Making and Breaking of Gels: Stimuli-Responsive Properties of Bis(Pyridyl-N-oxide Urea) Gelators

The structural modification of existing supramolecular architecture is an efficient strategy to design and synthesize supramolecular gels with tunable and predictable properties. In this work, we have modified bis(pyridyl urea) compounds with different linkers, namely hexylene and butylene, to their corresponding bis(pyridyl-N-oxide urea). The gelation properties of both the parent and the modified compounds were studied, and the results indicated that modification of the 3-pyridyl moieties to the corresponding 3-pyridyl-N-oxides induced hydrogelation. The stability of the parent and modified compounds were evaluated by sol-gel transition temperature (T_gel) and rheological measurements, and single-crystal X-ray diffraction was used to analyze the solid-state interactions of the gelators. The morphologies of the dried gels were analyzed by scanning electron microscopy (SEM), which revealed that the structural modification did not induce any prominent effect on the gel morphology. The stimuli-responsive behavior of these gels in the presence of salts in DMSO/water was evaluated by rheological experiments, which indicated that the modified compounds displayed enhanced gel strength in most cases. However, the gel network collapsed in the presence of the chloride salts of aluminum(III), zinc(II), copper(II), and cadmium(II). The mechanical strength of the parent gels decreased in the presence of salts, indicating that the structural modification resulted in robust gels in most cases. The modified compounds formed gels below minimum gel concentration in the presence of various salts, indicating salt-induced gelation. These results show the making and breaking ability of the gel network in the presence of external stimuli (salts), which explains the potential of using LMWGs based on N-oxide moieties as stimuli-responsive materials.     

Synergistic solvent extraction of Eu(III) and Tb(III) with mixtures of various organophosphorus extractants

Synergistic solvent extraction of Eu(III) and Tb(III) from thiocyanate solutions with mixtures of 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (EHPNA) and di-2-ethylhexylphosphoric acid (DEHPA) or tributyl phosphate (TBP) or trioctylphosphine oxide (TOPO) or triphenylphosphine oxide (TPhPO) in benzene has been studied. The mechanism of extraction can be explained by a simple chemically based model presented in this paper. The equilibrium constants of the mixed-ligand species of the various neutral donors have been determined by non-linear regression analysis.     

Determination of bromide and nitrite by indirect redox titration using phenyl iodosoacetate

Bromide has been determined by its oxidation with an excess of phenyl iodosoacetate in the presence of acetanilide to give bromine which subsequently reacts with acetanilide to form 4-bromoacetanilide. The residual amount of phenyl iodosoacetate was evaluated iodometrically. Thus, for every mol of bromide one mol of phenyl iodosoacetate was consumed. For the determination of bromine in organic compounds, the test substance was decomposed by fusion with alkali peroxide to liberate bromide which was then evaluated by the phenyl iodosoacetate method. For its determination, nitrite has been reacted with an excess of isoniazid in acid medium to form isonicotinyl azide (which does not react with phenyl iodosoacetate) and the residual amount of isoniazid was titrated with phenyl iodosoacetate in the presence of acidified bromide and methyl red indicator (when isoniazid and phenyl iodosoacetate react in a 12 molar ratio). Each mol of nitrite is equivalent to 2 mol of phenyl iodosoacetate.     

Triple-quantum magic angle spinning (27)Al NMR of aluminum hydroxides

We show that (27)Al triple-quantum magic angle spinning (3Q-MAS) experiments alleviate the second-order quadrupolar broadening to reveal the structure-building units of nonequivalent aluminum octahedra in the most extensively studied aluminum hydroxides, namely, gibbsite, bayerite, and boehmite. Further, aided by ab initio calculations of the electric field gradient tensors, the 3Q-MAS/MAS results are shown to lead to the assignment of (27)Al isotropic resonances to the aluminum positions in their X-ray-determined structures. The present work paves the way for future studies on various structurally transformed materials derived from these basic aluminum hydroxides.     

Differential pulse anodic stripping voltammetric determination of ziram (a dithiocarbamate fungicide)

A d.c. polarographic technique has been used previously for the determination of the pesticide, ziram, in aqueous samples, this paper reports differential pulse anodic stripping voltammetric determination of ziram zinc in rice samples using a static mercury drop electrode. The procedure developed distinguishes inorganic zinc and ziram zinc in sodium acetate-sodium chloride media. The procedure developed is suitable for the determination of concentrations as low as 10 ppb of ziram with a precision of 2.1% for five successive determinations of 150 ppb of ziram.     

Sensitive flotation-spectrophotometric method for the determination of vanadium (IV) with 3,5-dinitrosalicylic acid and rhodamine B

Vanadium(IV) is determined by reaction with 3,5-dinitrosalicylic acid and rhodamine B in weakly acidic medium. The flotation of the ternary ion-association complex is carried out with cyclohexane followed by dissolution in acetone for subsequent spectrophotometric determination. The molar absorptivity is 5.91×10⁵ l mole^–1 cm^–1 at 555 nm. Beer's law is obeyed in the range 0.05–1.5 g vanadium(IV) in 25 ml. The method is selective for vanadium(IV) in the presence of sodium fluoride and has been applied to standard reference materials.     

Study of single phase YBa2Cu3O7−δ compound around 1–2–3 stoichiometry

The structural changes accompanying small stoichiometric variations around 1–2–3 composition in the Y-Ba-Cu-O compound have been investigated. Ba-deficient composition is found to give considerable orientation along (001). This oriented powder gives a higher current density compared to the unoriented powder. The temperature has been correlated with stoichiometry.     

Ultratrace determination of europium in high-purity lanthanum, praseodymium and dysprosium oxides by luminescence spectrometry

A luminescence spectrometric method was developed for the determination of ultra trace amounts of europium (down to 1 x 10(-13) M) in high purity lanthanum, praseodymium and dysprosium oxides. This is based on the enhanced luminescence of europium-thenoyltrifluoroacetone (TTA)-dibenzo-18-crown-6 (DBC)-Triton X-100 in the presence of terbium. The fluorescence intensity is linear with europium concentration in the range 1 x 10(-11) - 1 x 10(-6) M under the recommended conditions. The optimized procedure is successfully utilized for the determination of ultratrace amounts of europium in lanthanium, praseodymium and dysprosium oxides.     

Spectrophotometric determination of trace amounts of cadmium in high purity zinc materials with iodide and rhodamine 6G

A highly selective and sensitive spectrophotometric procedure for the determination of cadmium is developed. This is based on the interaction of rhodamine 6G with tetraiodocadmate (II) anion to form a pink product which absorbs maximally at 575 nm that is stable for 24 hr when stabilized with gelatin. Cadmium concentrations as low as 0.01 ppm can be readily determined. The method is precise and has been applied to synthetic sea water samples and high purity zinc materials.     

Predicting performance measures for Markovian type of manufacturing systems with product failures

Optoelectronic products are typically assembled and tested in a flow shop environment with multiple processors at each stage. The first few stages are dedicated for assembly and the later stages are dedicated for calibration and testing. Whenever a product (or job) fails at a stage, it is routed back to one of the downstream stages or to the same stage (depending upon the nature of the failure). Consequently, the product could circulate several times between the current stage and the preceding stage(s) before moving to the next stage. Estimating the performance measures (such as WIP and flow time) of such manufacturing systems is not trivial. This paper presents analytical approximations to estimate the performance measures of a manufacturing system with multiple product classes, job circulations due to failures, and some resources being shared among different product classes. The analytical approximations were verified using simulation on several problem instances. The experimental study indicates that these approximations can be used by operations managers to estimate the performance measures of a manufacturing system with product failures.