The ionicity and transport properties of a series of diethylmethylamine (DEMA) based protic ionic liquids (PILs) were characterized, principally utilizing nuclear magnetic resonance (NMR) spectroscopy. PILs were formed via the protonation of DEMA by an array of acids spanning a large range of acidities. A correlation between the (1)H chemical shift of the exchangeable proton and the acidity of the acid used for the synthesis of the PIL was observed. The gas phase proton affinity of the acid was found to be a better predictor of the extent of proton transfer than the commonly used aqueous ΔpKa. Pulsed field gradient (PFG) NMR was used to determine the diffusivity of the exchangeable proton in a subset of the PILs. The exchangeable proton diffuses with the acid if the PIL is synthesized with a weak acid, and with the base if a strong acid is used. The ionicity of the PILs was characterized using the Walden analysis and by comparing to the ideal Nernst-Einstein conductivity predicted from the (1)H PFG-NMR results.

Effects of foliar sprays of zinc and manganese sulfates on the fruit yield and quality as well as leaf nutrients concentration of pomegranate were studied during 2010 growing season in an orchard with a soil pH of 7.5 and EC of 5.2 (dS m -1 ). Zinc and manganese sulfates were applied two times at the rate of 0, 0.3 and 0.6 percent under a factorial design on the base of completely randomized blocks. Mn sprays had positive significant effects on the fruit yield, the aril/peel ratio, TSS, weight of 100 arils, juice content of arils, anthocyanin index, fruit diameter and leaf area. Zn effects were also significant for TSS, TSS/TA ratio, juice content of arils and leaf area. Foliar spray of Mn significantly increased Mn and N but decreased Zn and Cu concentrations in leaves. Foliar sprays of Zn significantly increased Zn but decreased Mn and P concentrations in the leaves. According to the results, the suitable combination of these two micronutrients for studied characters of pomegranate under prevailing conditions was foliar spray of 0.6% MnSO 4 and 0.3% ZnSO 4 .

Protic ionic liquids are known to form extended hydrogen-bonded networks that can lead to properties different from those encountered in the aprotic analogous liquids, in particular with respect to the structure and transport behavior. In this context, the present paper focuses on a wide series of 1-alkyl-imidazolium bis­(trifluoromethylsulfonyl)­imide ionic liquids, [HC n Im]­[TFSI], with the alkyl chain length (n) on the imidazolium cation varying from ethyl (n = 2) to dodecyl (n = 12). A combination of several methods, such as vibrational spectroscopy, wide-angle X-ray scattering (WAXS), broadband dielectric spectroscopy, and 1H NMR spectroscopy, is used to understand the correlation between local cation–anion coordination, nature of nanosegregation, and transport properties. The results indicate the propensity of the −NH site on the cation to form stronger H-bonds with the anion as the alkyl chain length increases. In addition, the position and width of the scattering peak q1 (or the pre-peak), resolved by WAXS and due to the nanosegregation of the polar from the nonpolar domains, are clearly dependent on the alkyl chain length. However, we find no evidence from pulsed-field gradient NMR of a proton motion decoupled from molecular diffusion, hypothesized to be facilitated by the longer N–H bonds localized in the segregated ionic domains. Finally, for all protic ionic liquids investigated, the ionic conductivity displays a Vogel–Fulcher–Tammann dependence on inverse temperature, with an activation energy E a that also depends on the alkyl chain length, although not strictly linearly.

The need for reliable means of ordering and quantifying the Lewis basicity of anions is discussed and the currently available methods are reviewed. Concluding that there is need for a simple impurity-insensitive tool, we have sought, and here describe, a new method using NMR spectroscopy of a weak base, a substituted urea, 1,3-dimethyl-2-imidazolidinone (DMI), as it is protonated by Brønsted acids of different strengths and characters. In all cases studied the product of protonation is a liquid (hence a protic ionic liquid). NMR spectroscopy detects changes in the electronic structure of the base upon interaction with the proton donors. As the proton-donating ability, that is, acidity, increases, there is a smooth but distinct transition from a hydrogen-bonded system (with no net proton transfer) to full ionicity. The liquid state of the samples and high concentration of nitrogen atoms, despite the very low natural abundance of its preferred NMR-active isotope ((15) N), make possible the acquisition of (15) N spectra in a relatively short time. These (15) N, along with (13) C, chemical shifts of the carbonyl atom, and their relative responses to protonation of the carbonyl oxygen, can be used as a means, sensitive to anion basicity and relatively insensitive to impurities, to sort anions in order of increasing hydrogen bond basicity. The order is found to be as follows: SbF6 (-) ClO4 (-) >FSO3 (-)

We investigate the effect of adding different molecular cosolvents, water or imidazole, to the protic ionic liquid 1-ethylimidazolium bis(trifluoromethanesulfonyl)imide, i.e., [C 2 HIm][TFSI]. We explore how the added cosolvent distributes within the ionic liquid by means of molecular dynamics simulations and X-ray scattering. We also analyze the degree of short-range heterogeneity in the resulting mixtures, finding that while imidazole easily mixes with the protic ionic liquid, water tends to form small clusters in its own water-rich domains. These differences are rationalized by invoking the nature of intermolecular interactions. In aqueous mixtures water−water hydrogen bonds are more likely to form than water−ion hydrogen bonds (water−TFSI bonds being particularly weak), while imidazole can interact with both cations and anions. Hence, the cation−anion association is negligibly influenced by the presence of water, whereas the addition of imidazole creates solvent-separated ion pairs and is thus able to also increase the ionicity. As a consequence of these structural and interactional features, transport properties like self-diffusion and ionic conductivity also show different composition dependencies. While the mobility of both ions and solvent is increased considerably by the addition of water, upon adding imidazole this property changes significantly only for molar fractions of imidazole above 0.6. At these molar fractions, which correspond to a base-excess composition, the imidazole/[C 2 HIm][TFSI] mixture behaves as a glass-forming liquid with suppressed phase transitions, while homomixtures such as imidazole/[HIm][TFSI] can display a eutectic point.

The influence of foliar application of 1% urea and four rates of urea (100, 200, 300 and 400 g tree -1 ) as soil application (deep fertilizer placement) were studied on leaf nutrients concentrations, yield and fruit quality of 'Malas e Torsh e Saveh' pomegranate (Punica granatum L.) during 2010 and 2011 growing seasons. Trees that received 300 and 400 g urea as soil application showed positive significant response on fruit yield, average fruit weight, aril weight percent of fruit, 100 arils weight, fruit diameter and TSS. Foliar application of urea had also significant effects on average fruit weight, aril weight percent of fruit and 100 arils weight.Nitrogen concentration increased linearly in leaves with the increase in rate of urea-applied.According to results, deep soil application of urea under the conditions of this study was more effective on pomegranate fruit yield and quality characters than foliar application of urea.

Purpose The stresses and deformations in the periodontal ligament (PDL) under the realistic kinetic loading of the jaw system, i.e ., chewing, are difficult to be determined numerically as the mechanical properties of the PDL is variably present in different finite element (FE) models. This study was aimed to conduct a dynamic finite element (FE) simulation to investigate the role of the PDL (PDL) material models in the induced stresses and deformations using a simplified patient-specific FE model of a human jaw system. Methods To do that, a realistic kinetic loading of chewing was applied to the incisor point, contralateral, and ipsilateral condyles, through the experimentally proven trajectory approach. Three different material models, including the elasto-plastic, hyperelastic, and viscoelastic, were assigned to the PDL, and the resulted stresses of the tooth FE model were computed and compared. Results The results revealed the highest von Mises stress of 620.14 kPa and the lowest deformation of 0.16 mm in the PDL when using the hyperelastic model. The concentration of the stress in the elastoplastic and viscoelastic models was in the mid-root and apex of the PDL, while for the hyperelastic model, it was concentrated in the cervical margin. The highest deformation in the PDL regardless of the employed material model was located in the caudal direction of the tooth. The viscoelastic PDL absorbed the transmitted energy from the dentine and led to lower stress in the cancellous bone compared to the elastoplastic and hyperelastic material models. Conclusion These results have implications not only for understanding the stresses and deformations in the PDL under chewing but also for providing comprehensive information for the medical and biomechanical experts in regard of the role of the material models being used to address the mechanical behavior of the PDL in other components of the tooth.

Various numerical algorithms have been developed to solve the Khokhlov-Kuznetsov-Zabolotskaya (KZK) parabolic nonlinear wave equation. In this work, a generalized time-domain numerical algorithm is proposed to solve the diffraction term of the KZK equation. This algorithm solves the transverse Laplacian operator of the KZK equation in three-dimensional (3D) Cartesian coordinates using a finite-difference method based on the five-point implicit backward finite difference and the five-point Crank-Nicolson finite difference discretization techniques. This leads to a more uniform discretization of the Laplacian operator which in turn results in fewer calculation gridding nodes without compromising accuracy in the diffraction term. In addition, a new empirical algorithm based on the LU decomposition technique is proposed to solve the system of linear equations obtained from this discretization. The proposed empirical algorithm improves the calculation speed and memory usage, while the order of computational complexity remains linear in calculation of the diffraction term in the KZK equation. For evaluating the accuracy of the proposed algorithm, two previously published algorithms are used as comparison references: the conventional 2D Texas code and its generalization for 3D geometries. The results show that the accuracy/efficiency performance of the proposed algorithm is comparable with the established time-domain methods.