Evidence of Long-Range 13C-31P Couplings: A 13C NMR Investigation of Some Aryl Esters of Phosphor-Amidochloridic Acid and the Related Compounds

Abstract

In ¹³ NMR study organophosphorus compounds, sign and magnitude of ¹³ C-³¹ P spin-spin couplings has been of great interest to elucidate stereochemistry and electronic state of phosphorus central atom. However, a discussion about the mechanisms of carbon-phosphorus couplings is still complicated specially in the case of long-range couplings that also are not frequently observed. In this study, ¹³ C NMR chemical shifts and coupling constants have been determined for a series of aryl esters of phosphoramidochloridic acid with the general formula: R₂NP(O)(OAr)Cl, in which R = methyl and/or benzyl, Ar = p-tolyl. p-nitrophenyl, and phenyl. Besides usual W-couplings that could be found in these systems, we detected long-range couplings through five and six bonds. It has been shown that, these couplings are highly dependent on substituents on phosphorus nuclei. The data for some related compounds have been also obtained for a comparison.     

Theoretical study and atoms in molecule analysis of hydrogen bonded clusters of ammonia and isocyanic acid

Abstract  

Ab initio and density functional calculations were used to analyze the interaction between a molecule of the isocyanic acid with 1 up to 4 molecules of ammonia at the B3LYP/6-311++G(d,p) and MP2/6-311++G(d,p) computational levels. The cooperative effect is increased with the increasing size of studied clusters. Red shifts of the H–N stretching frequency for complexes involving the isocyanic acid as an H-donor were predicted. Atom in molecules was used to analyze cooperative effects on topological parameters.     

Kalman filtering for reliable estimation of BBB permeability

INTRODUCTION: The blood-brain barrier (BBB) plays an important role in the pathophysiology of a number of central nervous system disorders. In the past, a number of laboratory techniques have been proposed to quantify permeability coefficient ki, an important index of barrier function. Recently, magnetic resonance imaging (MRI) has been used to estimate ki based on graphical plot technique. The MR technique was found to be in good agreement with the gold standard, quantitative autoradiography (QAR). However, a reduced image signal-to-noise ratio, among other factors such as partial volume effects, did not allow reliable estimation of permeability coefficients. This proof-of-principle study proposes the use of Kalman filter as a filtering technique for a reliable estimation of permeability coefficients. The results are compared to those obtained using the Wiener filter technique. MATERIALS AND METHODS: MRI experiments were performed in Wistar rats (N=2) using a 4.7-T Bruker Biospec MR system (Bruker Biospin, Billerica, MA). After acquiring localizer images, T2-weighted diffusion-weighted imaging images were acquired. Finally, a rapid T1 mapping protocol was implemented to acquire one pre-gadolinium diethylenetriamine pentaacetic acid baseline data set followed by postinjection data sets at 3-min intervals for 45 min. Data were postprocessed with and without the application of Kalman and Wiener filters to obtain an estimate of ki. RESULTS AND DISCUSSION: Comparing T1 maps, Patlak plots and permeability maps with and without the Kalman filtering presented several interesting observations. Kalman-filtered Patlak plots, compared to nonfiltered plots, showed that discrete data points on the plot were closer to the line fit. The number of time points used for the construction of the graphical plot had no effect on permeability coefficient estimates when the Kalman filter was used. A box-and-whiskers plot showed longer Y-error bars for nonfiltered and Wiener data compared to Kalman-filtered data. These observations suggest that it may be possible to obtain reliable permeability coefficient estimates in a short study time by applying the Kalman filter to the data. Future work involves investigating the application of this filter on a large-sample-size animal study and evaluating the role of partial volume effects on BBB permeability estimation.     

Mono‐ and binuclear nickel catalysts for 1‐hexene polymerization

Polymerization of 1‐hexene was carried out using a mononuclear (MN) catalyst and two binuclear (BN₁ and BN₂) α‐diimine Ni‐based catalysts synthesized under controlled conditions. Ethylaluminium sesquichloride (EASC) was used as an efficient activator under various polymerization conditions. The highly active BN₂ catalyst (2372 g poly(1‐hexene) (PH) mmol^?1 cat) in comparison to BN₁ (920 g PH mmol^?1 cat) and the MN catalyst (819 g PH mmol^?1 cat) resulted in the highest viscosity‐average molecular weight (M_v) of polymer. Moreover, the molecular weight distribution (MWD) of PH obtained using BN₂/EASC was slightly broader than those obtained using BN₁ and MN (2.46 for BN₂ versus 2.30 and 1.96 for BN₁ and MN, respectively). These results, along with the highest extent of chain walking for BN₂, were attributed to steric, nuclearity and electronic effects of the catalyst structures which could control the catalyst behaviour. Differential scanning calorimetry showed that the glass transition temperatures of polymers were in the range ? 58 to ?81 °C, and broad melting peaks below and above 0 °C were also observed. In addition, longer α‐olefins (1‐octene and 1‐decene) were polymerized and characterized, for which higher yield, conversion and molecular weight were observed with a narrower MWD. The polymerization parameters such as polymerization time and polymerization temperature showed a significant influence on the productivity of the catalysts and M_v of samples.     

Introducing the theory of successful settling in order to evaluate and optimize the sedimentation tanks

A rectangular settling tank in full scale is investigated using the Fluent software to increase its efficiency. First, the pure water is simulated in the absence of particles. Then particles are injected into the flow field and tracked by means of the discrete phase model. Three methods are presented to optimize the settling tank: (1) adding a baffle which is mounted in the bottom and is extended up to the near of free surface, (2) adding a baffle which is mounted in the free surface and is extended up to the near of the tank bottom and (3) install a bi-directional baffle which is mounted in the free surface and is extended up to the near of the bottom. These three suggestions are checked using the short-circuiting phenomenon and the successful settling theory. The successful settling theory states that a particle can be accounted as a “trapped” particle if (1) settled particle stays static and stable in the tank bottom and (2) settled particle doesn’t return to purified sewage. Although the second method provided higher efficiency, the third method was selected as the most appropriate method in order to optimize the settling tank.     

New Correlative Models to Improve Prediction of Fracture Permeability and Inertial Resistance Coefficient

Presence of fracture roughness and occurrence of nonlinear flow complicate fluid flow through rock fractures. This paper presents a qualitative and quantitative study on the effects of fracture wall surface roughness on flow behavior using direct flow simulation on artificial fractures. Previous studies have highlighted the importance of roughness on linear and nonlinear flow through rock fractures. Therefore, considering fracture roughness to propose models for the linear and nonlinear flow parameters seems to be necessary. In the current report, lattice Boltzmann method is used to numerically simulate fluid flow through different fracture realizations. Flow simulations are conducted over a wide range of pressure gradients through each fracture. It is observed that creeping flow at lower pressure gradients can be described using Darcy’s law, while transition to inertial flow occurs at higher pressure gradients. By detecting the onset of inertial flow and regression analysis on the simulation results with Forchheimer equation, inertial resistance coefficients are determined for each fracture. Fracture permeability values are also determined from Darcy flow as well. According to simulation results through different fractures, two parametric expressions are proposed for permeability and inertial resistance coefficient. The proposed models are validated using 3D numerical simulations and experimental results. The results obtained from these two proposed models are further compared with those obtained from the conventional models. The calculated average absolute relative errors and correlation coefficients indicate that the proposed models, despite their simplicity, present acceptable outcomes; the models are also more accurate compared to the available methods in the literature.     

A boundary value problem associated to non-homogeneous operators in Orlicz-Sobolev spaces

We apply a three critical points theorem of B. Ricceri to establish the existence of at least three weak solutions for a class of non-homogeneous Neumann problems. Furthermore, by using another theorem of him, we prove that an appropriate oscillating behaviour of the nonlinear term ensures the existence of infinitely many weak solutions. Our analysis is based on recent variational methods for smooth functionals defined on Orlicz-Sobolev spaces.     

Preparation,magnetic properties and microwave absorption of Zr–Zn–Co substituted strontium hexaferrite and its nanocomposite with polyaniline

Russian Journal of Applied Chemistry - M-type strontium hexaferrite substituted by Zr4+, Zn2+, and Co2+ was firstly synthesized by a sol-gel auto combustion method. Then the polyaniline/hexaferrite...