation of H 2 O 2 converted the N,N-dimethyl-p-phenylenediamine (DMPD) probe into its colored DMPD•+ radical cation, which gave an absorbance maximum at λ = 553 nm. In the presence of antioxidants, •OH was partly scavenged by antioxidants and produced less DMPD• + , causing a decrease in the 553 nm-absorbance. Antioxidant concentrations were calculated with the aid of absorbance differences between the reference and sample solutions. The linear working ranges and trolox equivalent antioxidant capacity coefficients of different classes of antioxidants were determined by applying the developed method. In addition, binary and ternary mixtures of antioxidants were tested to observe the additivity of absorbances of mixture constituents. The method was applied to real samples such as orange juice and green tea. Student t-test, F tests, and the Spearman's rank correlation coefficient were used for statistical comparisons.

Novel Spectroscopic and Electrochemical Sensors and Nanoprobes for the Characterization of Food and Biological Antioxidants.

Since an unbalanced excess of reactive oxygen/nitrogen species (ROS/RNS) causes various diseases, determination of antioxidants that can counter oxidative stress is important in food and biological analyses. Optical/electrochemical nanosensors have attracted attention in antioxidant activity (AOA) assessment because of their increased sensitivity and selectivity. Optical sensors offer advantages such as low cost, flexibility, remote control, speed, miniaturization and on-site/in situ analysis. Electrochemical sensors using noble metal nanoparticles on modified electrodes better catalyze bioelectrochemical reactions. We summarize the design principles of colorimetric sensors and nanoprobes for food antioxidants (including electron-transfer based and ROS/RNS scavenging assays) and important milestones contributed by our laboratory. We present novel sensors and nanoprobes together with their mechanisms and analytical performances. Our colorimetric sensors for AOA measurement made use of cupric-neocuproine and ferric-phenanthroline complexes immobilized on a Nafion membrane. We recently designed an optical oxidant/antioxidant sensor using N,N-dimethyl-p-phenylene diamine (DMPD) as probe, from which ROS produced colored DMPD-quinone cationic radicals electrostatically retained on a Nafion membrane. The attenuation of initial color by antioxidants enabled indirect AOA estimation. The surface plasmon resonance absorption of silver nanoparticles as a result of enlargement of citrate-reduced seed particles by antioxidant addition enabled a linear response of AOA. We determined biothiols with Ellman reagent-derivatized gold nanoparticles.

Indirect Determination of Pentaerythritol Tetranitrate (PETN) with a gold nanoparticles-based colorimetric sensor.

Pentaerythritol tetranitrate (PETN) is the nitrate ester of pentaerythritol, used as an energetic and filling material for military and civilian purposes and rarely for terrorist actions. As there is no reliable nano-colorimetric method for PETN assay, we developed an indirect method based on the determination of nitrite, obtained by reduction of nitrate derived from the alkaline hydrolysis of PETN with H2O2. We colorimetrically determined the final product, nitrite, by both conventional Griess reaction and a recently developed gold nanoparticle-4-aminothiophenol-N-(1-naphthyl)-ethylenediamine (AuNP-4-ATP+NED) method. Nitramines (RDX and HMX), if present, could be degraded by alkaline hydrolysis, without affecting PETN. The analytical performance characteristics of the developed assays as molar absorptivity (ε), limits of detection (LOD) and quantification (LOQ) were: ɛ=1.06×105 L mol-1 cm-1, LOD=0.03mgL-1 and LOQ=0.11mgL-1 for indirect Griess method; ɛ=1.9×104Lmol-1 cm-1; LOD=0.12mgL-1 and LOQ=0.4mgL-1 for AuNP-4-ATP+NED method. Both methods were applied to a 1:1 (w/w) mixture of PETN and TNT (corresponding to the composition of military explosive 'Pentolite'). In order to eliminate the interference from TNT, the Meisenheimer anion of TNT formed in alkaline medium was retained on a strongly basic anion exchange resin column. As PETN had a very low solubility in water, common soil ions could be eliminated by prewashing the sample with water, or in acetone-water mixtures, Ca2+, K+, Cl-, SO42-, and NO3- could be tolerated at equal (1:1) mass ratios. Soil nitrates and nitrites, at a mass ratio of 50:1, could be separated from PETN with the aid of their insolubilities in acetone and of their retention affinity toward a strongly basic anion-exchange resin. The developed method was statistically validated against a reference GC-MS method.

Electrochemical Determination of Food Preservative Nitrite with Gold Nanoparticles/p-Aminothiophenol-Modified Gold Electrode.

Due to the negative impact of nitrate and nitrite on human health, their presence exceeding acceptable levels is not desired in foodstuffs. Thus, nitrite determination at low concentrations is a major challenge in electroanalytical chemistry, which can be achieved by fast, cheap, and safe electrochemical sensors. In this work, the working electrode (Au) was functionalized with p-aminothiophenol (p-ATP) and modified with gold nanoparticles (Au-NPs) to manufacture the final (Au/p-ATP-Aunano) electrode in a two-step procedure. In the first step, p-ATP was electropolymerized on the electrode surface to obtain a polyaminothiophenol (PATP) coating. In the second step, Au/p-ATP-Aunano working electrode was prepared by coating the surface with the use of HAuCl4 solution and cyclic voltammetry. Determination of aqueous nitrite samples was performed with the proposed electrode (Au/p-ATP-Aunano) using square wave voltammetry (SWV) in pH 4 buffer medium. Characteristic peak potential of nitrite samples was 0.76 V, and linear calibration curves of current intensity versus concentration was linear in the range of 0.5-50 mg·L(-1) nitrite with a limit of detection (LOD) of 0.12 mg·L(-1). Alternatively, nitrite in sausage samples could be colorimetrically determined with high sensitivity by means of p-ATP‒modified gold nanoparticles (AuNPs) and naphthylethylene diamine as coupling agents for azo-dye formation due to enhanced charge-transfer interactions with the AuNPs surface. The slopes of the calibration lines in pure NO2(-) solution and in sausage sample solution, to which different concentrations of NO2(-) standards were added, were not significantly different from each other, confirming the robustness and interference tolerance of the method. The proposed voltammetric sensing method was validated against the colorimetric nanosensing method in sausage samples.

Determination of triacetone triperoxide with a N,N-dimethyl-p-phenylenediamine sensor on nafion using Fe3O4 magnetic nanoparticles.

The explosive triacetone triperoxide (TATP) can be easily manufactured from readily accessible reagents and is extremely difficult to detect, owing to the lack of UV absorbance, fluorescence, or facile ionization. The developed method is based on the acidic hydrolysis of TATP into H2O2, pH adjustment to 3.6, and the addition of magnetite nanoparticles (Fe3O4 MNPs) to the medium to produce hydroxyl radicals from H2O2, owing to the peroxidase-like activity of MNPs. The formed radicals converted the N,N-dimethyl-p-phenylenediamine (DMPD) probe to the colored DMPD(+) radical cation, the optical absorbance of which was measured at a wavelength of 554 nm. The molar absorptivity (ε) of the method for TATP was 21.06 × 10(3) L mol(-1) cm(-1). The colored DMPD(+) product in solution could be completely retained on a cation-exchanger Nafion membrane, constituting a colorimetric sensor for TATP and increasing the analytical sensitivity. The proposed method did not respond to a number of hand luggage items like detergent, sweetener, sugar, acetylsalicylic acid (aspirin), and paracetamol-caffeine-based analgesic drugs. On the other hand, TATP could be almost quantitatively recovered from a household detergent and sweetener that can be used as camouflage for the analyte. Neither common soil and groundwater ions (e.g., Ca(2+), Mg(2+), K(+), Cl(-), SO4(2-), and NO3(-)) at 100-fold ratios nor nitro-explosives of trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and pentaerythritol tetranitrate (PETN) at 10-fold amounts interfered with the proposed assay. The method was statistically validated against the standard GC/MS reference method.

4-Aminothiophenol functionalized gold nanoparticle-based colorimetric sensor for the determination of nitramine energetic materials.

The heterocyclic nitramine compounds, hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), are two most important military-purpose high explosives. Differentiation of RDX and HMX with colorimetric methods of determination has not yet been made because of their similar chemical structures. In this study, a sensitive colorimetric method for the determination of RDX and HMX was proposed on the basis of differential kinetics in the hydrolysis of the two compounds (yielding nitrite as a product) followed by their colorimetric determination using 4-aminothiophenol (4-ATP) modified gold nanoparticles (AuNPs) and naphthylethylene diamine (NED) as coupling agent for azo-dye formation, abbreviated as "4-ATP-AuNP+NED" colorimetric method. After alkaline hydrolysis in a 1 M Na2CO3 + 0.04 M NaOH mixture solution at room temperature, only RDX (but not HMX) was hydrolyzed to give a sufficient colorimetric response in neutralized solution, the molar absorptivity (ε) at 565 nm and the limit of detection (LOD) for RDX being (17.6 ± 1.3) × 10(3) L mol(-1) cm(-1) and 0.55 µg mL(-1), respectively. On the other hand, hot water bath (at 60 °C) hydrolysis enabled both nitramines, RDX and HMX, to give substantial colorimetric responses; i.e., ε and LOD for RDX were (32.8 ± 0.5) × 10(3) L mol(-1)cm(-1) and 0.20 µg mL(-1) and for HMX were (37.1 ± 2.8) × 10(3) L mol(-1)cm(-1) and 0.24 µg mL(-1), respectively. Unlike other AuNP-based nitrite sensors in the literature showing absorbance quenching within a relatively narrow concentration range, the developed sensor operated with an absorbance increase over a wide range of nitrite. Synthetic mixtures of (RDX + HMX) gave additive responses, and the proposed method was statistically validated against HPLC using nitramine mixtures.

Spectrophotometric and chromatographic determination of insensitive energetic materials: HNS and NTO, in the presence of sensitive nitro-explosives.

As there are no molecular spectroscopic determination methods for the most widely used insensitive energetic materials, 2,2',4,4',6,6'-hexanitrostilbene (HNS) and 3-nitro-1,2,4-triazole-5-one (NTO), in the presence of sensitive nitro-explosives, two novel spectrophotometric methods were developed. For HNS and TNT mixtures, both analytes react with dicyclohexylamine (DCHA) forming different colored charge-transfer complexes, which can be resolved by derivative spectroscopy. The spectrophotometric method for NTO measures the 416-nm absorbance of its yellow-colored Na(+)NTO(-) salt formed with NaOH. TNT, if present, is pre-extracted into IBMK as its Meisenheimer anion forming an ion-pair with the cationic surfactant cetyl pyridinium (CP(+)) in alkaline medium, whereas the unextracted NTO is determined in the aqueous phase. The molar absorptivity (ε, L mol(-1)cm(-1)) and limit of quantification (LOQ, mg L(-1)) are as follows: for HNS, ε=2.75 × 10(4) and LOQ=0.48 (in admixture with TNT); for NTO, ε=6.83 × 10(3) and LOQ=0.73. These methods were not affected from nitramines and nitrate esters in synthetic mixtures or composite explosives. The developed methods were statistically validated against HPLC, and the existing chromatographic method was modified so as to enable NTO determination in the presence of TNT. These simple, low-cost, and versatile methods can be used in criminology, remediation/monitoring of contaminated sites, and kinetic stability modeling of munitions containing desensitized energetic materials.

Determination of peroxide-based explosives with copper(II)-neocuproine assay combined with a molecular spectroscopic sensor.

The two members of peroxide-based explosives, triacetone triperoxide (TATP) and hexamethylene triperoxide diamine (HMTD), can be manufactured from readily accessible reagents, and are difficult to detect by conventional analytical methods. TATP and HMTD were securely synthesized, taken up with acetone, hydrolyzed with 4 M HCl to hydrogen peroxide, the acidic solution containing H(2)O(2) was neutralized, and assayed by the copper(II)-neocuproine spectrophotometric method. The chromophore of the reaction was the Cu(I)-neocuproine chelate responsible for light absorption at 454 nm. The molar absorptivity (epsilon) of the method for TATP and HMTD was 3.45 x 10(4) and 4.68 x 10(4) L mol(-1) cm(-1), respectively. The TATP recovery from a synthetically contaminated loamy clay soil was 91-99%. The colorimetric method was also applied to a Cu(ii)-neocuproine-impregnated polymeric Nafion membrane sensor developed for the first time in this work for peroxide explosive assay. The absorbance-concentration response was perfectly linear, and the limit of detection (LOD) of the procedure for both TATP and HMTD was approximately 0.2 mg L(-1). Neither common soil ions (Ca(2+), K(+), Cl(-), SO(4)(2-), Mg(2+) and NO(3)(-)) at 100-fold amounts nor military-purpose nitro-explosives of TNT, RDX, and PETN at 10-fold amounts interfered with the proposed assay. Active oxygen constituents of laundry detergents (perborates and percarbonates), which normally interfered with the assay, could easily be separated from the analytes by solubility differences. The method was statistically validated against standard reference methods of TiOSO(4) colorimetry and GC-MS.