Halogen oxidation and nitrosylation of some aldimine and ketimine carbonyl complexes of chromium and molybdenum

Summary The halogen oxidation and nitrosylation of cis-[(SB)M-(CO)₄] [M = Cr or Mo, SB = N,N-ethylenebis(p-tolualideneimine), N,N-ethylenebis(p-N,N-dimethylaminobenzalideneimine) or N,N-ethylenebis(methyl-p-methoxyphenylketimine); M = Mo, SB = N,N-ethylenebis-(cinnamylideneimine) or N,N-ethylenebis(methyl-p-methylphenylketimine)] have been studied. Halogenation of [(SB)Cr(CO)₄] yielded [(SB)CrX₂] (X = Cl, Br or I) where-as [(SB)Mo(CO)₄] gave [(SB)Mo(CO)₃X₂] (X = Br or I) and [(SB)MoX _x ] (X = I, n = 2; X = Cl or Br, n = 4). NOCl produced [(SB)Cr(NO)₂Cl₂] and [(SB)Mo(CO)₂(NO)Cl] when reacted with the corresponding [(SB)M(CO)₄]. The complexes were characterized by physico-chemical and spectroscopic measurements.     

Mechanistic study of osmium(VIII) promoted oxidation of crotonic acid by aqueous alkaline solution of potassium bromate

Kinetics and mechanism of the Os(VIII) catalysed oxidation of crotonic acid (CA) by KBrO₃ in alkaline medium have been investigated. Zero order dependence in [KBrO₃] was observed, while first order with respect to CA in its lower concentration range tends to zero order at its higher concentration range. The order in [Os(VIII)] was found to be unity and a positive effect of [OH⁻] was observed. Variation of the ionic strength (μ) and dielectric constant of the medium and addition of Hg(OAc)₂ (used as Br⁻ scavenger) had an insignificant effect on the rate of reaction. Thermodynamic parameters have also been calculated and reported. A suitable mechanism consistent with the observed kinetic results has been suggested and the related rate law deduced.     

Thermal characterization of bismaleimide blends

4,4-bismaleimidophenyl methane (BM) and 3,3-bismaleimidophenyl sulfone (BS) were blended in solution using weight ratios 31 (MS31), 21 (MS21), 11 (MS11), 12 (MS12) and 13 (MS13). Chain extended bismaleimide resins were also prepared by treating BS/BM with 4,4-diaminodiphenyl ether in molar ratios of 10.3 (BM-E and BS-E resins). These resins were also blended with bismaleimides and the curing characteristics were evaluated by differential scanning calorimetry. Increase in BM content in BMBS blends or increase in chain extended bismaleimide content in BM-EBS or BS-E BM blends resulted in a reduction of melting and curing temperatures. Indication about the extent of cross-linking was obtained from solubility measurements (in DMF) of isothermally cured resins (180 °C, lh and 220 °C, lh in an air oven). Thermogravimetric analysis of samples isothermally cured at 180 °C and 220 °C (lh each) was carried out in nitrogen atmosphere. Improvement in thermal stability of chain extended bismaleimides was observed on blending.

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Zusammenfassung 4,4-Bismalimidophenyl-methan (BM) und 3,3-Bismalimidophenyl-sulfon (BS) wurden in Lösung in den Gewichtsverhältnissen 31 (MS31), 21 (MS21), 11 (MS11), 12 (MS12) und 13 (MS13) gemischt. Auch kettenpolymerisierten Bismalimid-Harze wurden durch Behandlung von BS/BM mit Diaminodiphenylether im Molverhältnis 10,3 dargestellt (BM-E- und BS-E-Harze). Die Kennwerte der Aushärtung von Mischungen dieser Harze mit den Bismalimiden wurden mittels DSC ermittelt. Eine Erhöhung des BM-Gehaltes in den BM BS-Mischungen oder des Gehaltes der BM-E BS oder BS-E-Mischungen an kettenpolymerisierten Bismalimiden führt zu einer Erniedrigung der Schmelz- und Aushärtetemperaturen. Hinweise über den Vernetzungsgrad wurden aus Löslichkeitsmessungen (in DMF) von Isotherm (je 1 Stunde bei 180 und 220 °C in Luft) gehärteten Harzen erhalten. Die thermogravimetrische Analyse der Isotherm bei 180 bzw. 220 °C 1 Stunde ausgehärteten Proben wurde in Stickstoffatmosphäre ausgeführt. Die thermische Stabilität der Bismalimide wird durch Verschneiden verbessert.

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4,4-- () 3,3-- () 31 (MC 31), 21 (MC 21), 11 (MC 11), 12 (MC 12) 13 (MC13). - / 4,4- 10,3 ( - C-). - . - - - - , . ( 1 180 220°) . . - .

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The financial assistance provided by Department of Science and Technology is gratefully acknowledged.     

Microdetermination of carbonyl compounds by reduction with alkaline sodium borohydride

Summary Alkaline sodium borohydride has been employed as a reducing reagent for the titrimetric determination of compounds containing the carbonyl function. The sample is dissolved in methanol and is then reduced with alkaline sodium borohydride. After completion of the reaction, the excess sodium borohydride is back titrated against standardized hydrochloric acid solution using methyl red as indicator. The stoichiometry between the carbonyl function and sodium borohydride is 41.

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Zusammenfassung Natriumborhydrid dient als Reduktionsmittel zur Titration von Carbonylverbindungen. Die Probe wird in Methanol gelöst und dann mit alkalischem Natriumborhydrid reduziert. Nach Ablauf der Reaktion wird der Überschuß mit Salzsäure gegen Methylrot zurücktitriert. Carbonylverbindung und Natriumborhydrid reagieren im Verhältnis 41.

     

Modeling of transient electroluminescence overshoot in bilayer organic light-emitting diodes using rate equations

When a voltage pulse is applied under forward biased condition to a spin-coated bilayer organic light-emitting diode (OLED), then initially the electroluminescence (EL) intensity appearing after a delay time, increases with time and later on it attains a saturation value. At the end of the voltage pulse, the EL intensity decreases with time, attains a minimum intensity and then it again increases with time, attains a peak value and later on it decreases with time. For the OLEDs, in which the lifetime of trapped carriers is less than the decay time of the EL occurring prior to the onset of overshoot, the EL overshoot begins just after the end of voltage pulse. The overshoot in spin-coated bilayer OLEDs is caused by the presence of an interfacial layer of finite thickness between hole and electron transporting layers in which both transport molecules coexist, whereby the interfacial energy barrier impedes both hole and electron passage. When a voltage pulse is applied to a bilayer OLED, positive and negative space charges are established at the opposite faces of the interfacial layer. Subsequently, the charge recombination occurs with the incoming flux of injected carriers of opposite polarity. When the voltage is turned off, the interfacial charges recombine under the action of their mutual electric field. Thus, after switching off the external voltage the electrons stored in the interface next to the anode cell compartment experience an electric field directed from cathode to anode, and therefore, the electrons move towards the cathode, that is, towards the positive space charge, whereby electron–hole recombination gives rise to luminescence. The EL prior to onset of overshoot is caused by the movement of electrons in the electron transporting states, however, the EL in the overshoot region is caused by the movement of detrapped electrons. On the basis of the rate equations for the detrapping and recombination of charge carriers accumulated at the interface expressions are derived for the transient EL intensity I, time t_m and intensity I_m corresponding to the peak of EL overshoot, total EL intensity I_t and decay of the intensity of EL overshoot. In fact, the decay prior to the onset of EL overshoot is the decay of number of electrons moving in the electron transporting states. The ratio I_m/I_s decreases with increasing value of the applied pulse voltage because I_m increases linearly with the amplitude of applied voltage pulse and I_s increases nonlinearly and rapidly with the increasing amplitude of applied voltage pulse. The lifetime τ_t of electrons at the interface decreases with increasing temperature whereby the dependence of τ_t on temperature follows Arrhenius plot. This fact indicates that the detrapping involves thermally-assisted tunneling of electrons. Using the EL overshoot in bilayer OLEDs, the lifetime of the charge carriers at the interface, recombination time of charge carriers, decay time of the EL prior to onset of overshoot, and the time delay between the voltage pulse and onset time of the EL overshoot can be determined. The intense EL overshoot of nanosecond or shorter time duration may be useful in digital communication, and moreover, the EL overshoot gives important information about the processes involving injection, transport and recombination of charge carriers. The criteria for appearance of EL overshoot in bilayer OLEDs are explored. A good agreement is found between the theoretical and experimental results.     

Synthesis and bioactivity evaluation of eugenol hybrids obtained by Mannich and 1,3 dipolar cycloaddition reactions

Design, synthesis, and bioactivity evaluation of novel mannich bases ( 2a-2j ) and triazole-chalcone derivatives ( 7a-7k ) of Eugenol 1 were reported. Among all the derivatives tested for antiproliferative activity, di-amine manich derivative 2b (32.92 μM), and 4-methoxy chalcone triazole derivative 7d (33.05 μM) significantly inhibited HepG2 cell lines when compared to the standard doxorubicin (37.29 μM). Whereas most of the compounds such as diethylamine 2a (17.75 μM), (aminomethyl) methane diamine 2b (17.02 μM), and bis (chloromethyl) amine 2c (20.12 μM) showed moderate to better inhibition towards MCF-7 cell lines. The synthesized analogues were also tested for antidiabetic and antiobesity potentials. Compounds 2f (55.50%), 2c (54.34%), 7g (55.5%), and 2a (55.5%) have shown moderate inhibitory potentials toward intestinal α-glucosidase enzyme when compared to the standard Acarbose (72.86%). Likewise, compounds 7d (82.95%), 7f (76.19%), 7g (74.81%), 7e (74.81%), and 2g (72.50%) have shown significant to moderate inhibitory potentials toward Pancreatic lipase enzyme when compared to the standard orlistat (91.10%). ROS induces life-threatening diseases like diabetes, cancer, etc., and antioxidants play a major role in controlling their production. Compounds 2c (99.81%), 2i (99.80%), 2d (99.26%), 2g (98.79%), and 2f (98.42%) have shown significant antioxidant profiles in ABTS assay when compared to the standard Trolox (99.07%). Further, In silico Molecular docking and pharmacokinetic screening of the eugenol derivatives complemented the in vitro results indicating the drug likeness of the obtained active compounds.     

Highly Selective and Sensitive Graphene Based Electrochemical Sensor for Quantification of Receptor Agonist Rizatriptan

A highly selective and sensitive electrochemical sensor has been developed by modification of a glassy carbon electrode (GCE) with graphene (GRP) for quantification of Rizatriptan. The significant increase of the peak current and the improvement of the oxidation peak potential indicate that the electrochemical sensor facilitates the electron transfer of Rizatriptan. The oxidation peak current was proportional to the Rizatriptan concentration in the range from 100 to 600 µg/mL with detection (LOD) and quantification limit (LOQ) of 36.52 and 121.73 µg/mL, respectively. The developed method was successfully employed for quantification of Rizatriptan in pharmaceutical formulations. The sensor shows great promise for simple, sensitive and quantitative detection of Rizatriptan.     

Sensitive and selective methods for determination of antipsychotic drug olanzapine in pharmaceuticals

Two simple and sensitive spectrophotometric methods have been developed for analysis of the antipsychotic drug olanzapine in pharmaceuticals. Method A is based on liberation of iodine by reaction between the drug and potassium iodate, followed by reaction with leuco crystal violet (LCV), the color of oxidized LCV being measured at 598 nm. Method B is based on oxidation of olanzapine with chloramine-T (CAT) in acidic medium, the unconsumed CAT being determined with rhodamine B, measuring the absorbance at 550 nm. Calibration graphs were linear over the ranges of 0.05–2.0 and 0.1–1.6 μg mL^?1 olanzapine for method A and B, respectively. The molar absorptivity, Sandell’s sensitivity, detection limit, and quantitation limit were found to be 1.59 × 10⁵, 0.00132, 0.038, and 0.117, respectively, for method A and 0.953 × 10⁵, 0.00221, 0.064, and 0.192, respectively, for method B. The optimum conditions and other analytical parameters were evaluated. The proposed methods have been applied successfully for analysis of olanzapine in pure form and its dosage forms, and no interference was observed from common excipients present in pharmaceutical formulations.     

Dynamic Mechanical Behaviour of Some Cholesteryl Liquid Crystals

Dynamic mechanical studies of cholesteric liquid crystalline substances in the solid state have been reported using Du Pont's Dynamic Mechanical Analyser, DMA-981. All the substances showed multiple transitions. There is no common transition though the parent structure was similar in the compounds. These weak transitions are not detectable by DSC and hence appear to be second order transitions possibly arising due to rotation of the molecules around the long axis. Alternatively the lattice defects may also be responsible for such transitions.