Green Downscaling of Solvent Extractive Determination Employing Coconut Oil as Natural Solvent with Smartphone Colorimetric Detection: Demonstrating the Concept via Cu(II) Assay Using 1,5-Diphenylcarbazide.

Coconut oil as a natural solvent is proposed for green downscaling solvent extractive determination. Determination of Cu(II) using 1,5-Diphenylcarbazide (DPC) was selected as a model for the investigation. Cu(II)-DPC complexes in aqueous solution were transferred into coconut oil phase. The change of the color due to Cu(II)-DPC complexes in coconut oil was followed by using a smartphone and image processing. A single standard concept was used for a series of Cu(II) standard solutions. A downscaling procedure using a 2 mL vial provided a calibration: color intensity = -142 [Cu(II)] + 222, (R2 = 0.98), 10% RSD. Using a well plate, a calibration was: color intensity = 61 [Cu(II)] + 68 (R2 = 0.91), 15% RSD. Both were for the range of 0-1 ppm Cu(II). Application of the developed procedure to water samples was demonstrated. The developed procedures provided a new approach of green chemical analysis.

A Robust Flow-Based System for the Spectrophotometric Determination of Cr(VI) in Recreational Waters.

A flow-based method for the spectrophotometric determination of chromium (VI) in recreational waters with different salinities was developed. Chromium can occur in the environment in different oxidation states with different related physiological properties. With regard to chromium, the speciation is particularly important, as the hexavalent chromium is considered to be carcinogenic. To achieve that purpose, the use of the diphenylcarbazide (DPC) selective colored reaction with the hexavalent chromium was the chosen strategy. The main objective was to develop a direct and simple spectrophotometric method that could cope with the analysis of different types of environmental waters, within different salinity ranges (fresh to marine waters). The potential interference of metal ions, that can usually be present in environmental waters, was assessed and no significant interferences were observed (<10%). For a complete Cr(VI) determination (three replicas) cycle, the corresponding reagents consumption was 75 µg of DPC, 9 mg of ethanol and 54 mg of sulfuric acid. Each cycle takes about 5 min, including the system clean-up. The limit of detection was 6.9 and 12.2 µg L−1 for waters with low and high salt content, respectively. The method was applied for the quantification of chromium (VI) in both fresh and marine water, and the results were in agreement with the reference procedure.

New method for hydrogel synthesis from diphenylcarbazide chitosan for selective copper removal.

In this work, a simple method was developed for hydrogel preparation from 1,5-Diphenylcarbazide (DPC) and chitosan (CS) through Diazotization reaction of CS as a selective adsorbent (DPCCS) for Cu(II) ions. CS was treated with sodium nitrate and subsequent crosslinking reaction with DPC for the preparation of DPCCS. Different techniques were used for characterization of DPCCS. Various parameters such as, temperature, pH, and concentration of Cu(II) were used for adsorption studies. Kinetics of Cu(II) ion on DPCCS follows the Pseudo second order and equilibrium of adsorption occurs in short time. The equilibrium data was best fitted with the Langmuir isotherm and the maximum adsorption capacity of DPCCS was 185.505 mg g-1. Thermodynamic parameters ΔG°, ΔH° and ΔS° suggested that the adsorption of Cu(II) ion on the surfaces of DPCCS was spontaneous, endothermic and randomness of Cu(II) ion in the solution was enhanced respectively. Regeneration of DPCCS and Cu(II) ion recovery were studied up to five cycles without the lost of the adsorption capacity.

Chromium Monitoring in Water by Colorimetry Using Optimised 1,5-Diphenylcarbazide Method.

Chromium contamination of drinking water has become a global problem due to its extensive use in industry. The most commonly used methods for chromium detection in water are laboratory-based methods, such as atomic absorption spectroscopy and mass spectroscopy. Although these methods are highly selective and sensitive, they require expensive maintenance and highly trained staff. Therefore, there is a growing demand for cost effective and portable detection methods that would meet the demand for mass monitoring. Microfluidic detection systems based on optical detection have great potential for onsite monitoring applications. Furthermore, their small size enables rapid sample throughput and minimises both reagent consumption and waste generation. In contrast to standard laboratory methods, there is also no requirement for sample transport and storage. The aim of this study is to optimise a colorimetric method based on 1,5-diphenylcarbazide dye for incorporation into a microfluidic detection system. Rapid colour development was observed after the addition of the dye and samples were measured at 543 nm. Beer's law was obeyed in the range between 0.03-3 mg·L-1. The detection limit and quantitation limit were found to be 0.023 and 0.076 mg·L-1, respectively.

FIA-coupled spectrophotometric method for determination of Cr (VI) traces in natural waters: application of in-line dissolution of 1,5-diphenylcarbazide after heat treatment and activated alumina as adsorbent for preconcentration.

This work proposes the quantification of Cr (VI) ions in natural waters in trace level, using activated alumina (Al2O3) as preconcentration support, controlled in-line dissolution of the solidified chromophore diphenylcarbazide after heat treatment and spectrophotometric detection. The manifold ensures high sensitivity of analytical response, good repeatability, and stability. In this work, optimization of experimental conditions of a flow injection system was chosen as the parameters for greater sensitivity and better selectivity. The selected optimized conditions were 0.30 mol L-1 for H2SO4 concentration, system flow rate as 0.40 mL min-1, sample injection volume of 192.50 µL, 2 min for preconcentration time, and 0.10 mol L-1 for eluent concentration. The analytical curves obtained for real sample analysis show linear range from 0.192 to 0.961 µM, linear correlation coefficient R = 0.9997 and LOD = 0.024 µM. The preconcentration factor of about four times was obtained through the passage of 800 µL of a standard solution containing 0.961 µM of Cr (VI) through mini-column of preconcentration followed by elution at 192.5 µL of NH4OH 0.1 mol L-1 solution. The solid chromogenic reagent presented high durability (weeks in daily use with mass of 0.0993 g) and good reproducibility in analytical signal. The reactivation of the mini-column of alumina should be executed after ten injections of eluent, using 800 µL of HCl 0.02 mol L-1 solution in flow through the same. Each cycle of injection and elution of the sample takes about 5 min on the proposed terms. Despite the length of each cycle still be high, low concentrations can be detected using a technique of relatively low cost. This is due in part, the association dissolution of the chromogenic reagent directly in the line and the preconcentration step. Another important factor is the economy of reagent chromogenic, low generation of reject contributing to better quality of the environment, and the high potential for applications to work in field.

Comparative performance of novel magnetic ion-imprinted adsorbents employed for Cd2+, Cu2+ and Ni2+ removal from aqueous solutions.

Novel magnetic ion-imprinted polymer was prepared by use of SBA-15 as functional monomer, ethylene glycol dimethacrylate as cross linker, diphenylcarbazide as ligand, and Cd2+, Cu2+, and Ni2+ as the template of ion source. The adsorption capacity of the synthesized adsorbent was 111, 95, and 87 mg g-1, respectively for cadmium, copper, and nickel. The selectivity of the adsorbents examined in the presence of different cations including Na+, K+, Ca2+, Mg2+, Zn2+, Co2+, Fe2+, Mn2+, Hg2+, and Pb2+ indicated that the synthesized ion-imprinted adsorbents were highly selective for the appropriate cations. Kinetic studies indicated that the adsorption process was very fast and the equilibrium was established within 5 min and followed the pseudo-second-order kinetic model. The used ion-imprinted adsorbent was readily regenerated by elution with 2 M HNO3, and the regenerated adsorbent retained most of its initial capacity. The calculated thermodynamic parameters indicated that the adsorption process was spontaneous and endothermic.

False-positive result when a diphenylcarbazide spot test is used on trivalent chromium-passivated zinc surfaces.

BACKGROUND: A colorimetric 1,5-diphenylcarbazide (DPC)-based spot test can be used to identify hexavalent chromium on various metallic and leather surfaces. DPC testing on trivalent chromium-passivated zinc surfaces has unexpectedly given positive results in some cases, apparently indicating the presence of hexavalent chromium; however, the presence of hexavalent chromium has never been confirmed with more sensitive and accurate test methods. OBJECTIVES: To examine the presence of hexavalent chromium on trivalent chromium-passivated zinc surfaces with a DPC-based spot test. METHODS: A colorimetric DPC spot test was used for the initial detection of hexavalent chromium on new and 1-year-aged trivalent chromium-passivated zinc surfaces. Then, X-ray photoelectron spectroscopy (XPS) was performed for all samples. RESULTS: The DPC spot test indicated the presence of hexavalent chromium in aged, but not new, trivalent chromium passivation on zinc; however, subsequent analysis by XPS could not confirm the presence of chromium in a hexavalent state. CONCLUSIONS: Unintended oxidation of DPC induced by atmospheric corrosion is suggested as a possible reason for the false-positive reaction of the DPC test on a trivalent chromium-passivated zinc surface. Further validation of the use of the DPC test for chromium-containing metallic surfaces is required.

Cloud point extraction and diffuse reflectance-Fourier transform infrared spectroscopic determination of chromium(VI): A probe to adulteration in food stuffs.

A new cloud point extraction (CPE) method for the determination of hexavalent chromium i.e. Cr(VI) in food samples is established with subsequent diffuse reflectance-Fourier transform infrared (DRS-FTIR) analysis. The method demonstrates enrichment of Cr(VI) after its complexation with 1,5-diphenylcarbazide. The reddish-violet complex formed showed λmax at 540nm. Micellar phase separation at cloud point temperature of non-ionic surfactant, Triton X-100 occurred and complex was entrapped in surfactant and analyzed using DRS-FTIR. Under optimized conditions, the limit of detection (LOD) and quantification (LOQ) were 1.22 and 4.02µgmL-1, respectively. Excellent linearity with correlation coefficient value of 0.94 was found for the concentration range of 1-100µgmL-1. At 10µgmL-1 the standard deviation for 7 replicate measurements was found to be 0.11µgmL-1. The method was successfully applied to commercially marketed food stuffs, and good recoveries (81-112%) were obtained by spiking the real samples.

Chromium(III) and chromium(VI) release from leather during 8 months of simulated use.

BACKGROUND: Chromium (Cr) release from Cr-tanned leather articles is a major cause of Cr contact dermatitis. It has been suggested that Cr(VI) release from leather is not necessarily an intrinsic property of the leather, but is strongly dependent on environmental conditions. OBJECTIVES: To test this hypothesis for long-term (8 months) simulated use. MATERIALS AND METHODS: The release of total Cr and Cr(VI) from Cr-tanned, unfinished leather was analysed in subsequent phosphate buffer (pH 8.0) immersions for a period of 7.5 months. The effect of combined ultraviolet treatment and alkaline solution (pH 12.1) was tested. Dry storage [20% relative humidity (RH)] was maintained between immersions. Atomic absorption spectroscopy, X-ray fluorescence and diphenylcarbazide tests were used. RESULTS: Cr(VI) release was dependent on previous dry storage or alkaline treatment, but not on duration or number of previous immersions. Cr(III) release decreased with time. Fifty-two percent of the total Cr released during the last immersion period was Cr(VI). Cr(VI) release exceeded 9 mg/kg in all immersion periods except in the first 10-day immersion (2.6 mg/kg). CONCLUSIONS: Cr(VI) release is primarily determined by environmental factors (RH prior to immersion, solution pH, and antioxidant content). The RH should be kept low prior to testing Cr(VI) release from leather.

Nitrite interference and elimination in diphenylcarbazide (DPCI) spectrophotometric determination of hexavalent chromium.

Cr(VI) is highly noted as a carcinogenic, mutagenic, and teratogenic pollutant. However, accurate determination of Cr(VI) in aqueous samples is difficult using the conventional diphenylcarbazide (DPCI) spectrophotometric method upon being interfered by co-existed nitrite. This paper illustrates how to eliminate the nitrite influence in a simple but efficient method based on a detailed analysis of interference mechanism. High-performance liquid chromatography analysis revealed that under acidic condition, DPCI was oxidized by nitrite to other substrates, which could not react with Cr(VI). The final oxidation product of DPCI was further purified by thin-layer chromatography and identified as diaryl carbodiazone by Fourier Transform Ion Cyclotron Resonance-Mass Spectrometry (FTICR-MS) and nuclear magnetic resonance. Consequently, an improved method was proposed by simply adding sulfamic acid for eliminating the nitrite interference in Cr(VI) determination. The proposed method was successfully confirmed by the accurate recovery of Cr(VI) from spiked water samples and further proven with inductively coupled plasma-atomic emission spectroscopy, which demonstrated a great potential for determining Cr(VI) concentration in aqueous samples containing nitrite.

Chromium(VI) release from leather and metals can be detected with a diphenylcarbazide spot test.

BACKGROUND: Along with chromium, nickel and cobalt are the clinically most important metal allergens. However, unlike for nickel and cobalt, there is no validated colorimetric spot test that detects chromium. Such a test could help both clinicians and their patients with chromium dermatitis to identify culprit exposures. OBJECTIVES: To evaluate the use of diphenylcarbazide (DPC) as a spot test reagent for the identification of chromium(VI) release. METHODS: A colorimetric chromium(VI) spot test based on DPC was prepared and used on different items from small market surveys. RESULTS: The DPC spot test was able to identify chromium(VI) release at 0.5 ppm without interference from other pure metals, alloys, or leather. A market survey using the test showed no chromium(VI) release from work tools (0/100). However, chromium(VI) release from metal screws (7/60), one earring (1/50), leather shoes (4/100) and leather gloves (6/11) was observed. We found no false-positive test reactions. Confirmatory testing was performed with X-ray fluorescence (XRF) and spectrophotometrically on extraction fluids. CONCLUSIONS: The use of DPC as a colorimetric spot test reagent appears to be a good and valid test method for detecting the release of chromium(VI) ions from leather and metal articles. The spot test has the potential to become a valuable screening tool.

Evaluation of bacterial biosensors to determine chromate bioavailability and to assess ecotoxicity of soils.

Chromate can be considered a potent environmental contaminant and consequently, an understanding of chromate availability and toxicity to soil biology is essential for effective ecological assessment of metal impact in soils. This study shows the response of two bacterial bioreporters, pCHRGFP1 Escherichiacoli and pCHRGFP2 Ochrobactrumtritici, to increasing concentrations of chromate in two different soils. The bioreporters, carrying the regulatory gene chrB transcriptionally fused to the gfp reporter system, exhibited different features. In both, the fluorescence signal and the chromate concentration could be linearly correlated but E. coli biosensor functioned within the range of 0.5-2 µM and O. tritici biosensor within 2-10 µM chromate. The bioreporters were validated through comparative measurements using the chemical chromate methods of diphenylcarbazide and ionic chromatography. The bacterial sensors were used for the estimation of bioavailable fraction of chromate in a natural soil and OECD artificial soil, both spiked with chromate in increasing concentrations of 0-120 mg Cr(VI) kg(-1) of soil. OECD soil showed a faster chromate decrease comparing to the natural soil. The toxicity of soils amended with chromate was also evaluated by ecotoxicological tests through collembolan reproduction tests using Folsomia candida as test organism. Significant correlations were found between collembolans reproduction and chromate concentration in soil (lower at high chromate concentrations) measured by biosensors. Data obtained showed that the biosensors tested are sensitive to chromate presence in soil and may constitute a rapid and efficient method to measure chromate availability in soils.

Confirmation of hydroxyl radicals (•OH) generated in the presence of TiO2 supported on AC under microwave irradiation.

In order to study the degradation mechanism of technology of microwave (MW) combined with TiO2 supported on activated carbon (TiO2/AC), the reactive oxygen species (ROS) was explored through oxidation of 1,5-diphenyl carbazide (DPCI) to 1,5-diphenyl carbazone (DPCO). Furthermore, 2,6-di-tert-butyl-4-methylphenol (BHT), Mannitol (MT) and Vitamin C (VC) were used as radical scavengers to confirm the generation of the hydroxyl radicals ((•)OH). In addition, the influence of some parameters such as TiO2 mass ratio content, irradiation time, material dose, DPCI concentration and MW power on the determination of (•)OH were examined. The results showed that the (•)OH could be generated under MW combined with loaded TiO2/AC. Also, anatase TiO2/AC can generate more (•)OH radicals than rutile TiO2/AC under MW irradiation. This work would provide new mechanistic insights on the enhanced degradation effect of organic pollutants in water using the supported TiO2/AC coupled with MW technology.

Requirement for Asn298 on D1 protein for oxygen evolution: analyses by exhaustive amino acid substitution in the green alga Chlamydomonas reinhardtii.

PSII generates strong oxidants used for water oxidation. The secondary electron donor, Y(Z), is Tyr161 on PSII reaction center D1 protein and mediates electron transfer from the oxygen-evolving Mn(4)CaO(5) cluster to the primary electron donor, P680. The latest PSII crystal structure revealed the presence of a hydrogen bond network around Y(Z), which is anticipated to play important roles in the electron and proton transfer reactions. Y(Z) forms a hydrogen bond with His190 which in turn forms a hydrogen bond with Asn298 on D1 protein. Although functional roles of Y(Z) and His190 have already been characterized, little is known about the functional role of Asn298. Here we have generated 19 mutants from a green alga Chlamydomonas reinhardtii, in which the Asn298 has been substituted by each of the other 19 amino acid residues. All mutants showed significantly impaired or no photosynthetic growth. Seven mutants capable of photosynthetic growth showed oxygen-evolving activity although at a significantly reduced rate. Interestingly the oxygen-evolving activity of these mutants was markedly photosensitive. The 19 mutants accumulated PSII at variable levels and showed a light-induced electron transfer reaction from 1,5-diphenylcarbazide (DPC) to 2,6-dichlorophenolindophenol (DCIP), suggesting that Asn298 is important for the function and photoprotection of the Mn(4)CaO(5) cluster.

A study of the phase transition of reheated diphenyl carbazide (DPC) by using UV spectroscopy.

Phase transition phenomenon in reheated diphenyl carbazide (DPC) is studied here using UV spectroscopy. The optical band gap for reheated DPC is obtained by measuring the optical diffused reflectance (DR) and equals to 3.55 eV. Also, the optical band gap is calculated using UV technique and equals to 3.548 eV. The absorbance of reheated DPC is studied at some selected temperatures in order to check the presence of phase transitions at 90°C and 125°C. According to the present work, the band gaps are calculated at 80°C, 110°C and 130°C and equal to 3.548 eV. But at 100°C, the optical band gap has changed to 4.139 eV. It was found that each phase of reheated DPC belongs to a certain definite crystal structure. The presence of the phase transitions are checked and confirmed by scanning electron microscopy (SEM). The structural properties and morphology of reheated diphenyl carbazide are investigated by SEM. The SEM images are taken at some selected temperatures to confirm the presence of phase transitions.

A microfluidic paper-based analytical device for rapid quantification of particulate chromium.

Occupational exposure to Cr is concerning because of its myriad of health effects. Assessing chromium exposure is also cost and resource intensive because the analysis typically uses sophisticated instrumental techniques like inductively coupled plasma-mass spectrometry (ICP-MS). Here, we report a novel, simple, inexpensive microfluidic paper-based analytical device (µPAD) for measuring total Cr in airborne particulate matter. In the µPAD, tetravalent cerium (Ce(IV)) was used in a pretreatment zone to oxidize all soluble Cr to Cr(VI). After elution to the detection zone, Cr(VI) reacts with 1,5-diphenylcarbazide (1,5-DPC) forming 1,5-diphenylcarbazone (DPCO) and Cr(III). The resulting Cr(III) forms a distinct purple colored complex with the DPCO. As proof-of-principle, particulate matter (PM) collected on a sample filter was analyzed with the µPAD to quantify the mass of total Cr. A log-linear working range (0.23-3.75 µg; r(2)=0.998) between Cr and color intensity was obtained with a detection limit of 0.12 µg. For validation, a certified reference containing multiple competing metals was analyzed. Quantitative agreement was obtained between known Cr levels in the sample and the Cr measured using the µPAD.

Speciation of chromium in soils near Sheba Leather Industry, Wukro Ethiopia.

A study on speciation of chromium in soils near Sheba Leather Industry was performed by Flame Atomic Absorption (FAAS) after selective extraction of Cr(VI) using the EPA 3060A method, and oxidizing the Cr(III) residue in the soils with HNO3 and H2O2. The extraction method was evaluated using the spiking method with satisfactory results (recoveries>95% and RSDs<5%). The limit of detection (LOD) for Cr(VI) based on three times the standard deviations of the blank (for n=5) was 0.56 µg g(-1). Statistical evaluation indicated that the comparison of the sum of the concentrations of chromium species to that of the total concentration of chromium do not show any difference at 95% level of confidence. Besides, no statistically significant difference at 95% confidence level was observed between the UV-vis spectrophotometry and FAAS results for Cr(VI). However, it is observed that selective extraction of Cr(VI) using EPA 3060A and subsequent determination by FAAS is simple and faster compared to the other method. Furthermore, for comparison and as control two soil samples collected from a distance of about 2 km from the main Industry and effluent stream. The results indicate that higher total chromium content was observed in soils collected from the target area. Nevertheless, the maximum concentrations of Cr(VI) found in soil samples collected around Sheba Leather Industry was 9.9 µg g(-1) and are within the acceptable level of 10 µg g(-1) in accordance with the WHO.

Application of multiwalled carbon nanotubes modified by diphenylcarbazide for selective solid phase extraction of ultra traces Cd(II) in water samples and food products.

A novel sorbent for separation of cadmium ions was prepared by functionalizing multiwall carbon nanotubes with diphenylcarbazide and underutilised to develop a solid-phase extraction method to separate and concentrate trace amounts of cadmium ions from some real samples by flame atomic absorption spectrophotometry measurements. The optimum experimental conditions such as pH, flow rates, type and the smallest amount of eluent for elution of cadmium ions, break through volume and effect of coexisting ions on the separation and determination of cadmium ions were evaluated. In the proposed method, the extraction efficiency for cadmium ions were greater than 97% and limit of detection (LOD) was 0.05 ng mL(-1). The preconcentration factor was 360 for cadmium and the relative standard deviation (RSD) of the method was 2.4%. The adsorption capacity of the modified MWCNT was 86 mg g(-1) for cadmium ions. Validation of the outlined method was performed by analysing certified reference material soil (NCS DC 73323). The practical applicability of the developed sorbent was examined in some real samples.

IR spectroscopic analysis of the new organic silver complex C13H13N4OAg.

IR analysis in the frequency range 400-4000 cm(-1) is used here to investigate the changes in different modes of thermally treated new metal complex (diphenyl carbazide silver complex DPCAg, C13H13N4OAg) during the glass transition at 91 °C and the high temperature phase transition at 167 °C. These two phase transitions in this new metal compound are studied here by detecting the changes in some IR spectroscopic parameters (e.g., mode shift, band contour, peak height and peak intensity) during the elevation of temperature. All of the vibrations of DPCAg were found to be due to ionic fundamentals 3311 cm(-1), 3097 cm(-1), 3052 cm(-1), 1677 cm(-1), 1602 cm(-1), 1492 cm(-1), 1306 cm(-1), 1252 cm(-1), 887 cm(-1) and 755 cm(-1). The results obtained can be considered as the first spectroscopic analysis of this new metal complex. These results strongly confirmed that the thermally treated DPCAg transverse a glass transition at 91 °C and a high temperature phase transition at 167 °C. Anomalous spectroscopic changes near the glass transition temperature Tg could be recorded. A temperature dependence of peak intensity of the two modes 810 cm(-1) and 3440 cm(-1) could be observed beyond Tg. Also, the high temperature phase modification at 167 °C showed anomalous change in the spectroscopic parameters before and after the phase transition process. A proposed silver position in the new silver complex DPCAg has been presented.