Cationic surfactant-selective potentiometric sensors based on neutral ion-pair carrier complexes

Poly(vinyl chloride) (PVC) membrane electrodes to determine monomer concentrations of tetradecyltrimethylammonium ion (TTA⁺) and hexadecylpyridinium ion (HPy⁺) based on neutral ion-pair carrier complexes of tetradecyltrimethylammonium dodecyl sulfate (TTA⁺-DS⁻) and hexadecylpyridinium dodecyl sulfate (HPy⁺-DS⁻), respectively, are reported here. The electrodes exhibit a Nernstian slope of 59 mV per decade for TTA⁺ and a sub-Nernstian slope of 34.5 mV per decade for HPy⁺ ions. The TTA⁺ ion-selective electrode (ISE) and the HPy⁺-ISE can determine the monomer units down to concentrations as low as 4.0×10⁻⁴M and 1.66×10⁻⁵ M, respectively. The effect of various additives, such as the anionic polyelectrolyte sodium dextran sulfate and macrocyclic β-cyclodextrin, on the surface activity exhibited by the cationic surfactants TTA⁺-DS⁻ and HPy⁺-DS⁻, in the presence of background concentrations of NaCl was also examined with surfactant-selective sensors. The Gibbs free energy of micelle formation (ΔG _m ) of both surfactants in the presence of various additives was calculated and found to be less favorable with respect to an increase in the amount of additives due to less availability of cationic surfactant monomer units. The ion-pair complexes TTA⁺-DS⁻ and HPy⁺-DS⁻ were found to behave as selective carrier compounds in PVC membranes in determining the concentration of monomer units of both TTA⁺ and HPy⁺, respectively. The proposed sensors worked well at a fairly acidic pH of 1–6.5 with response time of 60 s. The sensors responded well to the surfactant ions even in the presence of additives at lower concentration. The lifetime of the sensors is 3 mon.     

Phase‐transfer‐agent‐aided polymerization and graft copolymerization of acrylamide

The use of phase‐transfer catalysts, with water‐insoluble initiators, for polymerization and graft copolymerization reactions was explored. The polymerization of a water‐soluble vinyl monomer, acrylamide (AAm), and the graft copolymerization of AAm onto a water‐insoluble polymer backbone, isotactic polypropylene (IPP), with a water‐insoluble initiator, benzoyl peroxide (BPO), and a phase‐transfer catalyst, tetrabutyl ammonium bromide (Bu₄N⁺Br^?), were carried out in a water/xylene binary solvent system. The conversion percentage of AAm into polyacrylamide (PAAm) and the percentage of grafting of AAm onto IPP were determined as functions of various reaction parameters, such as the BPO, AAm, and phase‐transfer‐catalyst concentrations, the amounts of water and xylene in the water/xylene mixture, the time, and the temperature. The graft copolymer, IPP‐g‐PAAm, was characterized with IR spectroscopy and thermogravimetric analysis. By a comparison of the results of the phase‐transfer‐catalyzed graft copolymerization of AAm onto IPP and the preirradiation method, it was observed that the optimum reaction conditions were milder for the phase‐transfer‐catalyst‐aided graft copolymerization. Milder reaction conditions, including the temperature, the time of reaction, and a moderate initiator (BPO), in comparison with high‐energy γ‐rays, led to better quality products, and the reaction proceeded smoothly with high productivity. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2364–2375, 2004     

Moisture Adsorption Isotherms of Watermelon Seed and Kernels

The moisture adsorption isotherms of watermelon seeds and kernels from Citrullus lanatus Cv Mateera and Citrullus vulgaris Cv Sugar baby were obtained using standard static method with saturated salt solutions over a range of water activities from 0.113 to 0.92 at 20–60°C. The adsorption capacity of seeds decreased with the increase in temperature at constant water activity. Sorption models were used to explain the adsorption behavior involving water activity and moisture content (Type I) and also temperature (Type II). Oswin's models gave best fit among Type I with coefficient of determination of 0.953–0.995, standard error of 0.031–0.0571, mean relative error of 0.071–0.152, and scattered residual plots. Modified Oswin was the best fit model among Type II for the seeds and kernels of both the cultivars with coefficient of determination of 0.997–0.999, standard error of 0.151–0.255, mean relative error of 0.018–0.244, and scattered residual plots. The net isoelectric heat of adsorption, estimated from Clausius-Clapeyron decreased from about 27.0 to 0.5 kJ/mol in kernels and 18.0 to 0.5 kJ/mol in seeds of both the cultivars as the moisture content increased from 5 to 25% (dry basis).     

Sorption Isotherms and Drying Characteristics of Tomato Peel Isolated from Tomato Pomace

Tomato peel was separated from pomace by sedimentation and dried in cabinet and fluidized-bed dryer at 50–70°C using 4–12 kg/m²tray load. The drying of tomato peel took place under the falling rate period and the drying behavior was well described by Page's model with coefficient of determination greater than 0.99 and standard error of 0.003–0.016. A fluidized-bed dryer was much more efficient than a cabinet dryer to dry tomato peel. The moisture adsorption isotherms of tomato peel were obtained by equilibrating above saturated salt solutions of known a _w (0.113–0.92) at 20–60°C. The data were analyzed using fifteen sorption models based on coefficient of determination, standard error, and residual plots. Modified Henderson was the best model for tomato peel with coefficient of determination >0.99, standard error <0.210, and a scattered residual plot. The net isostearic heat of sorption, estimated using the Clausius-Clapeyron equation, was 0.74–23.23 kJ/mol at 2.0–2.5% moisture content (dry basis).     

Rheology of polyacrylonitrile‐based precursor polymers produced from controlled (RAFT) and conventional polymerization: Its role in solution spinning

Polymer solutions in dimethyl sulfoxide (DMSO) as a solvent, made from reversible addition fragmentation chain transfer (RAFT)‐mediated polyacrylonitrile (RAFT^¥ PAN) terpolymer with molecular weight (MW) of 260,000 g/mol and dispersity (Ð) of 1.29, behave differently under applied shear stress than polymer solutions made from conventional PAN (Control PAN) with similar MW (258,000 g/mol) but Ð of 2.05 in the same solvent. The unique rheology of RAFT PAN is because of the reduced amount of high MW polymer fractions. Specifically, a 25% (w/v) polymer solution of RAFT PAN had a viscosity of 198 Pas while the equivalent control PAN polymer solution had a viscosity of 968 Pas at a shear rate of 1 s^?1. Also, RAFT PAN polymer solutions had a longer Newtonian plateau than control PAN polymer solutions. This exhibits more liquid character in RAFT PAN polymer solutions than control PAN polymer solutions at same temperature and concentration. In dynamic tests, RAFT PAN polymer solutions gelled slower than their equivalent control PAN polymer solutions because of their longer polymer chain relaxation times. Slow gelling and higher liquid character in RAFT PAN polymer solutions can result in obtaining stronger and finer precursor fibers during wet spinning. Since RAFT PAN polymer solutions exhibit low viscosity and higher liquid character when compared to its equivalent control PAN at same concentration and temperature, these can allow a wider working window for wet spinning and can also allow higher solid content in the polymer solutions that remain easy to wet spin. This is expected to lead to compact and finer fibers with less voids and higher strength. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44273.     

Whale Optimization Algorithm Approach for Performance Optimization of Novel Xmas Tree-Shaped FinFET

Silicon - Today, Fin shaped Field Effect Transistors (FinFETs) are the framework of the sub-nanometer technology node. The leading semiconductor industry deploys it in low-power (LP) and...     

Synthesis,characterization and use of polymer‐supported phase transfer catalyst in organic reactions

A polymer‐supported (PS) phase transfer catalyst, polyethylene‐g‐quaternary ammonium salt (PE‐g‐Q_N⁺), is prepared through a three‐step graft copolymerization of maleic anhydride (MAn) onto polyethylene (PE) by photochemical method using 1% benzophenone (Bz) as photosensitizer. Post grafted acid hydrolysis of polyethylene‐g‐maleic anhydride (PE‐g‐MAn) results in the preparation of PE‐g‐succinic acid which on further treatment with tetrabutylammonium bromide (TBAB) under basic conditions in tetrahydrofuran (THF) gives PE‐g‐Q_N⁺. Optimum conditions pertaining to maximum percentage of grafting have been evaluated as a function of concentration of maleic anhydride, amount of photosensitizer, and time of reaction. Maximum percentage of grafting (25%) was obtained using 3.57 mol of MAn and 0.5 mL of 1% Bz in 120 min. The PE and graft copolymers, PE‐g‐MAn, and PE‐g‐Q_N⁺ were characterized by FTIR Spectroscopy and thermogravimetric analysis (TGA). The ionic nature of quaternary ammonium salt, PE‐g‐Q_N⁺ has also been confirmed by conductance measurements. PE‐g‐Q_N⁺ reagent have been used successfully for polymerization, amidation, and esterification reactions. The products obtained were characterized by FTIR and H¹NMR spectral methods. The reagent was reused for the further reactions and it was observed that the polymeric reagent polymerize, amidate, and esterificate the compounds successfully but with little lower product yield. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Polymers from renewable resources: Kinetics studies of the radiochemical graft copolymerization of styrene onto cellulose extracted from pine needles and the effect of some additives on the grafting parameters in an aqueous medium

In an attempt to develop an alternative to petro‐based polymers, we graft‐copolymerized cellulose isolated from the needles of Pinus roxburghii with styrene in a limited aqueous medium in air by simultaneous irradiation using gamma rays as the initiator. The optimum conditions for obtaining maximum grafting were determined as a function of monomer concentration, total dose of irradiation, and amount of water. Maximum percentage of grafting (P_g; 79.9) was obtained at a total dose of 1.152 × 10⁴ Gy with 1.325 × 10^?4 mol of styrene. The effect of methanol, LiNO₃, Cu(NO₃)₂, Mohr's salt, H₂SO₄, HNO₃, and AcOH on P_g was studied. All the additives were found to decrease graft yield, contrary to some reported studies. Total percentage conversion and rates of polymerization, grafting, and homopolymerization were evaluated. Evidence of grafting was provided by the characterization of cellulose and its graft copolymers by Fourier transform infrared spectroscopy, thermogravimetry, and observation of the swelling behavior in some solvents. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1490–1500, 2002     

Phase immiscibility induced enhanced fluorescence in spin-coated PVP/PPO polyblends

We report on the effect of phase immiscibility on the structure and optical properties of spin-coated polyvinylpyrrolidone (PVP) and polyphenylene oxide (PPO) polyblends using X-ray diffraction, IR absorption, optical absorption and florescence spectroscopic techniques. The broad diffraction halos in the X-ray diffraction patterns reveal the semi-crystalline nature for the synthesized polyblends. The change in q value for both the deconvoluted halos confirms the variation in the molecular interactions while the decrease in their fwhm values signify the enhancement in crystalline nature with the blending. The infrared absorption studies were used to elucidate the interaction of functional groups in the spin-coated polyblends. The position of three excitonic bands and the red shift in the optical absorption edge with the increase in the PPO content has been observed for these polyblends. The six time enhancement in fluorescence peak intensity in visible region (~500 nm) for immiscible blend (50/50) composition has been of importance for the design of low cost luminescent and photovoltaic devices.