Extensional viscosity from entrance pressure drop measurements

Extensional rheological properties are important in characterization and processing of polymeric liquids. The use of entrance pressure drop to obtain extensional viscosity is particularly attractive because it can be applied to both low and high viscosity liquids using the Bagley correction obtained from a conventional capillary rheometer.Low density polyethylene of three different melt index values, including IUPAC-X (a different batch of IUPAC-A), and a high density polyethylene were tested using a commercial capillary rheometer. The entrance pressure drop (P _en ) was obtained with a zero-length orifice die with an abrupt contraction. The contraction ratio was 12:1. Predictions from several approximate analyses to calculate the uniaxial extensional viscosity _u (using an axisymmetric contraction) from P _en were compared. These comparisons are summarized in the appendices.Due to the transient nature of contraction flows, _u is also a function of the strain (). This was examined by comparing _u from P _en (Cogswell's analysis was chosen for convenience) with transient extensional viscosity ( _u ⁺) at different magnitudes of from fiber-windup technique (Padmanabhan et al., 1996). _u ⁺ at 3 was found to be close to _u from P _en (using Cogswell's analysis) for two LDPE samples that had fiber-windup data available. The magnitude of the strain in the contraction did not vary with strain rate.Dedicated to the memory of Tasos Papanastasiou     

Performance evaluation of artificial neural network approaches in forecasting reservoir inflow

This study investigates the potential of Time Lag Recurrent Neural Networks (TLRN) for modeling the daily inflow into Eleviyan reservoir, Iran. TLRN are extended with short term memory structures that have local recurrent connections, thus making them an appropriate model for processing temporal (time-varying) information. For this study, the daily inflow into Eleviyan reservoir between years 2004–2007 was considered. To compare the performance of TLRN, a back propagation neural network was used. The TLRN model with gamma memory structure, eight input layer nodes, two hidden layer and one output layer (8-2-1) was found performing best out of three different models used in forecasting daily inflow. A comparison of results with back propagation neural network suggest that neither TLRN nor back propagation approaches were good in forecasting high inflow but, both approaches perform well when used to forecast low inflow values. However, statistical test suggests that both TLRN and back propagation neural network models were able to reproduce similar basic statistics as that of the actual data.     

Complexes of hydrazine and substituted hydrazines with some oxocations

Summary Several new polymeric complexes of general composition MO_n(L)₄X₂ (where M = V, Zr and U; n = 1 or 2; X = Cl, Br, I, NO₃ and NCS and L = N₂H₄, PhNHNH₂ and Me₂NNH₂ have been synthesised and characterized by elemental and d.t. analyses and by magnetic measurements, electronic and i.r. spectra. The vanadyl(IV) complexes exhibit subnormal magnetic moments (1.26–1.36BM) possibly because of exchange interaction between vanadium(IV) ions. The thermal stability of hydrazine complexes fall in the order: Cl>Br>NCS>I. The M-N bond strength, as revealed, by v(M-N), decreases as: Me₂NNH₂>N₂H₄>PhNHNH₂.Presented in symposium on Frontiers of coordination chemistry, Allahabad University, Allahabad, Dec. 6–8, 1979.     

Single robust RP-HPLC analytical method for quantification of curcuminoids in commercial turmeric products,Ayurvedic medicines,and nanovesicular systems

A single robust reversed-phase high-performance liquid chromatography (RP-HPLC) method was developed and validated as per International Conference on Harmonization guidelines for the accurate quantification of curcuminoids in commercial turmeric products, Ayurvedic medicines, and nanovesicular systems. The proposed chromatographic method was found to be specific, linear (r²?≥?0.999), precise at intra- and inter-day levels (percentage relative standard deviation <2.0%), accurate (percentage recovery 99.14–102.29%), and robust. The limits of detection and quantification were found to be 7.40 and 24.70?ng?mL^?1 for curcumin, 9.24 and 30.80?ng?mL^?1 for demethoxycurcumin, and 6.48 and 21.61?ng?mL^?1 for bisdemethoxycurcumin, respectively. Among different commercial turmeric products and Ayurvedic medicines tested, the contents of curcumin (3.54?±?0.06–25.8?±?0.08?mg?g^?1), demethoxycurcumin (1.28?±?0.02–9.97?±?0.03?mg?g^?1), and bisdemethoxycurcumin (0.50?±?0.01–5.97?±?0.01?mg?g^?1) varied significantly. The developed method was effectively applied to the determination of encapsulation efficiency of curcuminoids (ranged between 84.33?±?3.50 and 96.59?±?2.53%) in the nanovesicular systems. In conclusion, the reported method is suitable for the analysis of curcuminoids in a wide variety of turmeric products and used for the quality control of products that contain curcuminoids.     

Yb(OTf)3 catalyzed new cascade reaction: a facile assembly of fused quinazolinones

A one-pot Yb(III)-mediated cascade reaction has been developed leading to small molecules based on a novel structural motif, i.e. quinazolin-4-one moiety fused with an isoquinoline ring, for potential inhibition of TNF-α.     

The kinetics of oxidation of N(2-hydroxyethyl)ethylenediaminetriacetatocobaltate(II) by peroxodisulfate ion in aqueous acidic solutions

Summary Peroxodisulfate ion readily oxidises Co^II-YOH [YOH =N(2-hydroxyethyl)ethylenediaminetriacetate] with the formation of an intermediate complex. The kinetics of the electron-transfer step follow the rate law: Rate = 2k_HK_H[H⁺][S₂O₈]²-[Co^II-YOH]/(1 + K_H[H⁺]) where [S₂O₈]^2– is the total peroxodisulfate concentration, k_H is the rate constant for the electron-transfer process, and K_H is the pre-equilibrium protonation constant. Activation parameters have been evaluated. The intermediate, which was identified spectrophotometrically, slowly rearranges to the quinquedentate species Co(YOH)(H₂O). The rate of this rearangement has also been measured.     

Density functional theory study of ω phase in steel with varied alloying elements

The presence of a long-abandoned hexagonal omega (ω) phase in steel samples is recently gaining momentum owing to the advances in transmission electron microscopy (TEM) measurements, even though it is already reported in other transition-metal alloys. The stabilization of this metastable phase is mainly investigated in presence of C, even though the formation of the ω phase is attributed to the combined effect of many factors, one among which is the enrichment of solute elements such as Al, Mn, Si, C, and Cr in the nanometer-sized regimes. The present study investigates the effect of the above alloying elements in ω-Fe using density functional theory (DFT) calculations. It is seen that the magnetic states of the atoms play a major role in the stability of ω-Fe. Cohesive energy calculations show that the alloying elements affect the energetics and stabilization of ω-Fe. Further, density of states calculations reveal the variation in d-band occupancy in the presence of alloying elements, which in turn affects the cohesive energy. Phonon band structure calculations show that only ω-Fe with substitutional C shows positive frequencies and hence possess thermodynamic stability. Finally, we confirm the existence of ω-Fe using TEM measurements of a steel sample containing the same alloying elements. Our results can shed light on the stabilization of the ω in other transition-metal alloys as well, in the presence of minor alloying elements.     

Diastereoselective synthesis of (+)-nephrosterinic acid and (+)-protolichesterinic acid

A diastereoselective synthesis of (+)-nephrosterinic acid and (+)-protolichesterinic acid, common members of the paraconic acids is described. The synthesis is based on a diastereoselective orthoester Johnson–Claisen rearrangement of a (Z)-allyl alcohol with a vicinal dioxolane moiety as key steps. The synthesis is completed in 10 steps and with overall yields of 15.9% for (+)-nephrosterinic acid and 16.4% for (+)-protolichesterinic acid.     

Synthesis and characterization of polyurethane–polyvinylbenzyl chloride multiblock copolymers and their cationomers using a polyurethane macroiniferter

Polyurethane iniferter prepared from isocyanate end capped prepolymer and 1,1,2,2-tetraphenyl-1,2-ethanediol, has been used to polymerize vinylbenzyl chloride to obtain polyurethane-polyvinylbenzyl chloride multiblock copolymers. Formation of the block copolymers proceeds with increase in both molecular weight and conversion with increasing polymerization time showing that the polymerization proceeds via a “living” radical mechanism. The block copolymers so obtained were converted into their cationomers by the treatment of triethylamine. The block copolymers and their cationomers have been characterized by FTIR, FTNMR, TGA, and DSC studies. The effect of thermal energy on the molecular weight of the macroiniferter in the absence of monomer has been studied in order to understand the mechanism of formation of the block copolymers. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1237–1244, 1997