Ultrasensitive optical detection of trinitrotoluene by ethylenediamine-capped gold nanoparticles

This study found that 1,2-ethylenediamine (EDA) as a primary amine could be modified onto the surface of citrate-stabilized gold nanoparticles (Au NPs), and the EDA-capped Au NPs were successfully used as an ultrasensitive optical probe for TNT detection. The strong donor–acceptor (D–A) interactions between EDA and trinitrotoluene (TNT) at the Au NP/solution interface induced significant aggregation of the EDA-capped Au NPs, and enabled to easily realize the direct colorimetric detection of ultratrace TNT. The results showed that such a color change was readily seen by the naked eye, and the colorimetric detection could be down to 400 pM level of TNT with excellent discrimination against other nitro compounds. UV–vis absorption spectroscopy was used to examine the TNT-induced changes in local surface plasmon resonance (LSPR) of EDA-capped Au NPs, and a new LSPR band at ca. 630 nm arose along with the addition of TNT, which produced a detection limit of TNT down to ca. 40 pM. Furthermore, dynamic light scattering measurements evidenced the ultratrace TNT-induced small changes in the size of the EDA-capped Au NPs, and realized the quick and accurate detection of TNT in 0.4 pM level. These results demonstrated the ultrahigh sensitivity of this optical probe for TNT detection. Moreover, this optical probe is sample, stable, low-cost, and these excellent properties make it quite promising for infield and rapid detection of TNT.     

Selective spectrophotometric determination of TNT in soil and water with dicyclohexylamine extraction

Contaminated land and groundwater remediation in military waste dumping sites often necessitates the use of simple, cost-effective, and rapid tests for detecting trinitrotoluene (TNT) residues in the field along with their dinitro-analogues. A simple, rapid, low-cost, and field-adaptable (on-site) colorimetric method was developed for quantifying TNT in the presence of RDX, PETN, picric acid, 2,4-DNT (dinitrotoluene), dinitrophenol, and dinitroaniline. Most commercialized methods for TNT assay-with the exception of Cold Regions Research and Engineering Laboratory of the U.S. Army (CRREL) method-use proprietary chemicals, and the color stability and intensity are highly dependent on the composition of the organic solution comprised of acetone or methanol. The developed colorimetric method is based on the extraction of TNT from water-acetone solution into an organic solvent mixture of dicyclohexylamine (DCHA)-isobutyl methyl ketone (IBMK) (10:1, v/v), filtration through a filter paper into a stoppered optical cell containing anhydrous sodium sulfate, and measurement of the absorbance of the organic extract at 531 nm after 5 min. The red-violet color of the extract was due to intermolecular charge-transfer (CT) between the electron attracting TNT and electron-donating DCHA, and the molar absorptivity for TNT in final organic solution was (1.16 ± 0.02) × 10⁴ L mol⁻¹ cm⁻¹.The R.S.D. of the slope of calibration line was 0.7%. The LOD of the method in the final organic phase was 0.38 μM TNT, and LOD values expressed on the basis of original soil TNT content were 0.5, 1.3, and 1.5 ppm (μg g⁻¹) for clay, loamy clay, and sandy soils, respectively. Unlike other spectrophotometric methods, the developed assay was basically tolerant to common cations and anions found in soil and water at 100-fold weight ratios, and to soil humic acids. Among a number of compounds that may be encountered in polynitro-explosive storage and waste reclaimation sites such as picric acid, dinitrophenol, 2,4-dinitrotoluene, dinitroaniline, RDX, PETN, and tetryl, only tetryl interfered with the developed TNT assay. Water tolerance and exploitability over a wide pH range were other superiorities over the CRREL method. The CT-complex was relatively stable, as the absorbance of the organic extract was not significantly influenced from the dilution of the water-acetone phase. Aside from the extractive-photometric procedure established for aqueous solutions, a simulated field colorimetric assay for TNT directly applicable to soil was also devised, based on direct color development in a 4:1 (v/v) acetone-dicyclohexylamine organic extract of soil at a liquid-to-solid ratio of 5 mL g⁻¹.     

Selective spectrophotometric determination of TNT using a dicyclohexylamine-based colorimetric sensor

Because of the extremely heterogeneous distribution of explosives in contaminated soils, on-site colorimetric methods are efficient tools to assess the nature and extent of contamination. To meet the need for rapid and low-cost chemical sensing of explosive traces or residues in soil and post-blast debris, a colorimetric absorption-based sensor for trinitrotoluene (TNT) determination has been developed. The charge-transfer (CT) reagent (dicyclohexylamine, DCHA) is entrapped in a polyvinylchloride (PVC) polymer matrix plasticised with dioctylphtalate (DOP), and moulded into a transparent sensor membrane sliced into test strips capable of sensing TNT showing an absorption maximum at 530 nm when placed in a 1-mm spectrophotometer cell. The sensor gave a linear absorption response to 5-50 mg L⁻¹ TNT solutions in 30% aqueous acetone with limit of detection (LOD): 3 mg L⁻¹. The sensor is only affected by tetryl, but not by RDX, pentaerythritoltetranitrate (PETN), dinitrotoluene (DNT), and picric acid. The proposed method was statistically validated for TNT assay against high performance liquid chromatography (HPLC) using a standard sample of Comp B. The developed sensor was relatively resistant to air and water, was of low-cost and high specificity, gave a rapid and reproducible response, and was suitable for field use of TNT determination in both dry and humid soil and groundwater with a portable colorimeter.     

Electrospun nanofiber based colorimetric probe for rapid detection of Fe in water

An imidazole derivative, 2-(2′-pyridyl)imidazole (PIMH), was developed as a colorimetric probe for the qualitative analysis of Fe²⁺ in aqueous solution. PIMH was then used to post-functionalize poly(vinylbenzyl chloride) (PVBC) nanofibers after electrospinning so as to afford a solid state colorimetric probe. Upon treatment with Fe²⁺ the probe displayed a distinctive color change both in liquid and solid platforms. The linear dynamic range for the colorimetric determination of Fe²⁺ was 0.0988–3.5 μg mL⁻¹. The ligand showed a high chromogenic selectivity for Fe²⁺ over other cations with a detection limit of 0.102 μg mL⁻¹ in solution (lower than the WHO drinking water guideline limit of 2 mg L⁻¹), and 2 μg mL⁻¹ in the solid state. The concentration of Fe²⁺ in a certified reference material (Iron, Ferrous, 1072) was found to be 2.39 ± 0.01 mg L⁻¹, which was comparable with the certified value of 2.44 ± 0.12 mg L⁻¹. Application of the probe to real samples spiked with Fe²⁺ achieved recoveries of over 97% confirming accuracy of the method and its potential for on-site monitoring.     

Spectrophotometric determination of cyclotrimethylenetrinitramine (RDX) in explosive mixtures and residues with the Berthelot reaction

On-site colorimetric methods are a valuable, cost-effective tool to assess the nature and extent of contamination in remediated sites and to enable on-site screening for police criminology laboratories. The existing colorimetric method for cyclotrimethylenetrinitramine (RDX) based on a Griess reaction suffers from the non-quantitative reduction to nitrite and from the unstable character of HNO₂ in acidic medium. Thus we propose a novel spectrophotometric RDX assay in explosive mixtures and residues, based on (Zn + HCl) reduction of RDX in a microwave oven, followed by neutralization of the reduction products to ammonia and low molecular-weight amines, and Berthelot reaction of these amine-compounds with phenol and hypochlorite in alkaline medium to give an intensely blue indophenol dye absorbing at 631 nm. The molar absorptivity and limit of detection (LOD) for RDX were (1.08 ± 0.04) × 10⁴ L mol⁻¹ cm⁻¹ and 0.18 mg L⁻¹, respectively. Application of the method to synthetic mixture solutions of RDX and trinitrotoluene (TNT) at varying proportions showed that there was minimal interference from TNT (which could be compensated for by dicyclohexylamine colorimetry), since the Berthelot reaction was essentially non-responsive to m-substituted anilines derived from TNT upon (Zn + HCl) reduction. The proposed method was successfully applied to military-purpose explosive mixtures of (RDX + inert matter) such as Comp A5, Comp C4, and Hexal P30, and to (RDX + TNT) mixtures such as Comp B. The molar absorptivity of RDX was much higher than that of either ammonium or nitrate; RDX could be effectively separated from ammonium and nitrate in soil mixtures, based on solubility differences. The Berthelot method for RDX was statistically validated using Comp B mixtures against standard HPLC equipped with a Hypersil C-18 column with (40% MeOH-60% H₂O) mobile phase, and against gas chromatography-thermal energy analysis (GC-TEA) system.     

Fabrication of a novel immunosensor using functionalized self-assembled monolayer for trace level detection of TNT by surface plasmon resonance

We have developed a new immunosensor based on self-assembly chemistry for highly sensitive and label-free detection of 2,4,6-trinitrotoluene (TNT) using surface plasmon resonance (SPR). A monolayer of amine terminated poly(ethylene glycol) hydrazinehydrochloride (PEG-NH₂) thiolate was constructed on an activated gold surface and immobilized with trinitrophenyl-β-alanine (TNPh-β-alanine) by amide coupling method. The binding interaction of a monoclonal anti-TNT Ab (M-TNT Ab) with TNPh-β-alanine immobilized thiolate monolayer surface was monitored and evaluated for detection of TNT based on the principle of indirect competitive immunoreaction. Here, the competition between the self-assembled TNT derivative and the TNT in solution for binding with antibody yields in the response signal that is inversely proportional to the concentration of TNT in the linear detection range. With the present immunoassay format, TNT could be detected in the concentration range from 0.008 ng/ml (8 ppt) to 30 ng/ml (30 ppb). The response time for an immunoreaction was 2 min and one immunocycle could be done with in 4 min including surface regeneration. Bound antibodies could be easily eluted from the self-assembled immunosurface at high recoveries (more than 100 cycles) using pepsin solution without any damage to the TNT derivatives immobilized on the surface. The compact self-assembled monolayer was highly stable and prevented the non-specific adsorption of proteins on the surface favoring error free measurement.     

Using unmodified Au nanoparticles as colorimetric probes for TNT based on their competitive reactions with melamine

Gold nanoparticles(Au NPs) can serve as visualized colorimetric probes for various targets and modification-free sensing strategies are preferred.The donor–acceptor interaction between the electron-rich melamine(MA) and the electron-deficient trinitrotoluene(TNT) allows formation of a supramolecule in aqueous solution.Melamine alone makes the initially individual reddish Au NPs aggregate into gray/blue Au NP assemblies due to melamine forming multiple ligand sites toward the Au NPs.Interestingly,the preformed supramolecule of MA–TNT disenables aggregation of the Au NPs.Therefore the unmodified Au NPs provide facile colorimetric probes for TNT detection in aqueous solution.Rapid identification of TNT is established by naked eye inspection.By using spectrophotometer tools,quantification of TNT is accomplished with a linear range of 80 mmol Là1to 1.2 mmol Là1and a limit of detection(LOD) of 27 mmol Là1.In contrast to previous strategy with surface-modified Au NPs,here a modification-free sensing strategy for TNT assay has been developed with greater convenience,rapidity,and cost-effectiveness.     

Surface plasmon resonance-based trace detection of small molecules by competitive and signal enhancement immunoreaction

A surface plasmon resonance (SPR)-immunosensor for detection of the low molecular weight compound 2,4-dinitorophenol (DNP) at ultra-low concentration has been developed. The sensor strategy is based on a competitive immunoreaction between DNP and a DNP-protein conjugate, namely DNP-bovine serum albumin conjugate (DNP-BSA). Anti-DNP monoclonal antibody was immobilized on a gold thin-film coated SPR-sensor chip by means of a chemical coupling process. DNP-BSA, on contact with the anti-DNP antibody immobilized SPR-immunosensor chip causes an increase in the resonance angle of the sensor chip. The optimum concentration of immobilized antibody on the SPR-sensor chip is 100 μg mL⁻¹. The SPR-immunosensor response for free DNP determination using the competitive immunoreaction had a response time of ca. 15 min. Using this method, DNP could be determined in the concentration range 1 ppt to 1 ppb. The SPR signal for ppt levels of DNP was enhanced by a factor of three by subsequently treating immuno-bound DNP-BSA with a secondary anti-DNP antibody.     

Chromium(III, VI) speciation analysis with preconcentration on a maleic acid-functionalized XAD sorbent

Chromium may exist in environmental waters as Cr(III) and Cr(IV), the latter being the toxic and carcinogenic form. Since atomic absorption spectrometry (AAS) and inductively coupled plasma atomic emission spectrometry can only yield information on total Cr concentration, a polymer resin bearing O,O-donor chelating groups such as the maleic acid-functionalized XAD(CO)CHCHCOOH resin was synthesized to selectively retain Cr(III) at pH 4.0-5.5. The dynamic breakthrough capacity of the resin for Cr(III) at pH 5.0 was 7.52 mg g⁻¹, and the preconcentration factor extended to 250-300. Chromium(III) in the presence of 250-fold Cr(VI)—which was not retained—could be effectively preconcentrated on the NH₄⁺-form of the resin and determined by AAS or diphenylcarbazide (DPC) spectrophotometry. When Cr(VI) was reduced to Cr(III) with Na₂SO₃ solution brought to pH 1 by the addition of 1 M H₂SO₄, and preconcentrated on the resin, total Cr could be determined. The developed method was validated with a blended coal sample CRM-1632. Since the adsorption behavior as a function of pH of possible interferent metal ions, e.g. Ni(II), Co(II), Cu(II), Cd(II), Zn(II), Pb(II) and Fe(III), was similar to that of Cr(III), selective elution of Cr(III) from the resin was realized using a mixture of 1 wt.% H₂O₂+1 M NH₃. The eluate containing Cr as chromate could be directly analyzed by diphenyl carbazide spectrophotometry without any adverse effect from the common interferents of this method, i.e. Fe(III), Cu(II) Hg(II), VO₃⁻, MoO₄²⁻ and WO₄²⁻. Various synthetic waste solutions typical of electroplating bath effluents containing Cr, Cu, Ni, Zn, Na, Ca, cyanide (and chemical oxidation demand (COD), achieved by glucose addition) were subjected to pretreatment procedures such as hypochlorite oxidation (of cyanide) and catalytic oxidation (of COD) with peroxodisulfate. Chromium determination gave satisfactory results. The combined column preconcentration—selective elution—diphenylcarbazide spectrophotometric determination was also successfully applied to the determination of Cr in artificial and real seawater.     

Homogeneous, unmodified gold nanoparticle-based colorimetric assay of hydrogen peroxide

An unmodified gold nanoparticle-based colorimetric assay system in homogeneous format has been developed using hydrogen peroxide (H₂O₂) as a model analyte. H₂O₂ is added to o-phenylenediamine/horseradish peroxidase solution, and allowed to react for 10 min. Then, unmodified gold nanoparticles that serve as “reaction indicators” are added to the reaction solution. The resulting mixture color changes dramatically from red to blue. The reason is that azoaniline, a horseradish peroxidase-catalyzed oxidation product, induces the nanoparticle aggregation. Using this approach, H₂O₂ can be semiquantitatively determined over the concentration range of ∼4 orders of magnitude by the naked eye. If the observed peak intensity at 420 nm is used for the construction of the calibration plot, hydrogen peroxide can be accurately determined down to concentration levels of 1.3 × 10⁻⁶ M. Compared with the conventional electrochemical protocol, this sensing system offers several important advantages: (1) ability to be monitored by the naked eye, (2) avoiding the need of surface modification of electrodes or gold nanoparticles and (3) detection in homogeneous solution. It is worthy of note that this efficient and convenient strategy is also suitable for the detection of other species, such as glucose and cholesterol.     

Analyte-induced photoreduction method for visual and colorimetric detection of tyrosine

A new method based on photochemical formation of silver nanoparticles (AgNPs) was developed for detection of tyrosine (Tyr). To selectively detect Tyr and to simplify the detection procedure, the photoactivity of Tyr was utilized to trigger the photochemical reduction in production of AgNPs. The drastic change of solution color caused by the surface plasmon resonance (SPR) absorption band of the formed AgNPs was used to extract the quantitative information of Tyr. This developed method is simple in detection, while both the sensitivity and selectivity are significant improved. Meanwhile, the solution color was changed from colorless to dark yellow after the formation of AgNPs, which allows a much higher sensitivity in visual identification when compared with the SPR band shifting technique commonly, used in conventional colorimetric methods. To optimize the detection system and to understand the mechanism in this proposed method, parameters such as irradiation time, intensity of light source, and the concentration of Tyr were systematically examined. Results indicated that these factors mainly affected the reaction rate of photoreduction. The morphologies of the formed AgNPs were similar, but with small differences in particle sizes. In the examination of selectivity, sixteen other amino acids were examined. Results indicated that only amino acids of tryptophan, cysteine and histidine are photoactive and possess potential interferences in analysis of Tyr. Quantitative studies indicated that a linear response up to 10 μM with a detection limit of 100 nM could be obtained. For visually detection, color change could be observed with a concentration as low as 500 nM of Tyr.     

Selective determination of melamine in milk samples using 3-mercapto-1-propanesulfonate-modified gold nanoparticles as colorimetric probe

A novel and sensitive colorimetric method for determination of melamine in milk samples was developed by a 3-mercapto-1-propanesulfonate-modified gold nanoparticles (MPS-GNPs) probe. Melamine molecule has multiple -NH₂ groups. These functional groups can interact with MPS to form strong hydrogen bonding and induce the aggregation of the MPS-GNPs, resulting in a dramatic color change from red to blue. Therefore, the concentration of melamine in milk samples can be quantitatively detected by the naked eyes or a UV-vis spectrometer. Moreover, investigations have revealed that the sensitivity of the detection could be clearly improved by adding NaCl to the modified GNPs solution, which leads to a more rapid color change in the NaCl-optimized GNPs system. It is worth noting that the absorption ratio (A₆₅₀/A₅₂₀) of the modified GNPs in the NaCl-optimized system exhibited a linear correlation with melamine concentration and the limit of detection is 8 nM, well below the safety limit (1 ppm for infant formula in China).     

Optimization of the photocatalytic activity of CdO + CdTiO3 coupled oxide thin films obtained by sol-gel technique

In the preparation of CdO + CdTiO₃ polycrystalline thin films by the sol-gel method, the optical, structural and crystalline properties, as well as the photocatalytic activity (PA) depends strongly on the sintering temperature (Ts) of the films and of the Ti/Cd ratio used in the precursor solution. In this work, CdO + CdTiO₃ thin films were prepared using a Ti/Cd constant ratio in the precursor solution. The films were sintered at six different Ts in the 450-550 °C range, in an open atmosphere. The structure of the films was characterized by X-ray diffraction and the PA was evaluated by the photobleaching of methylene blue in an aqueous solution using a UV-vis spectrometer. The relative intensity of the diffraction peaks associated with CdO and CdTiO₃, change with the Ts. The better photocatalytic activities were obtained for the films sintered at 490 °C and 550 °C. When the CdO was removed from the films by chemical etching the PA decreased, showing the importance of coupling both oxides.     

Colorimetric detection of potassium ions using aptamer-functionalized gold nanoparticles

Herein, a simple and novel colorimetric method for detection of potassium ions (K⁺) was developed. The colorimetric experiments revealed that upon the addition of K⁺, the conformation of anti-K⁺ aptamer in solution changed from random coil structure to compact rigid G-quadruplex one. This compact rigid G-quadruplex structure could not protect AuNPs against K⁺-induced aggregation, and thus the visible color change from wine-red to blue-purple could be observed by the naked eye. The linear range of the colorimetric aptasensor covered a large variation of K⁺ concentration from 5 nM to 1 μM and the detection limit of 5 nM was obtained. Moreover, this assay was able to detect K⁺ with high selectivity and had great potential applications.     

Label-free colorimetric sensing of ascorbic acid based on Fenton reaction with unmodified gold nanoparticle probes and multiple molecular logic gates

A label-free strategy based on Fenton reaction with unmodified gold nanoparticles (AuNPs) as probe is demonstrated for ascorbic acid (AA) sensing. AuNPs is stable in the presence of single stranded DNA (ssDNA) which prevents salt-induced aggregation of AuNPs in solution. The hydroxyl free radicals generated by Fenton reaction lead to ssDNA cleavage into different sequence fragments which induce aggregation of AuNPs to produce a red-to-blue color change. As an efficient biological antioxidant, AA could effectively scavenge free radicals to avoid the cleavage of ssDNA, so that it prevents color change of the AuNPs solution. Thus, the color change of AuNPs in the presence and absence of AA provides a new approach for the detection of AA. The absorbance ratio at two wavelengths, A₆₇₀/A₅₂₀, decreases linearly with AA content within 1–15 μM, giving rise to a detection limit of 0.3 μM and a RSD of 2.8% (10 μM). The color display of AuNPs solution makes it feasible for the estimation of AA content by naked eye visualization. Moreover, based on Fenton reaction and unmodified gold nanoparticles, a multiple logic gate system includes two logic operations, i.e., INHIBIT and NOR, has been designed with small molecules (AA, l-cysteine, glutathione) as inputs and the colorimetric changes of AuNPs solution as outputs.     

Ultrasensitive detection of TNT in soil, water, using enhanced electrogenerated chemiluminescence

The ultrasensitive detection of 2,4,6-trinitrotoluene (TNT) was accomplished on the basis of sandwich-type TNT immunoassay combined with electrogenerated chemiluminescence (ECL) technology. Biotinylated anti-TNT species were attached to the surface of 1-μm diameter streptavidin-coated magnetic beads (MB) and 10-μm diameter avidin-coated polystyrene microspheres/beads (PSB) pre-loaded with ECL labels (∼7 billion hydrophobic ruthenium(II) tris(2,2′-bipyridine) (Ru^II) molecules per bead) to form anti-TNT ↔ MB and anti-TNT ↔ PSB(Ru^II) conjugates, respectively. Sandwich-type PSB(Ru^II) ↔ anti-TNT < TNT > anti-TNT ↔ MB aggregates were formed when PSB(Ru^II) ↔ anti-TNT was mixed with anti-TNT ↔ MB conjugates in the presence of analyte TNT and 2.0% bovine serum albumin blocking agent. The newly formed aggregates were magnetically separated from the aqueous reaction media and dissolved in acetonitrile containing 0.10 M tri-n-propylamine ECL coreactant-0.055 M trifluoroacetic acid-0.10 M tetrabutylammonium tetrafluoroborate electrolyte. ECL as well as cyclic voltammetric measurements were carried out with a potential scan from 0 to 2.8 V vs Ag/Ag⁺, and the integrated ECL intensity was found to be linearly proportional to the analyte TNT concentration over the range of 0.10-1000 ppt (pg mL⁻¹). The limit of detection (≤0.10 ± 0.01 ppb) is about 600× lower as compared with the most sensitive TNT detection method in the literature, and the absolute detection limit in mass (∼0.1 pg) is only ∼0.5% of that from mass spectroscopy. The approach coupled with the standard addition method was applied to measure the TNT contaminations in soil and creek water samples collected from a military training base.     

Development and validation of HPLC method for determination of clotrimazole and its two degradation products in spray formulation

A novel simple isocratic HPLC method with UV detection for the determination of three compounds in spray solution (active component clotrimazole and two degradation products imidazole and (2-chlorophenyl)diphenylmethanol) using ibuprofen as an internal standard was developed and validated. The complications with different acido-basic properties of the analysed compounds in HPLC separation - while clotrimazole has pK_a 4.7, imidazole has pK_a 6.9 compared to relatively more acidic (2-chlorophenyl)diphenylmethanol - were finally overcome using a 3.5 μm Zorbax^® SB-Phenyl column (75 mm × 4.6 mm i.d., Agilent Technologies).The optimal mobile phase for separation of clotrimazole, degradation products imidazole and (2-chlorophenyl)diphenylmethanol and ibuprofen as internal standard consists of a mixture of acetonitrile and water (65:35, v/v) with pH* conditioned by phosphoric acid to 3.5. At a flow rate of 0.5 ml min⁻¹ and detection at 210 nm, the total time of analysis was less than 6 min.The method was applied for routine analysis (batch analysis and stability tests) in commercial spray solution.     

Selective determination of penicillamine by on-line vapor-phase generation combined with Fourier transform infrared spectrometry

In this work, an on-line system with vapor-phase generation (VPG) and Fourier transform infrared (FTIR) spectrometric detection has been developed as a direct and highly selective analytical technique for the assay of penicillamine (PA). Potassium iodate solution was injected into a reactor, heated at 75 °C, containing PA. The CO generated under these conditions was transported by means of N₂ gas carrier stream to an infrared gas cell and corresponding FTIR spectra were acquired in a continuous mode. The maximum absorbance of CO band at 2170 cm⁻¹, corrected by a baseline established between 2240 and 2000 cm⁻¹ at a nominal resolution of 2 cm⁻¹, was selected as a measurement criterion. Initially, the effect of different chemical, physical and spectroscopic parameters, such as concentration and volume of oxidant, pH, equilibrium time, reactor temperature, reactor volume, N₂ carrier flow rate and number of scans on the analytical signals were evaluated by using a short path length (10 cm) IR gas cell. At optimum experimental conditions, the method provided a relatively broad linear dynamic range of 4-380 mg L⁻¹, a limit of detection of 0.5 mg L⁻¹, a sampling frequency of 15 h⁻¹ and a relative standard deviation (R.S.D.) of 1.6%. Further, the method was successfully applied to the determination of PA in pharmaceutical formulations and results compared well with those obtained by a reference colorimetric method.     

Visual detection of melamine in milk products by label-free gold nanoparticles

A simple, rapid, field-portable colorimetric method for the detection of melamine based on melamine-induced color change of label-free gold nanoparticles (Au NPs) was developed in this study. Melamine can induced the aggregation of Au NPs and results in the color change from wine-red to purple, which provided a platform for rapid and field-portable colorimetric detection of melamine. The proposed method can be used to detect melamine in liquid milk and infant formula with a detection limit of 1.0 and 4.2 ppm, respectively, within 30 min by naked eyes observation without the aid of any advanced instrument and the need of any complex pretreatment, and detect as low as 0.15 ppm of melamine in liquid milk and 2.5 ppm of melamine in infant formula with UV-vis-spectroscopy. The proposed method is promising for on-site screening of melamine adulterant in milk products.     

2,2′-Bipyrimidine transition metal complexes: Synthesis, reaction chemistry and solid state structures

2,2′-Bipyrimidine metal complexes with Ti, Mo, Fe, Ru, Pt, Ag, and Cu transition metal atoms have been synthesized and structurally characterized. These molecules were prepared by following synthesis methodologies. The reaction of 2,2′-bipyrimidine (1; bipym) with {[Ti](μ-σ,π-CCSiMe₃)₂}AgOTf ([Ti] = (η⁵-C₅H₄SiMe₃)₂Ti, OTf = OSO₂CF₃) (2) in a 1:1 molar ratio gave [{[Ti](μ-σ,π-CCSiMe₃)₂}Ag(bipym)]OTf (3) which on further treatment with another equivalent of 2 produced [({[Ti](μ-σ,π-CCSiMe₃)₂}Ag)₂(μ-1,2,3,4-bipym)](OTf)₂ (4). As consequence thereof, the coordination number of Ag(I) was changed from 3 to 4. A platinum-bipym complex with two acetylide substituents was accessible by the gradual reaction of 1 with K₂[PtCl₄] (5) and two equivalents of HCCR (7a, R = SiMe₃; 7b, R = Fc; 7c, R = Rc; Fc = (η⁵-C₅H₄)(η⁵-C₅H₅)Fe; Rc = (η⁵-C₅H₄)(η⁵-C₅H₅)Ru) in di-iso-propylamine and in presence of [CuI]. Originating from cis-[(bipym)Pt(CCR)₂] (8a, R = SiMe₃; 8b, R = Fc; 8c, R = Rc) diverse multinuclear complexes with two, three or four different transition metals could be obtained. These are: [((CO)₄Mo)(μ-1,2,3,4-bipym)Pt(CCFc)₂] (10), [(AgClO₄)(μ-1,2,3,4-bipym){[Pt(μ-σ,π-CCFc)₂]AgOClO₃}] (12), [(McCC)₂Pt(μ-1,2,3,4-bipym)({[Ti](μ-σ,π-CCSiMe₃)₂}M)]X (15a, Mc = Fc, M = Cu, X = PF₆; 15b, Mc = Rc, M = Cu, X = PF₆; 15c, Mc = Fc, M = Ag, X = ClO₄), and [(McCC)₂Pt(μ-1,2,3,4-bipym)PtCl₂] (17). Like other organometallic Pt-Ag tweezer complexes, compound 12 decomposed to give FcCC-CCFc (13). During prolonged stirring of 15a and 15b, respectively, [(McCC)₂Pt(μ-1,2,3,4-bipym)({[Ti](μ-σ,π-CCSiMe₃)(μ-σ,π-CCH)}M)]X (15′a, M = Cu, X = PF₆; 15′b, M = Cu, X = PF₆) was formed.The structures of 8b, 8c, 15a′, and 15b′ in the solid state are reported. All complexes exhibit the anticipated planar dinuclear Pt-M structure (M = Pt, Cu, Ag) with the 2,2′-bipyrimidine unit in a μ-1,2,3,4-bridging mode.Electrochemical investigations were carried out with 8a, 8b, and 8c and show that no significant influence of R on the bipym redox potentials exists. The typical redox behavior for the bipym, ferrocene, ruthenocene units and platinum were observed.