An Easy Spectrophotometric Method for the Determination of Hypochlorite Using Thionin

A simple, rapid, and sensitive spectrophotometric method has been developed for the determination of hypochlorite using thionin. The method is based on the reaction of hypochlorite with potassium iodide in acidic medium to liberate iodine. The liberated iodine bleaches the violet color of thionin, which is measured at 600 nm. The decrease in absorbance is directly proportional to the concentration of hypochlorite. Beer’s law is obeyed in the range 0.2– 1.2 µg/mL of hypochlorite. The molar absorptivity, Sandell’s sensitivity, detection limit, and quantitation limit are found to be 1.489 × 10⁴ L/(mol cm), 3.25 × 10⁻³ µg cm⁻², 0.1026 µg/mL, and 0.3112 µg/mL, respectively. The method has been successfully applied to the determination of hypochlorite in various samples of natural water, tap water, milk, etc.__________From Zhurnal Analiticheskoi Khimii, Vol. 60, No. 8, 2005, pp. 798–801.Original English Text Copyright © 2005 by Narayana, Mathew, Vipin, Sreekumar, Cherian.The text was submitted by the authors in English.     

Mesoporous aluminosilicate promoted protection and deprotection of carbonyl compounds

Mesoporous aluminosilicates are efficient heterogeneous catalysts for both the formation and hydrolysis of a range of acetals under mild conditions and in short reaction times.     

Average termination rate coefficients in emulsion polymerization: Effect of compartmentalization on free‐radical lifetimes

A method is presented by which the time‐dependent average termination rate coefficient in an emulsion polymerization may be calculated as an appropriate average of the chain‐length‐dependent termination rate coefficients. The method takes advantage of the fact that the overall termination rate is dominated by terminations between rapidly moving short radicals and much slower long ones. This termination rate coefficient is suitable for use in the Smith–Ewart equations describing the compartmentalization of radicals in an emulsion polymerization. Rate data in emulsion polymerizations can be quantitatively interpreted if the kinetics fall into one of two categories: zero–one (showing compartmentalization; intraparticle termination is not rate‐determining) or pseudo‐bulk (no compartmentalization; intraparticle termination is rate‐determining). The new method can be used to interpret rate data for systems falling between these categories and also can be used to find termination rate coefficients from Monte Carlo simulations of termination kinetics. The latter is especially useful for predicting and understanding kinetics in controlled radical polymerizations in disperse media. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1076–1089, 2005     

Stereoselective synthesis of highly substituted tetrahydrofuran derivatives via Huisgen 1,3-dipolar cycloaddition of acyclic carbonyl ylides to activated styrenes

Stereoselective synthesis of highly functionalized tetrahydrofurans via the 1,3-dipolar cycloaddition reaction of acyclic carbonyl ylides to activated alkenes is described.     

FT‐IR,FT‐Raman and DFT calculations of the salicylanilide derivate 4‐chloro‐2‐(4‐bromophenylcarbamoyl)phenyl acetate

FT‐IR and FT‐Raman spectra of 4‐chloro‐2‐(4‐bromophenylcarbamoyl)phenyl acetate were recorded and analyzed. The vibrational wavenumbers and corresponding vibrational assignments were examined theoretically using the Gaussian03 set of quantum chemistry codes. The red shift of the NH stretching wavenumber in the infrared (IR) spectrum from the computed wavenumber indicates the weakening of the NH bond resulting in proton transfer to the neighbouring oxygen atom. The simultaneous IR and Raman activations of the CO stretching mode give the charge transfer interaction through a π‐conjugated path. Optimized geometrical parameters of the title compound are in agreement with similar reported structures. From the optimized structure, it is clear that the hydrogen bonding decreases the double bond character of CO bond and increases the double bond character of the C N bonds. The first hyperpolarizability, predicted infrared intensities and Raman activities are reported. The calculated first hyperpolarizability is comparable with the reported values of similar derivatives and is an attractive object for future studies of non‐linear optics. The assignments of the normal modes are done by potential energy distribution (PED) calculations. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis,Characterization, and Electron-Transfer Properties of Ferrocene–BODIPY–Fullerene Near-Infrared-Absorbing Triads: Are Catecholopyrrolidine-Linked Fullerenes a Good Architecture to Facilitate Electron-Transfer?

A series of covalent ferrocene–BODIPY–fullerene triads with the ferrocene groups conjugated to the BODIPY π-system and the fullerene acceptor linked at the boron hub by a common catecholpyrrolidine bridge were prepared and characterized by 1D and 2D NMR, UV/Vis, steady-state fluorescence spectroscopy, high-resolution mass spectrometry, and, for one of the derivatives, X-ray crystallography. Redox processes of the new compounds were investigated by electrochemical (CV and DPV) methods and spectroelectrochemistry. DFT calculations indicate that the HOMO in all triads was delocalized between ferrocene and BODIPY π-system, the LUMO was always fullerene-centered, and the catechol-centered occupied orbital was close in energy to the HOMO. TDDFT calculations were indicative of the low-energy, low-intensity charge-transfer bands originated from the ferrocene–BODIPY core to fullerene excitation, which explained the similarity of the UV/Vis spectra of the ferrocene–BODIPY dyads and ferrocene–BODIPY–fullerene triads. Photophysical properties of the new triads as well as reference BODIPY–fullerene and ferrocene–BODIPY dyads were investigated by pump-probe spectroscopy in the UV/Vis and NIR spectral regions following selective excitation of the BODIPY-based antenna. Initial charge transfer from the ferrocene to the BODIPY core was shown to outcompete sub-100 fs deactivation of the excited state mediated by the catechol bridge. However, no subsequent electron transfer to the fullerene acceptor was observed. The initial charge separated state relaxes by recombination with a time constant of 150–380 ps.     

The influence of nanocellulosic fiber,extracted from <Emphasis Type=Italic>Helicteres isora</Emphasis>, on thermal,wetting and viscoelastic properties of poly(butylene succinate) composites

In this study, the thermal, wetting and viscoelastic properties of biodegradable poly(butylene succinate)–isora nanofibril (PBS–INF) composites were investigated. Optical polarizing microscopy showed that incorporating INF in PBS enhanced the number of nucleation sites while also reducing its spherulitic size. Wide-angle X-ray diffraction results showed the influence of INF on the crystal structure of PBS. Dynamic mechanical analysis results revealed increases in storage and loss moduli with increasing INF content. Differential scanning calorimetry analysis showed that incorporating INF facilitated crystallization at higher temperatures. INF slightly enhanced the melting behavior of PBS matrix. Thermogravimetric analysis results demonstrated no definitive change in the thermal stability of PBS upon inclusion of INF. Contact angle studies showed enhancement in the hydrophilic nature of PBS–INF composites. Overall, INF had a positive influence on the thermophysical properties of PBS providing a feasibility for using PBS–INF composites in automotive interiors, food packaging and related applications.     

Boxicity of line graphs

The boxicity of a graph H, denoted by , is the minimum integer k such that H is an intersection graph of axis-parallel k-dimensional boxes in R^k. In this paper we show that for a line graph G of a multigraph, , where Δ(G) denotes the maximum degree of G. Since G is a line graph, Δ(G)≤2(χ(G)−1), where χ(G) denotes the chromatic number of G, and therefore, . For the d-dimensional hypercube Q_d, we prove that . The question of finding a nontrivial lower bound for was left open by Chandran and Sivadasan in [L. Sunil Chandran, Naveen Sivadasan, The cubicity of Hypercube Graphs. Discrete Mathematics 308 (23) (2008) 5795–5800].The above results are consequences of bounds that we obtain for the boxicity of a fully subdivided graph (a graph that can be obtained by subdividing every edge of a graph exactly once).     

Photolysis of acetyl esters of 2,2′-dinitrodiphenyl-carbinols in protic and aprotic solvents

Irradiation ofacetyl esters of 2,2′-dinitrodiphenyl-carbinols (1a-d) in aprotic medium like 2-propanol yielded dibenzol [c,f]-[1,2]diazepin-11-one-5-oxides (5a-d) as the major product. Dibenzoi[c,f]-[1,2]diazepin-11-one (2a-d), 2,2′-dinitrobenzophenones (3a-d), 2-amino-2′-nitrobenzophenones (4a-d), and N-hydroxyacridones (6a-d) were also formed in varying amounts. Irradiation of 1a-d in an aprotic medium like benzene yielded the above products along with benzisoxazoles (7a-d) also. When triethylamine was used as the solvent the major product obtained was N-hydroxyacridones (6a-d). Plausible mechanisms for the formation of the products are discussed