Chitosan-based magnetic molecularly imprinted polymer: synthesis and application in selective recognition of tricyclazole from rice and water samples

A tricyclazole selective chitosan/Fe₃O₄ magnetic molecularly imprinted polymer (MMIP) was synthesized using non-covalent binding polymerization involving methacrylic acid (MAA) as functional monomer, divinylbenzene (DVB-80) as crosslinker, 2,2'-azobisisobutyronitrile as initiator, acetonitrile/toluene (75:25, v/v) as porogenic solvent and tricyclazole as template. Surface morphology and magnetic characterization of the prepared imprinted and non-imprinted polymers were done using scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectrometry and vibrating sample magnetometry, respectively. The adsorption kinetic data fitted best in pseudo-second-order model. The adsorption equilibrium was achieved in 30 min and the maximum binding capacity was 4579.9 µg/g. The Freundlich isotherm model was found suitable for explaining the binding isotherm data (R² > 0.99). Negative values of thermodynamic parameters ∆G (Gibb’s free energy), ∆H (enthalpy), and ∆S (entropy) revealed exothermic and spontaneous nature of adsorption processes. It also revealed decreased randomness at the solid–liquid interface during sorption. The scatchard plot analysis suggested heterogeneity of binding sites on MMIPs. The molecular recognition selectivity of MMIPs towards tricyclazole was much higher, as compared to its structural analogues, tebuconazole (α = 28.58) and hexaconazole (α = 37.16). The MMIPs were successfully applied to separate and enrich tricyclazole from fortified samples of rice and water, with a recovery percentage of 89.4% and 90.9%, respectively. These reusable imprinted polymers possessing high selectivity and specificity can be utilized as an adsorbent for solid-phase extraction in sample preparation for tricyclazole residue analysis in complex environmental matrices.

     

Identification of the pathway of α-oxidation of cerebronic acid in peroxisomes

Cerebronic acid (2-hydroxytetracosanoic acid), an α-hydroxy very long-chain fatty acid (VLCFA) and a component of cerebrosides and sulfatides, is unique to nervous tissues. Studies were carried out to identify the pathway and the subcellular site involved in the oxidation of cerebronic acid. The results from these studies revealed that cerebronic acid was catabolized by α-oxidation to CO₂ and tricosanoic acid (23:0). Studies with subcellular fractions indicated that cerebronic acid was α-oxidized in fractions having particulate bound catalase and enzyme systems for the β-oxidation of VLCFA (e.g., lignoceric acid), suggesting peroxisomes as the subcellular organelle responsible for α-oxidation of cerebronic acid. Etomoxir, an inhibitor of mitochondrial fatty acid oxidation, had no effect on cerebronic acid α-oxidation. Further, cerebronic acid oxidation was found to be dependent on the presence of NAD⁺ but not FAD, NADPH, ATP, Mg²⁺, or CoASH. Intraorganellar localization studies indicated that the enzyme system for the α-oxidation of cerebronic acid was associated with the peroxisomal limiting membranes. Studies on cultured fibroblasts from normal subjects and patients with peroxisomal disorders indicated an impairment of α-oxidation of cerebronic acid in cell lines that lack peroxisomes [e.g., Zellweger syndrome (ZS)]. On the other hand, α-oxidation of cerebronic acid was found to be normal in cell lines from X-linked adrenoleukodystrophy, adult Refsum disease, and rhizomelic chondrodysplasia punctata. Our results clearly demonstrate that α-oxidation of α-hydroxy VLCFA (cerebronic acid) is a peroxisomal function and that this oxidation is impaired in ZS. Furthermore, this α-oxidation enzyme system is distinct from the one for the α-oxidation of β-carbon branched-chain fatty acids (e.g., phytanic acid).     

Harmony search algorithm for infinite impulse response system identification

In this paper, optimal sets of filter coefficients are searched by a meta-heuristic optimization technique called Harmony Search (HS) algorithm for infinite impulse response (IIR) system identification problem. For different optimization problems, HS algorithm undergoes three basic rules; namely Random Selection (RS), Harmony Memory Consideration (HMC), and Pitch Adjustment (PA) rules, which are inspired from the process that the musicians use to improvise a perfect state of harmony with the consummate skill of blending notes in tune. With the help of the properly selected control parameters, a perfect balance is achieved in exploration and exploitation in searching phases. The detailed analysis of simulation results emphasizes the strength of HS algorithm to find the near-global optimal solution, quality of convergence profile and the speed of convergence while tested against standard benchmark examples for same and reduced order models.     

Sand corrosion,thermal expansion,and ablation of medium- and high-entropy compositionally complex fluorite oxides

Sand corrosion, thermal expansion, and ablation properties of a new class of medium- and high-entropy compositionally complex fluorite oxides (CCFOs) are examined as potential protective coating materials. Five binary oxides were mixed and sintered into dense, single-phase CCFOs of the general formula: [Hf_(1-2x)/3Zr_(1-2x)/3Ce_(1-2x)/3Y_xYb_x]O_2-δ (x = 0.2, 0.074, and 0.029). These CCFOs exhibit decreased molten sand infiltration and interaction at intermediate temperatures (1200-1300°C) in comparison with a cubic yttria-stabilized zirconia (YSZ) reference; however, at higher temperatures, the trend is reversed due to the increased chemical reactivity. The equimolar high-entropy (Hf_0.2Zr_0.2Ce_0.2Y_0.2Yb_0.2)O_2-δ exhibits no grain boundary penetration by molten sand at all examined temperatures (1200°C-1500°C), although reaction and precipitation are significant. Moreover, these CCFOs exhibit higher intrinsic thermal expansion coefficients (CTE) than the YSZ reference, thereby being more compatible with Ni-based superalloys. The 8YSZ-like (Hf_0.284Zr_0.284Ce_0.284Y_0.074Yb_0.074)O_2-δ exhibits the highest CTE in this series of CCFOs due to oxygen clustering effects. Finally, these CCFOs also exhibit lower emissivities and form unique faceted microstructures in ablative environments.     

Temporal persistence and stability of surface soil moisture in a semi-arid watershed

Satellite soil moisture products, such as those from Advanced Microwave Scanning Radiometer (AMSR), require diverse landscapes for validation. Semi-arid landscapes present a particular challenge to satellite remote sensing validation using traditional techniques because of the high spatial variability and potentially rapid rates of temporal change in moisture conditions. In this study, temporal stability analysis and spatial sampling techniques are used to investigate the representativeness of ground observations at satellite scale soil moisture in a semi-arid watershed for a long study period (March 1, 2002 to September 13, 2005). The watershed utilized, the Walnut Gulch Experimental Watershed, has a dense network of 19 soil moisture sensors, distributed over a 150 km² study region. In conjunction with this monitoring network, intensive gravimetric soil moisture sampling conducted as part of the Soil Moisture Experiment in 2004 (SMEX04), contributed to the calibration of the network for large-scale estimation during the North American Monsoon System (NAMS). The sensor network is shown to be an excellent estimator of the watershed average with an accuracy of approximately 0.01 m³/m³ soil moisture. However, temporal stability analysis indicated that while much of the network is stable, the soil moisture spatial pattern, as represented by mean relative difference, is not replicated by the network mean relative difference pattern. Rather, the network is composed of statistical samples. Geophysical aspects of the watershed, including topography and soil type are also examined for their influence on the soil moisture variability and stability. Soil type, as characterized by bulk density, clay and sand content, was responsible for nearly 50% of the temporal stability. Topographic effects were less important in defining representativeness and stability.     

Application of evolutionary optimization techniques for finding the optimal set of concentric circular antenna array

In this paper the maximum sidelobe level (SLL) reductions, optimal beam patterns and optimal beam widths of various designs of three-ring planar concentric circular antenna arrays (PCCAA) are examined using three different classes of evolutionary optimization techniques to finally determine the global optimal three-ring PCCAA design and then establish some sort of ranking among the techniques. Apart from physical construction of a PCCAA, one may broadly classify its design into two major categories: uniformly excited arrays and non-uniformly excited arrays. The present paper assumes non-uniform excitations and uniform spacing of excitation elements in each three-ring PCCAA design and a design goal of maximizing SLL reduction associated with optimal beam patterns and beam widths. The design problem is modeled as an optimization problem for each PCCAA design and solved using different evolutionary optimization techniques to determine an optimum set of normalized excitation weights for PCCAA elements, which, when incorporated, results in a radiation pattern with optimal (maximum) SLL reduction. Among the various PCCAA designs, one which yields the global minimum SLL with global minimum first null beamwidth is the global optimal design. In this work the three-ring PCCAA containing (N₁ = 4, N₂ = 6, N₃ = 8) elements proves to be such global optimal design. The optimization techniques employed are real coded GA (RGA), canonical PSO (CPSO), craziness based PSO (CRPSO), evolutionary programming (BEP), hybrid evolutionary programming (HEP). While ranking the techniques after 30 total runs for each design, HEP, CRPSO, RGA, CPSO, BGA hold the first five ranks in order of optimization capability. HEP yields global minimum SLL (?32.86 dB) and global minimum BWFN (77.0°) for the optimal design. BEP often changes the rank from second to fifth depending on the design set. Further, when compared to a uniformly excited PCCAA having equal number of elements and same radii a reduction of major lobe beamwidth is also observed in the optimal non-uniformly excited case.     

Soil moisture estimates from TRMM Microwave Imager observations over the Southern United States

The lack of continuous soil moisture fields at large spatial scales, based on observations, has hampered hydrologists from understanding its role in weather and climate. The most readily available observations from which a surface wetness state could be derived is the Tropical Rainfall Measuring Mission (TRMM) Microwave Imager (TMI) observations at 10.65 GHz. This paper describes the first attempt to map daily soil moisture from space over an extended period of time. Methods to adjust for diurnal changes associated with this temporal variability and how to mosaic these orbits are presented. The algorithm for deriving soil moisture and temperature from TMI observations is based on a physical model of microwave emission from a layered soil-vegetation-atmosphere medium. An iterative, least-squares minimization method, which uses dual polarization observations at 10.65 GHz, is employed in the retrieval algorithm. Soil moisture estimates were compared with ground measurements over the U.S. Southern Great Plains (SGP) in Oklahoma and the Little River Watershed, Georgia. The soil moisture experiment in Oklahoma was conducted in July 1999 and Little River in June 2000. During both the experiments, the region was dry at the onset of the experiment, and experienced moderate rainfall during the course of the experiment. The regions experienced a quick dry-down before the end of the experiment. The estimated soil moisture compared well with the ground observations for these experiments (standard error of 2.5%). The TMI-estimated soil moisture during 6-22 July over Southern U.S. was analyzed and found to be consistent with the observed meteorological conditions.     

Polyacrylonitrile solution homogeneity study by dynamic shear rheology and the effect on the carbon fiber tensile strength

Poly(acrylonitrile‐co‐methacrylic acid) (PAN‐co‐MAA)/N,N‐dimethylformamide (DMF) solutions were prepared and dynamic shear rheology of these solutions were investigated. With increasing stirring time up to 72 h at 70°C, the polymer solution became less elastic (more liquid‐like) with a ～60% reduction in the zero‐shear viscosity. Relaxation spectra of the PAN‐co‐MAA/DMF solutions yield a decrease in relaxation time (disentanglement time, τ_d), corresponding to an about 8% decrease in viscosity average molecular weight. The log‐log plot of G′ (storage modulus) versus G″ (loss modulus) exhibited an increase in slope as a function of stirring time, suggesting that the molecular level solution homogeneity increased. In order to study the effect of solution homogeneity on the resulting carbon fiber tensile strength, multiple PAN‐co‐MAA/DMF solutions were prepared, and the precursor fibers were processed using gel‐spinning, followed by continuous stabilization and carbonization. The rheological properties of each solution were also measured and correlated with the tensile strength values of the carbon fibers. It was observed that with increasing the slope of the G′ versus G″ log‐log plot from 1.471 to 1.552, and reducing interfilament fiber friction during precursor fiber drawing through the addition of a fiber washing step prior to fiber drawing, the carbon fiber strength was improved (from 3.7 to 5.8 GPa). This suggests that along with precursor fiber manufacturing and carbonization, the solution homogeneity is also very important to obtain high strength carbon fiber. POLYM. ENG. SCI., 56:361–370, 2016. © 2016 Society of Plastics Engineers