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1.
New synthesized reagent 2,6‐diacetylpyridine bis‐4‐phenyl‐3‐thiosemicarbazone (2,6‐DAPBPTSC) is proposed as a sensitive and selective analytical reagent for the extractive spectrophotometric determination of cobalt(II). Cobalt(II) forms a reddish brown colored complex with 2,6‐DAPBPTSC, which is extracted into isoamylalcohol, under optimum conditions. The maximum absorption of the isoamylalcohol extract is measured at 400 nm. Beer's law is applied in the range 0.6‐6.0 ppm of cobalt(II). The molar absorptivity and Sandell's sensitivity of the complex is calculated as 2.2 × 104 L mol?1 cm?1 and 2.68 × 10?3 μg cm?2, respectively. An adequate linearity with a correlation coefficient value of 0.969 is obtained for the Co(II)‐2,6‐DAPBPTSC complex. The instability constant of the complex, calculated from Asmus' method is 3.75 × 10?4 The precision and accuracy of the method is checked with calculation of relative standard deviation (n = 5), 0.388 and the detection limit a value is 0.0028 μg mL?1. The method is successfully employed for the determination of cobalt(II) in real samples, such as vegetables, soil, water samples, standard alloy samples, and the performance of the present method was evaluated in terms of Student ‘t’ test and Variance ‘f’ test, which indicates the significance of the present method is an inter comparison of the experimental values, using atomic absorption spectrometer (AAS).  相似文献   

2.
The electrochemical redox properties of a surface‐confined thin solid film of nanostructured cobalt(II) tetracarboxyphthalocyanine integrated with multiwalled carbon nanotube (nanoCoTCPc/MWCNT) have been investigated. This novel nanoCoTCPc/MWCNT material was characterized using SEM, TEM, zeta analysis and electrochemical methods. The nanoCoTCPc/MWCNT nanohybrid material exhibited an extra‐ordinarily high conductivity (15 mS cm?1), which is more than an order of magnitude greater than that of the MWCNT‐SO3H (527 µS cm?1) and three orders of a magnitude greater than the nanoCoTCPc (4.33 µS cm?1). The heterogeneous electron transfer rate constant decreases as follows: nanoCoTCPc/MWCNT (kapp≈19.73×10?3 cm s?1)>MWCNT‐SO3H (kapp≈11.63×10?3 cm s?1)>nanoCoTCPc (kapp≈1.09×10?3 cm s?1). The energy‐storage capability was typical of pseudocapacitive behaviour; at a current density of 10 µA cm?2, the pseudocapacitance decreases as nanoCoTCPc/MWCNT (3.71×10?4 F cm?2)>nanoCoTCPc (2.57×10?4 F cm?2)>MWCNT‐SO3H (2.28×10?4 F cm?2). The new nanoCoTCPc/MWCNT nanohybrid material promises to serve as a potential material for the fabrication of thin film electrocatalysts or energy‐storage devices.  相似文献   

3.
《Analytical letters》2012,45(4):823-833
Abstract

A simple, sensitive, and specific spectrophotometric method for the measurement of nitrite in water has been developed and optimum reaction conditions along with other analytical parameters have been evaluated. The azo dye, 4‐(1‐methyl‐1‐mesitylcylobutane‐3‐yl)‐2‐(p‐N,N‐dimethylazobenzene)‐1,3‐thiazole was synthesized with the reaction of 4‐(1‐methyl‐1‐mesitylcylobutane‐3‐yl)‐2‐aminothiazole and N,N‐dimethyl aniline in acidic medium. Obtained azo dye has been characterized by infrared (IR), 1H nuclear magnetic resonance (NMR), and microanalysis methods. The dye shows an absorption maximum at 482 nm. The method is optimized for acid concentration, pH, amount of reagents required, time, and interfering species. All the determinations were carried out at this wavelength throughout the work. At an analytical wavelength of 482 nm, Beer's law is obeyed over the concentration range 0.05 to 2.00 µg nitrite per mL analyte. The molar absorptivity, Sandell's sensitivity, and relative standard deviation are 2.03×104 L mol?1 cm?1±251.3 (95%), 2.28×10?3 µg cm?2, and 2.74% (n=10), respectively. The detection limit of the method is 0.012 µg ml?1 of nitrite ion. The method was succesfully applied to the determination of nitrite in tap water and lake water.  相似文献   

4.
A new sensitive spectrophotometric method for the determination of glyphosate herbicide in environmental and agricultural samples is developed. The reaction is based on diazotization followed by coupling of glyphosate with p-dimethyl amino benzaldehyde. The resulted complex absorption spectra was observed at λmax = 420 nm. The effects of other metal ions and pesticides were also tested for selective determination of glyphosate. The analytical parameters were optimized and have been successfully applied for determination of glyphosate in various environmental samples such as soil, water and vegetables. This method has a lower limit detection of 6 μg of glyphosate. Beer's law is obeyed over the concentration range of 6.0 μg–24.0 μg glyphosate in 25 mL of the final solution at 420 nm. The standard deviation and relative standard deviation calculated are 0.0055 and 1.023, respectively. The molar absorptivity of the colored system is 1.91 × 1010 L mol?1cm?1 and Sandell's sensitivity is found 0.408 × 10?5 μg cm?2. The proposed method is simple, sensitive, highly reproducible and time saving as compare to those complicated time consuming methods.  相似文献   

5.
The imidoylnitrene 8 , N‐methyl‐C‐phenylimidoylnitrene, has been generated by laser photolysis of 1‐methyl‐5‐phenyltetrazole 6 at 5 K and characterized by its ESR spectrum (|D/hc|=0.9602, |E/hc|=0.0144 cm?1). In addition, the triplet excited states of 6 and of 2‐methyl‐5‐phenyltetrazole 11 were also observed by ESR spectroscopy in the 5 K matrices ( 6 : |D/hc|=0.123 cm?1, E/hc=0.0065 cm?1, 11 : |D/hc|=0.126 cm?1, |E/hc|=0.0056 cm?1). The imidoylnitrene 8 is unstable both thermally (disappearing at 80 K) and photochemically (disappearing on continued irradiation at 266 nm). Methyl(phenyl)carbodiimide is the end product of photolysis.  相似文献   

6.
The gas permeability and n‐butane solubility in glassy poly(1‐trimethylgermyl‐1‐propyne) (PTMGP) are reported. As synthesized, the PTMGP product contains two fractions: (1) one that is insoluble in toluene and soluble only in carbon disulfide (the toluene‐insoluble polymer) and (2) one that is soluble in both toluene and carbon disulfide (the toluene‐soluble polymer). In as‐cast films, the gas permeability and n‐butane solubility are higher in films prepared from the toluene‐soluble polymer (particularly in those films cast from toluene) than in films prepared from the toluene‐insoluble polymer and increase to a maximum in both fractions after methanol conditioning. For example, in as‐cast films prepared from carbon disulfide, the oxygen permeability at 35 °C is 330 × 10?10 cm3 (STP) cm/(cm2 s cmHg) for the toluene‐soluble polymer and 73 × 10?10 cm3 (STP) cm/(cm2 s cmHg) for the toluene‐insoluble polymer. After these films are conditioned in methanol, the oxygen permeability increases to 5200 × 10?10 cm3 (STP) cm/(cm2 s cmHg) for the toluene‐soluble polymer and 6200 × 10?10 cm3 (STP) cm/(cm2 s cmHg) for the toluene‐insoluble polymer. The rankings of the fractional free volume and nonequilibrium excess free volume in the various PTMGP films are consistent with the measured gas permeability and n‐butane solubility values. Methanol conditioning increases gas permeability and n‐butane solubility of as‐cast PTMGP films, regardless of the polymer fraction type and casting solvent used, and minimizes the permeability and solubility differences between the various films (i.e., the permeability and solubility values of all conditioned PTMGP films are similar). © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2228–2236, 2002  相似文献   

7.
Rate constants for the reactions of Cl atoms with two cyclic dienes, 1,4‐cyclohexadiene and 1,5‐cyclooctadiene, have been determined, at 298 K and 800 Torr of N2, using the relative rate method, with n‐hexane and 1‐butene as reference molecules. The concentrations of the organics are followed by gas chromatographic analysis. The ratios of the rate constants of reactions of Cl atoms with 1,4‐cyclohexadiene and 1,5‐cyclooctadiene to that with n‐hexane are measured to be 1.29 ± 0.06 and 2.19 ± 0.32, respectively. The corresponding ratios with respect to 1‐butene are 1.50 ± 0.16 and 2.36 ± 0.38. The absolute values of the rate constants of the reaction of Cl atom with n‐hexane and 1‐butene are considered as (3.15 ± 0.40) × 10?10 and (3.21 ± 0.40) × 10? 10 cm3 molecule?1s?1, respectively. With these, the calculated values are k(Cl + 1,4‐cyclohexadiene) = (4.06 ± 0.55) × 10?10 and k(Cl + 1,5‐cyclooctadiene) = (6.90 ± 1.33) × 10?10 cm3 molecule?1 s?1 with respect to n‐hexane. The rate constants determined with respect to 1‐butene are marginally higher, k(Cl + 1,4‐cyclohexadiene) = (4.82 ± 0.80) × 10? 10 and k(Cl + 1,5‐cyclooctadiene) = (7.58 ± 1.55) × 10? 10 cm3 molecule?1 s?1. The experiments for each molecule were repeated three to five times, and the slopes and the rate constants given above are the average values of these measurements, with 2σ as the quoted error, including the error in the reference rate constant. The relative rate ratios of 1,4‐cyclohexadiene with both the reference molecules are found to be higher in the presence of oxygen, and a marginal increase is observed in the case of 1,5‐cyclooctadiene. Benzene is identified as one major product in the case of 1,4‐cyclohexadiene. Considering that the cyclohexadienyl radical, a product of the hydrogen abstraction reaction, is quantitatively converted to benzene in the presence of oxygen, the fraction of Cl atoms that reacts by abstraction is estimated to be 0.30 ± 0.04. The atmospheric implications of the results are discussed. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 431–440, 2011  相似文献   

8.
A validated, selective and sensitive spectrophotometric method has been developed for the determination of labetalol hydrochloride in commercial dosage forms. The method is based on the coupling reaction of positive diazonium ion of 4‐aminobenzenesulfonic acid with phenolate ion of labetalol to form a colored azo compound which absorbs maximally at 395 nm. Under the optimized experimental conditions, the color is stable up to 2 h and Beer's law is obeyed in the concentration range of 0.8–17.6 μg mL?1 with a linear regression equation of A = 4.84 × 10?4 + 7.864 × 10?2 C and coefficient of correlation, r = 0.9999. The molar absorptivity and Sandell's sensitivity are found to be 2.874 × 104 L mol?1 cm?1 and 0.013 μg cm?2 per 0.001‐absorbance unit, respectively. The limits of detection and quantitation of the proposed method are 0.08 and 0.23 μg mL?1, respectively. The intra‐day and inter‐day precision variation and accuracy of the proposed method is acceptable with low values of standard analytical error. The recovery results obtained by the proposed method in drug formulations are acceptable with mean percent recovery ± RSD of 99.97 ± 0.52 ‐ 100.03 ± 0.63%. The results of the proposed method compared with those of Bilal's spectrophotometric method indicated excellent agreement with acceptable true bias of all samples within ± 2.0%.  相似文献   

9.
Simple, rapid and reliable method for the determination of albendazole (ABZ) was described. This includes the utility of some Π‐acceptors such as 2,3‐dichloro‐5,6‐dicyano‐p‐benzoquinone (DDQ) and 3,6‐dichloro‐2,5‐dihy‐ droxy‐p‐benzoquinone (p‐CLA) for estimation of ABZ drug (act as donor). The experimental conditions were optimized and the system obeys Beer's law for 7.50–80 and 10.00–85.00 µg·mL?1 of ABZ using DDQ and p‐CLA, respectively. The molar absorptivity and Sandell sensitivity were calculated to be 1.83×103 and 1.12×103 L·mol?1·cm?1, and 2.60 and 3.40 ng·cm?2 using DDQ and p‐CLA, respectively. The limits of detection and quantification were calculated to be (7.42 and 6.73) and (9.94 and 4.13) µg·mL?1 using DDQ and p‐CLA, respectively. The proposed methods were successfully applied to the determination of ABZ in commercially available dosage forms. The reliability of the assays was established by parallel determination by the official method and recovery studies. The chemical structures of the solid charge‐transfer (CT) complexes formed via reaction between ABZ under study and Π‐acceptors, have been elucidated using elemental analyses (C, H and N), IR, 1H NMR and mass spectra.  相似文献   

10.
A simple sensitive spectrophotometric method has been developed for the determination of atrazine in herbicide formulations and real samples. The method was based on the reaction of atrazine with pyridine to form a quaternary halide which in the presence of alkali forms a carbinol base. The heterocyclic ring of the carbinol base breaks and forms the glutaconic dialdehyde. The glutaconic dialdehyde group was coupled with sulfanilic acid to form a yellow coloured product having λ max 450 nm or coupled with aniline to form a orange red coloured product having λ max 480 nm. The Beer's law was obeyed over the range from 0.1 to 25 µg mL?1 and molar absorptivity 1.5 × 104 L mol?1 cm?1 for sulfanilic acid, and from 0.08 to 12 µg mL?1 and molar absorptivity 1.3 × 104 L mol?1 cm?1 for aniline were observed. The reaction conditions and other analytical parameters were optimised. The proposed method has been successfully applied for the analysis of commercial formulations and real samples.  相似文献   

11.
A new reagent system using rhodamine‐B dye for the determination of selenium is described. The method is based on the reaction of selenium with acidified potassium iodide to liberate iodine. The liberated iodine bleaches the pink colour rhodamine‐B, which is measured at 555 nm. Beer's law is obeyed over the concentration range of 1–10 μg of selenium final solution volume of 25 mL (0.04–0.4 ppm) and the apparent molar absorptivity and Sandell's sensitivity was found to be 1.96× 105 l mol?1 cm?1 and 0.0004 μg cm?2, respectively. The method is simple, sensitive, and selective and is satisfactorily applied to micro‐level determination of selenium in various environmental and cosmetic samples.  相似文献   

12.
The objective of this research work was to develop a simple, highly sensitive and precise method for spectrophotometric determination of osmium(IV). O-Methylphenyl thiourea (OMPT) coordinates with osmium(IV) as a 1:1 (osmium(IV)–OMPT) complex in hydrochloric acid media (0.8 mol l?1). The novelty of the investigated method is instant complex formation at room temperature with no need of heating or standing. The complex is stable for more than 8 days. The method is applicable over a wide linearity range (up to 110 µg ml?1). A low reagent concentration is required (2 ml, 0.009 mol l?1 in ethanol). The complex exhibits maximum absorption in the range of wavelength 510–522 nm and 514 nm was selected for further study. The molar absorptivity was 1.864 × 103 l mol?1 cm?1, Sandell’s sensitivity was 0.102 µg of osmium(IV) cm?2. Proposed method was successfully applied for separation and determination of osmium(IV) from binary and ternary synthetic mixtures containing associated metal ions. A scheme for mutual separation of osmium(IV), rhodium(III) and platinum(IV) is developed.  相似文献   

13.
A series of highly sulfonated, ether‐containing polybenzimidazoles (SOPBI) with controlled sulfonation degrees were synthesized from various stoichiometric ratio mixtures of sodium 6,6'‐oxybis(3‐carboxybenzenesulfonate) (SODBA), 4,4'‐oxydibenzoic acid (ODBA), and 3,3'‐diaminobenzidine (DAB) by solution copolycondensation in poly(phosphoric acid). The resulting sulfonated polymers were further sulfonated by grafting of pendant sulfonic acid chains via a reaction of 1,3‐propane sultone with lithiated‐N of the imidazole rings in the polymer backbone, yielding materials with high, absolute IEC values (3.42–4.15 meq g?1). Due to self‐neutralization, the solid state polymers possessed “free” acid content of 1.40 to 2.15 meq g?1, were soluble in organic solvents yet insoluble in aqueous solution, while displaying proton conductivites (11–47 mS cm?1) at elevated temperatures (80 °C, 95% RH). © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3654–3666  相似文献   

14.
Greener electrochemical detection method developed for chemical warfare agent (CWA) nitrogen mustard‐2 (NM‐2) using room temperature ionic liquid (RTIL). The diffusion coefficient calculated for NM‐2 in acetonitrile and RTIL was 1.57×10?4 cm2/s and 1.82×10?10 cm2/s, respectively. NM‐2 addition to RTIL enhanced RTIL conductivity. Moreover, heterogeneous rate constant (0.192 s?1), transfer coefficient (0.231) and the number of electron involved (1.0) were deduced for NM‐2 in RTIL. The calibration plot showed linearity between 2.94×10?5 and 1.17×10?3 M with detection limit 1.47 ×10?5 M (S/N=3). The large number of available RTIL can be used for greener detection of toxic CWAs.  相似文献   

15.
To the determination of trace amount of Cd(II) present in food and water samples, a selective and extractive spectrophotometric method were developed with 2,6‐diacetylpyridine‐bis‐4‐phenyl‐3‐thiosemicarbazone as a complexing agent. The yellowish orange colored metal complex, Cd(II)‐2,6‐DAPBPTSC with 1:1 (M:L) composition was extracted in to cyclohexanol at pH 9.5 and was shows maximum absorbance at λmax 390 nm. This method obeys Beer's law in the range of 1.12‐11.25 ppm with 0.972 correlation coefficient of Cd(II)‐2,6‐DAPBPTSC complex, which is indicates linearity between the two variables. The molar absorptivity and sandell's sensitivity were found to be 6.088 × 104 L mol?1 cm?1 and 0.0018 μg cm?2, respectively. The instability constant calculated from Asmus' method (1.447 × 10?4)at room temperature. The precision and accuracy of the method were checked by relative standard deviation (n = 5), 0.929 and its detection limit, 0.0060 μg mL?1. The interfering effects of various cations and anions were also studied. The proposed method was successfully applied to the determination of Cd(II) in foods and water samples, and was evaluated its performance in terms of Student ‘t’ test and Variance ‘f’ test, which indicates the significance of present method. The inter comparison of the experimental values, using atomic absorption spectrometer (AAS), was also repoted.  相似文献   

16.
Abstract

Nitrite ion at low concentration is determined spectrometrically by diazotization of p-aminobenzo-phenone and coupling of the resulting diazonium cation with N-(1-naphthy1)-ethylene-diamine to form a reddish-violet coloured water-soluble azo dye with maximum absorption at 555 nm. The method is suitable for the determination of nitrite over the range of 0.04–1.00 ppm. Beer's law is obeyed over this range of concentrations. The observed molar absorptivity and Sandell's sensitivity of the azo dye are 7.0 × 104 mol?1 cm?1 and 6.5 × 10?4 μg cm?2, respectively. Interferences due to other ions were studied to test the selectivity.  相似文献   

17.
《Electroanalysis》2004,16(4):289-297
The polymer film of N,N‐dimethylaniline (DMA) is deposited on the electrochemically pretreated glassy carbon (GC) electrode by continuous electrooxidation of the monomer. This poly N,N‐dimethylaniline (PDMA) film‐coated electrode can be used as an amperometric sensor of ascorbic acid (AA). The polymer film (thickness (?): 0.3±0.02 μm) having positive charge in its backbone attracts the anionic species AA. Thus, the anodic peak potential (350 mV vs. Ag|AgCl|NaCl(sat)) for the oxidation of AA at the bare electrode is largely shifted to the negative value (150 mV) at this electrode. The PDMA film‐coated electrode is stable in acidic, alkaline and neutral media and can sense AA at different pH's. The diffusion coefficients of AA in solution (D) and in film (Ds) were estimated by rotating disk electrode voltammetry: D=(5.5±0.1)×10?6 cm2 s?1 and Ds=(6.3±0.2)×10?8, (6.0±0.2)×10?8 and (4.7±0.2)×10?8 cm2 s?1 for 0.5, 1.5 and 3.0 mM AA, respectively. A permeability of AA through the PDMA film was found to decrease with increasing the concentration of AA in the solution. In the chronoamperometry, the current response for the oxidation of AA at different times elapsed after potential‐step application is linearly increased with the increase in AA concentration in a wide range of its concentration from 25 μM to 1.65 mM. In the hydrodynamic amperometry, a successive addition of 10 μM AA caused the successive increase in current response with equal amplitude and the sensitivity was calculated as 0.178 μA cm?2 μM?1. So, the fouling of the electrode surface caused by the oxidized product of AA is markedly eliminated at this PDMA film‐coated electrode. A flow injection analysis based on the present electrode was performed to estimate the concentration of vitamin C in fruit juice.  相似文献   

18.
A simple, rapid, cost effective and extraction‐free spectrophotometric method has been developed for the determination of zolmitriptan in pharmaceutical raw and dosage forms. The method is based on the charge‐transfer reaction of zolmitriptan in acetonitrile medium with 0.2% 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone to form a colored product peaking at 555 nm. Beer's law is obeyed in the concentration range 10‐250 μg mL?1 with molar absorptivity of 1.7 × 103 L mole?1 cm?1. The effects of variables such as reagent concentration, time of reaction, color stability and interferences have been investigated to optimize the procedure. The results have been validated analytically and statistically. The proposed method has been successfully applied for the determination of zolmitriptan in pharmaceutical formulations. Results indicate that the method is accurate, precise and reproducible (relative standard deviation < 2%).  相似文献   

19.
Two new electron‐rich molecules based on 3,4‐phenylenedioxythiophene (PheDOT) were synthesized and successfully adopted as hole‐transporting materials (HTMs) in perovskite solar cells (PSCs). X‐ray diffraction, absorption spectra, photoluminescence spectra, electrochemical properties, thermal stabilities, hole mobilities, conductivities, and photovoltaic parameters of PSCs based on these two HTMs were compared with each other. By introducing methoxy substituents into the main skeleton, the energy levels of PheDOT‐core HTM were tuned to match with the perovskite, and its hole mobility was also improved (1.33×10?4 cm2 V?1 s?1, being higher than that of spiro‐OMeTAD, 2.34×10?5 cm2 V?1 s?1). The PSC based on MeO‐PheDOT as HTM exhibits a short‐circuit current density (Jsc) of 18.31 mA cm?2, an open‐circuit potential (Voc) of 0.914 V, and a fill factor (FF) of 0.636, yielding an encouraging power conversion efficiency (PCE) of 10.64 % under AM 1.5G illumination. These results give some insight into how the molecular structures of HTMs affect their performances and pave the way for developing high‐efficiency and low‐cost HTMs for PSCs.  相似文献   

20.
A new and highly sensitive spectophotometric method is developed for the determination of parts per million levels of widely used organophosphorus pesticide monocrotophos. The method is based on alkaline hydrolysis of monocrotophos to N‐methylacetoacetamide followed by coupling with diazotized p‐amino acetophenone in alkaline medium. The absorption maxima of the reddish‐violet coloured compound formed is measured at 560 nm. Beer's law is obeyed over the concentration range of 1.2 to 6.8 μg in a final solution volume of 25 mL. The molar absorptivity and Sandell's sensitivity were found to be 7.1 × 105 (±100) L mole?1 cm?1 and 0.008 μg cm?2, respectively. The standard deviation and relative standard deviation were found to be ± 0.005 and 2.05%, respectively. The method is simple, sensitive and free from interferences of other pesticides and diverse ions. The method has been satisfactorily applied to the determination of monocrotophos in environmental, agricultural and biological samples.  相似文献   

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