Use of organofunctionalized nanoporous silica gel to improve the lifetime of carbon paste electrode for determination of copper(II) ions

A new functionalized nanoporous silica gel with dipyridyl group (DPNSG) was synthesized. Then, the potentiometric response of the copper(II) ion was investigated at a carbon paste electrode chemically modified with this newly designed functionalized nanoporous silica gel. The electrodes with DPNSG proportions of 15.0% (w/w) demonstrated very stable potentials. Calibration plots with Nernstian slopes for Cu²⁺ were observed, 28.4 (±1.0) mV decade⁻¹, over a wide linear concentration range (1.0 × 10⁻⁷ to 1.0 × 10⁻² M). The electrode exhibited a detection limit of 8.0 × 10⁻⁸ M. Moreover, the selectivity coefficients measured by the match potential method in acetate buffer, pH 5.5, were investigated. The electrode presented a response time of ∼50 s, high performance, high sensitivity in a wide range of cation activities and good long-term stability (more than 9 months). The method was satisfactory and was used to determine the copper ion concentration in waste waters, contaminated by this metal.     

Investigation of stresses and normal stress differences behavior on symmetric and asymmetric polymeric fluid flow through planar gradual expansions

A numerical study of stress distribution of polymeric viscoelastic fluids passing through planar gradual expansion channels is conducted. To model the viscoelastic behavior in geometries with 1:3 expansion ratios, the exponential form of Phan-Thien Tanner model is employed as the constitutive equation. The PISO algorithm is used to solve the flow field distribution. Three different expansion angles of 30°, 45° and 60° are considered to probe the effects of the gradual expansion and its effect on the stress field distribution. The main purpose of the current study is to analysis the combined effects of the rheological properties and inertia on the normal stress distribution. To achieve this aim, different expansion angles and different ranges of Weissenberg and Reynolds numbers are studied.     

An Existence Result for a Class of Chemically Reacting Systems with Sign-Changing Weights

We prove the existence of positive solutions for the system$$\begin{align*}\begin{cases}-\Delta_{p} u =\lambda a(x){f(v)}{u^{-\alpha}},\qquad x\in \Omega,\\-\Delta_{q} v = \lambda b(x){g(u)}{v^{-\beta}},\qquad x\in \Omega,\\u = v =0, \qquad x\in\partial \Omega,\end{cases}\end{align*}$$where $\Delta_{r}z={\rm div}(|\nabla z|^{r-2}\nabla z)$, for $r>1$ denotes the r-Laplacian operator and $\lambda$ is a positive parameter, $\Omega$ is a bounded domain in $\mathbb{R}^{n}$, $n\geq1$ with sufficiently smooth boundary and $\alpha, \beta \in (0,1).$ Here $ a(x)$ and $ b(x)$ are $C^{1}$ sign-changingfunctions that maybe negative near the boundary and $f,g $ are $C^{1}$ nondecreasing functions, such that $f, g :\ [0,\infty)\to [0,\infty);$ $f(s)>0,$ $g(s)>0$ for $s> 0$, $\lim_{s\to\infty}g(s)=\infty$ and$$\lim_{s\to\infty}\frac{f(Mg(s)^{\frac{1}{q-1}})}{s^{p-1+\alpha}}=0,\qquad \forall M>0.$$We discuss the existence of positive weak solutions when $f$, $g$, $a(x)$ and $b(x)$ satisfy certain additional conditions. We employ the method of sub-supersolution to obtain our results.     

Adsorptive Stripping Voltammetric Determination of Nanomolar Concentration of Cerium(III) at a Carbon Paste Electrode Modified by N′‐[(2‐Hydroxyphenyl)Methylidene]‐2‐Furohydrazide

The aim of this work was to obtain an adsorptive stripping voltammetric method for the Ce(III) determination at a carbon paste electrode, chemically modified with N'‐[(2‐hydroxyphenyl)methylidene]‐2‐furohydrazide (NHMF). The electroanalytical procedure comprised two steps: the Ce(III) chemical accumulation at ?200 mV followed by the electrochemical detection of the Ce(III)/NHMF complex, using anodic stripping voltammetry. The factors, influencing the adsorptive stripping performance, were optimized including the modifier quantity in the paste, the electrolyte concentrations, the solution pH and the accumulation potential or time. The resulting electrode demonstrated a linear response over a wide range of Ce(III) concentration (5.0–90 nmol dm^?3). The detection limit was found to be 0.8 nmol dm^?3 on the basis of a signal to noise ratio of 3. The precision for six determinations of 10 and 55 nmol dm^?3 Ce(III) was 5.6% and 2.1% (relative standard deviation), respectively. Application of the procedure to the determination of cerium in phosphate rock and wastewater samples gave good results.     

A new Tb-selective fluorescent sensor based on 2-(5-(dimethylamino)naphthalen-1-ylsulfonyl)-N-henylhydrazinecarbothioamide

A novel fluorescent chemosensor 2-(5-(dimethylamino)naphthalen-1-ylsulfonyl)-N-phenylhydrazinecarbothioamide (L) has been synthesized, which revealed an emission of 530 nm and when excited at 360 nm. The fluorescent probe undergoes a fluorescent emission intensity quenching upon binding to terbium ions in MeCN solution. The fluorescence quenching of L is attributed to the 1:1 complex formation between L and Tb(III) which has been utilized as the basis for the selective detection of Tb(III). The linear response range covers a concentration range of Tb(III) from 4.0 × 10⁻⁷ to 1.0 × 10⁻⁵ M and the detection limit is 1.4 × 10⁻⁷ M. The association constant of the 1:1 complex formation for L–Tb⁺³ was calculated to be 6.01 × 10⁶ M⁻¹, and the fluorescent probe exhibits high selectivity over other common metal ions mono-, di-, and trivalent cations indicate good selectivity for Tb(III) ions over a large number of interfering cations.     

Determination of the formation constant for the inclusion complex between Lanthanide ions and Dansyl chloride derivative by fluorescence spectroscopy: Theoretical and experimental investigation

In this paper, a sensitive, easy, efficient, and suitable method for the calculation of K_f values of complexation between one derivative of Dansyl chloride [5-(dimethylamino) naphthalene-1-sulfonyl 4-phenylsemicarbazide] (DMNP) and Lanthanide(III) (Ln) ions is proposed, using both spectrofluorometric and spectrophotometric methods. Determination of K_f showed that DMNP was mostly selective towards the erbium (III) ion. The validity of the method was also confirmed calculating the Stern–Volmer fluorescence quenching constants (K_sv) that resulted in the same consequence, obtained by calculating the K_f of complexation values. In addition, the UV–vis spectroscopy was applied for the determination of K_f only for the Ln ions that had interactions with DMNP. Finally, the DFT studies were done on Er³⁺ and the DMNP complex for distinguishing the active sites and estimating the pair wise interaction energy. It can be concluded that this derivative of Dansyl chloride with inherent high fluorescence intensity is a suitable reagent for the selective determination of the Er³⁺ ion which can be used in constructing selective Er³⁺ sensors.     

On the comparative optimal analysis and synthesis of four-bar function generating mechanism using different heuristic methods

In this research, optimal synthesis of function generation of four-bar linkages is investigated using different heuristic optimization methods. The novelty of this study is that we considered the five precision point’s distribution and both stroke angles of the follower and crank links as the optimization variables. Therefore, a non-linear optimization was done with seven variables. Different optimization techniques, including heuristic and gradient based methods were used for optimization and were completely compared. Finally, general solutions were found and distribution of precision points for some desired functions was rationalized. GA-Hybrid seems to be the best method in finding global optimums in cases that the problem is sorely nonlinear, and also it is fast. Even it seems that distribution of precision points is independent of stroke angles of the follower and crank links. Some precision points are out of the design domain, and they are sorted in a way that they can describe the behavior of desired function better.     

Facile controlled synthesis and growth mechanisms of flower-like and tubular MnO2 nanostructures by microwave-assisted hydrothermal method

Birnessite flower-like and α-type tubular MnO(2) nanostructures were selectively synthesized through simple decomposition of KMnO(4) under hydrochloric acid condition by controlling reaction temperature using a microwave-assisted hydrothermal method. The as-prepared samples were characterized in detail by various techniques including X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, Fourier transform-infrared spectroscopy, and Raman scattering spectroscopy. While the growth of flower-like birnessite-MnO(2) might follow a widely accepted Ostwald ripening process, we proposed a formation mechanism of the nanotubular α-MnO(2) based on our evidence, which was assembly of nanorods through an "oriented attachment" process.     

Determination of Sulfite in Real Sample by an Electrochemical Sensor Based on Ni/Poly(4-Aminobenzoic Acid)/Sodium Dodecylsulfate/Carbon Paste Electrode

In this research, a modified electrode has been produced during the electropolymerization of 4-Aminobenzoic acid in the presence of sodium dodecylsulfate (SDS) and then Ni(II) ions were incorporated to the polymer by immersion of the modified electrode in a 0.1 M Ni(II) ions solution. The electrochemical behavior of Ni/poly(4-aminobenzoic acid)/sodium dodecylsulfate/carbon paste electrode (Ni/poly(4-AB)/SDS/CPE) was investigated by using cyclic voltammetry. The experimental results exhibited the stable redox behavior of the Ni(III)/Ni(II) couple immobilized at the polymeric electrode. This polymeric modified electrode has a very good activity toward the sulfite electrooxidation in a phosphate buffer solution (pH 11). By comparison of the different responses to sulfite oxidation using electrodes Ni/poly(4-AB)/SDS/CPE, poly(4-AB)/SDS/CPE and CPE, we observed that the former electrode is a more effective catalyst for the electrooxidation of sulfite. Under optimal experimental conditions, the peak current response increased linearly with sulfite concentration over the range of 0.1–1 and 1–10 mM. The detection limit of the method was 0.063 mM. Finally, the method was applied to the determination of sulfite in weak liquor sample.     

Highly selective and sensitive monohydrogen phosphate membrane sensor based on molybdenum acetylacetonate

In this work, a highly selective and sensitive monohydrogen phosphate membrane sensor based on a molybdenum bis(2-hydroxyanil) acetylacetonate complex (MAA) is reported. The sensor shows a linear dynamic range between 1.0 × 10⁻¹ and 1.0 × 10⁻⁷ M, with a nice Nernstian behavior (−29.5 ± 0.3 mV decade⁻¹) in pH of 8.2. The detection limit of the electrode is 6.0 × 10⁻⁸ M (∼6 ppb). The best performance was obtained with a membrane composition of 32% poly(vinyl chloride), 58% benzyl acetate, 2% hexadecyltrimethylammonium bromide and 8% MAA. The sensor possesses the advantages of short response time, low detection limit and especially, very good selectivity towards a large number of organic and inorganic anions including salicylate, citrate, tartarate, acetate, oxalate, fluoride, chloride, bromide, iodide, sulfite, sulfate, nitrate, nitrite, cyanide, thiocyanate, perchlorate, metavanadate, and bicarbonate ions. The electrode can be used for at least 10 weeks without any considerable divergence in its slope and detection limit. It was used as an indicator electrode in potentiometric titration of monohydrogenphosphate ion with barium chloride. The proposed sensor was successfully applied to direct determination of monohydrogenphosphate in two fertilizer samples (NPK).