Diisopropyl fluorophosphate (DFP) degradation activity using transition metal–dipicolylamine complexes

Transition metal complexes have been extensively used as catalysts for organophosphorus agent decomposition to reduce their toxicity with their performance being strongly dependent on the nature of the metal ion. To investigate this dependence, we prepared dipicolylamine (DPA)‐containing complexes of Cu(II), Zn(II), Ni(II), Co(II), and Fe(II) and analyzed their activities for the degradation of diisopropyl fluorophosphate (DFP), a nerve agent surrogate compound. Cu(II)‐DPA complex showed fastest reaction kinetics while Zn(II)‐DPA and Ni(II)‐DPA exhibited more slower reactions. This observation can be explained using frontier molecular orbital (FMO) theory, which revealed that the nucleophilicity of the oxygen atom in water molecules in these transition metal complexes was well matched with reactivity order observed in experiments. These investigations combined with theoretical study provide valuable information for designing and predicting the activity of new transition metal–organic ligand complexes as a catalyst to decompose and reduce toxicity of organophosphorus nerve agents.     

Hysteresis loops predicted by isoenergy density theory for polycrystals. Part I: fundamentals of non-equilibrium thermal–mechanical coupling effects

When a polycrystal is stressed or strained at fifty percent of the corresponding yield value, damage will be inflicted non-homogeneously in the material due to the fact that the stress and/or strain distribution is non-uniform even if isotropy and homogeneity are assumed for the initial microstructure. This effect will be cumulated for each cycle of the load if the applied stress or strain is repeated continuously. Nucleation of microcracks can eventually lead to the propagation of a macrocrack.The process of damage accumulation in fatigue is defined to be sufficiently slow such that inhomogeneity of material behavior created by loading is a significant factor that can not be arbitrarily dismissed without a good reason. What this means specifically is that the difference of the stress and strain behavior at each point in a fatigue specimen must be accounted for in the analytical model in order to predict the correct cumulative effect. Such a requirement translates into a non-equilibrium formulation where the constitutive relations for each point and loading cycle must be determined separately. In this sense, the true problem of fatigue cannot be completely treated by the classical continuum mechanics approach that is limited to equilibrium mechanics for a closed system. Having said this, the isoenergy density theory will be applied to estimate the hysteresis loops of a hour-glass profile cylindrical bar specimen as recommended by the American Society for Testing and Materials (ASTM) for low-cycle fatigue.The work will be divided into two parts. Part I will cover the fundamentals of a non-equilibrium theory where the continuum elements are finite in size; they do not vanish in the limit. Therefore, size effects are immediately encountered as a function of time. General expressions for the rate change of volume of these elements with surface area are derived such that they can be computed from the nine displacement gradients. These elements can differ in size and must fit together without discontinuities or gaps to form the continuum. The condition of isoenergy energy density is invoked such that the size of these individual elements under large and finite deformation and rotation can be determined without loss in generality. The existence of such a space having the property of the same isoenergy density in all directions is thus proved. This enables the establishment of the one dimensional energy state with that in three dimensions without restriction, the absence of which has prevented the development of a complete non-linear theory of mechanics that can be solved in a direct fashion in contrast to the inverse method of assuming the displacement field. Illustration is provided for deriving the constitutive relation incrementally for a given location for the hour-glass specimen made of 6061-T6 aluminum. Once the specimen is loaded, each material point will follow a different stress and strain curve according to the local displacement rate. Hence, the method applies to material with non-homogeneous microstructure if their individual expressions can be assessed and fed into the computer.Part II computes for the non-equilibrium temperature and an entropy-like quantity that can be positive and negative. This implies that the system can absorb or dissipate energy with reference to the surrounding. Additional data for hysteresis loops are given for 6061-T6 aluminum, SAE 4340 steel and Ti–8Al–1Mo–1V titanium. Accumulation of the local hysteresis energy per cycle is found to be the highest near the surface of the uniaxial specimen where load symmetry prevails. This is a consequence of the difference in accumulation of the energy density due to distortion in contrast to dilatation at the specimen center. This is why fatigue cracks tend to nucleate near the specimen surface, at a small distance towards the interior. Another distinct feature of fatigue is that the non-equilibrium temperature is found to oscillate about the ambient temperature while the local stress states fluctuate between tension and compression. This temperature reversal behavior is typical of non-equilibrium behavior and also occurs under monotonic loading. The space and time variations of the dissipated energy density for different materials are found to be related to the initial monotonic energy density or area under the true stress and true strain curve.What will be demonstrated is that no special consideration need to be made when applying the isoenergy density theory for analyzing the nucleation of micro and macrocracks in addition to failure of the specimen. Crack nucleation under fatigue is assumed to occur when the total hysteresis energy reaches a critical value. It is possible to establish a relation between the average hysteresis energy per cycle and the number of cycles to failure. The proposed method requires only a knowledge of the initial monotonic energy density curve for a given material. Predicted results for the fatigue of cylindrical bar specimens with hour-glass profile are given and they can be found in Part II of this work.     

A potentiometric sensor of silver ions based on the Schiff base of diphenol

A potentiometric sensor based on the Schiff base 2,2′-(1E,1′E)-(1,1′-binaphthyl-2,2′-diylbis(azan-1-yl-1-ylidene))bis(methan-1-yl-1-ylidene)diphenol was synthesized and tested as an ionophore PVC-based membrane sensor selective towards silver ions (Ag⁺). Potentiometric testing demonstrated the high affinity of this receptor to silver ions. Seven membranes were fabricated with different compositions, with best performance shown by that with an ionophore composition (w/w) of 1.0?mg, PVC 33.0?mg, 2-nitrophenyl octyl ether 66?mg, and potassium tetrakis(p-chlorophenyl)borate 50?mol% in 1.0?mL tetrahydrofuran. The sensor worked well over a wide range of concentrations (1.0?×?10^?2 to 1.0?×?10^?6?M Ag⁺) at pH?6, showing a slope of 60.99?mV/dec with rapid response times of less than 3?s. The sensor also showed good selectivity towards Ag⁺ in the presence of interfering cations, with the highest selectivity coefficient observed for Hg²⁺ (2.7). A low detection limit of 3.4?×?10^?7?M Ag⁺ was established.     

Plasma surface functionalization of poly[bis(2,2,2-trifluoroethoxy)phosphazene] films and nanofibers

Polyphosphazenes are a class of hybrid organic-inorganic macromolecules with high thermo-oxidative stability and good solubility in many solvents. Fluoroalkoxy phosphazene polymers also have high surface hydrophobicity. A method is described to tune this surface property while maintaining the advantageous bulk materials characteristics. The polyphosphazene single-substituent polymer, poly[bis(2,2,2-trifluoroethoxy)phosphazene], with flat film, fiber mat, or bead mat morphology was surface functionalized using an atmospheric plasma treatment with oxygen, nitrogen, methane, or tetrafluoromethane/hydrogen gases. Surface chemistry changes were detected by static water contact angle (WCA) measurements as well as X-ray photon spectroscopy (XPS). It was found that changes in the WCA of as much as 150 degrees occurred, accompanied by shifts in the ratio of elements on the polymer surface as detected by XPS. Overall this plasma technique provides a convenient method for the generation of specific surface characteristics while maintaining the hydrophobicity of the bulk material.     

Highly sensitive and selective chemosensor for Hg2+ based on the rhodamine fluorophore

A novel tren-based tripodal chemosensor 1 bearing a rhodamine and two tosyl groups was synthesized and its sensing behavior toward metal ions was investigated by UV/vis and fluorescence spectroscopies. Addition of a Hg2+ ion to a CH3CN solution of 1 gave a visual color change as well as significantly enhanced fluorescence, while other ions including Pb2+, Zn2+, Cu2+, Ca2+, Ba2+, Cd2+, Co2+, Mg2+, Ag+, Cs+, Li+, and Na+ induced no or much smaller color/spectral changes, which constituted a Hg2+-selective fluorescent chemosensor (OFF-ON).     

Simple extraction method using syringe filter for detection of ethephon in tomatoes by negative‐ion mode liquid chromatography with tandem mass spectrometry

In this study, a simple, rapid, and sensitive method was developed for the extraction of ethephon from homogenized tomatoes that does not require a cleanup procedure. In a syringe filter, three distinct layers – aqueous, acetonitrile, and n‐hexane – are clearly separated after storage at ?80 °C for 5–10 min. A Dionex IonPac column was used to separate the analyte before detection using negative‐ion mode liquid chromatography with tandem mass spectrometry (LC/MS/MS). The matrix effect of the tested analyte was negligibly small and the matched calibration showed a good linearity over a concentration range of 0.01–1.0 mg/kg with a correlation coefficient (R²) of 0.9998. The recovery at three fortification levels (0.1, 0.5 and 1.0 mg/kg) was between 82.9 and 108.6% with relative standard deviations (RSDs) <5.0%. The limit of quantification (0.03 mg/kg) was lower than the maximum residue limit (3 mg/kg) set by the Ministry of Food and Drug Safety, Republic of Korea. From a field trial, the method developed herein was applied to calculate the decline pattern and predict the pre‐harvest residue limits of ethephon in tomatoes. In conclusion, the proposed sample preparation is feasible for the detection of hydrophilic analytes in tomatoes. Copyright © 2015 John Wiley & Sons, Ltd.