Copper-catalyzed asymmetric allylic substitution with aryl and ethyl Grignard reagents

Phenyl- and ethyl-magnesium bromides undergo regioselective asymmetric allylic substitution with high enantioselectivity under the catalysis of chiral amidophosphane-copper(I) complexes.     

Mössbauer and electronic spectral characterization of homo-bimetallic Fe(III) complexes of unsymmetrical [N10] and [N12] macrocyclic ligands

The homo-bimetallic complexes of stoichiometry Fe2(L)ClO4(ClO4)2 where L are novel unsymmetrical [N10] (L1.2HClO4) and [N12] (L2.2HClO4) macrocyclic ligands, have been prepared. The ligands were obtained from an in situ capping reaction of the reactive substrate, N,N'-bis(N-ethylaniline)hydrazine-1,2-diimine with a mixture of aniline or 1,3-diaminopropane and HCHO in presence of HClO4. The compounds have been characterized by elemental analyses, conductometric, IR, FAB-mass and electronic spectral studies. IR data of complexes suggest coordination from unsymmetrical aza sites as a tridentate (N,N,N) or tetradentate (N,N,N,N) ligand. mu(eff) values of the complexes suggest presence of antiferromagnetically coupled (Fe3+-Fe3+=S5/2-S5/2) spin exchange. M?ssbauer parameters of the complexes support (+/-3/2)-->(+/-1/2) nuclear transition in high-spin configurations of Fe(III) nuclei of the homo-bimetallic complexes with the presence of Kramer's double degeneracy.     

The effects of gum arabic oral treatment on the metabolic profile of chronic renal failure patients under regular haemodialysis in Central Sudan

This study aimed at assessing the effect of gum arabic (Acacia senegal) oral treatment on the metabolic profile of chronic renal failure (CRF) patients. A total of 36 CRF patients (under regular haemodialysis) and 10 normal subjects participated in this study. The patients were randomly allocated into three groups-group A: 12 CRF patients under low-protein diet (LPD) (<40 g day(-1)) and gum arabic (50 g day(-1)) treatment; group B: 14 CRF patients under LPD and gum arabic, iron (ferrous sulphate, 200 mg day(-1)) and folic acid (5 mg day(-1)) treatment; group C (control group): 10 CRF patients under LPD and iron and folic acid treatment and group D: 10 normal volunteers (on normal diet) under daily dose of 50 g gum arabic. Each of the above treatments was continued for three consecutive months. Blood samples were collected from each subject before treatment and twice per month "pre-dialysis" for 3 months. Biochemical parameters measured were: serum urea, serum creatinine, serum uric acid, serum calcium and serum phosphorus. By the end of the 3 months of treatment, serum urea levels significantly decreased by 31.2 and 44.18% for group A and B, respectively, compared with the baseline (0.01 < p < 0.001) and control group (p < 0.05). Serum creatinine levels significantly decreased in the groups of gum users (A, B and D) by 9.94, 12.65 and 11.7%, respectively, compared with the control group (p < 0.001). There was a significant decrease (p < 0.05) in serum uric acid levels by 14 and 19.9% for group A and B, respectively, compared with the baseline. Serum calcium levels increased by 12.64, 15.75 and 8.75% for group A, B and D, respectively, and these increases were significantly different (0.05 < p < 0.001) from baseline and control group for groups A and B. Serum phosphorus levels significantly decreased by 22.54% for group A, 17.69% for group B and 7.71% for group D, compared with the baseline (0.05 < p < 0.001). From this study, we conclude that oral administration of gum arabic could conceivably alleviate adverse effects of CRF.     

On the analysis of a kind of nonlinear Sobolev equation through locally applied pseudo‐spectral meshfree radial point interpolation

In this study, we develop an approximate formulation for two‐dimensional nonlinear Sobolev problems by focusing on pseudospectral meshless radial point interpolation (PSMRPI) which is a kind of locally applied radial basis function interpolation and truthfully a meshless approach. In the PSMRPI method, the nodal points do not need to be regularly distributed and can even be quite arbitrary. It is easy to have high order derivatives of unknowns in terms of the values at nodal points by constructing operational matrices. The convergence and stability of the technique in some sense are studied via some examples to show the validity and trustworthiness of the PSMRPI technique.     

The MR detection of neuronal depolarization during 3-Hz spike-and-wave complexes in generalized epilepsy

Previously, an analysis of activations observed in a patient with idiopathic generalized epilepsy using electroencephalogram-correlated functional magnetic resonance imaging (MRI) during runs of 3-Hz generalized spike–wave discharge (GSWD) was presented by Salek-Haddadi. Time-locked, bilateral, thalamic blood oxygenation level-dependent increases were reported to be accompanied by widespread, symmetric, cortical deactivation with a frontal maximum. In light of recent investigations into MRI detection of the magnetic field perturbations caused by neuronal current loops during depolarization, we revisited the analysis of the data of Salek-Haddadi as a preliminary search for a neuroelectric signal. We modeled the MRI response as the sum of a fast signal and a slower signal and demonstrated significant MRI activity at a time scale of the order of 30 ms associated with GSWDs. Further work is necessary before firm conclusions may be drawn about the nature of this signal.     

Ionic N-B-N- and B-N-B-substituted benzene analogues: a theoretical analysis

Calculations are presented on six-π-electron N-B-N- and B-N-B-substituted benzene rings, [C(3)BN(2)H(6)](+) and [C(3)NB(2)H(6)](-), and their isomers. These compounds display a wide range of thermodynamic stability in those molecules, with N-B-N connectivity favored strongly in the cation, B-N-B in the anion. That stability order is easily understood using the charge distribution in a benzene polarized by heteroatom substitutions or the underlying allyl anion and cation. Deprotonation at N in [C(3)BN(2)H(6)](+) leads to a set of BN-substituted pyridines. The calculations predicted three B-N-substituted pyridines clearly more stable thermodynamically than those synthesized so far. The order of stability of the B-N-B-substituted benzenoid systems, which are as yet not well known experimentally, shows similar features. We investigated in a preliminary way the reactivity and potential stabilization by substitution of the energetically most stable structures and by examining possible escape routes by dimerization. Our study suggests new N-B-N and B-N-B molecules that could be made.     

Preconcentration and selective extraction of chromium species in water samples using amino modified mesoporous silica

Speciation and separation of chromium (VI) and chromium (III) from aqueous solutions were investigated using amino-propyl functionalised mesoporous silica (AP-MCM-41) as an adsorbent. The as-synthesised adsorbent was produced following a simple synthesis method at room temperature prior to template removal using microwave digestion. The maximum adsorption capacity at 111.1mg/g was calculated according to the Langmuir isotherm model, suggesting a 1:1 monolayer adsorption mechanism. Moreover, AP is a simple chelate, yet it can extract Cr (VI) exclusively from solutions containing other mixed metal ions simply by tuning the solution pH. Recovery of Cr (VI) from loaded sorbents is equally easy to perform with 100% extraction efficiencies allowing reuse of the sorbent and recovery of Cr (VI) from aqueous solutions containing a complex mixture of ions. The material would find use in environmental remediation applications, as a selective adsorbent of Cr (VI) or even as a solid-phase extraction stationary phase to remove and pre-concentrate Cr (VI) from aqueous solutions; this study demonstrates enrichment factors of 100 although higher levels are also possible.     

Enhancement in sensitivity of nitro blue tetrazolium polyvinyl alcohol film dosimeters by sodium formate and Triton X-100

Nitro blue tetrazolium polyvinyl alcohol film dosimeters, NBT-PVA were prepared and evaluated based on radiation-induced reduction of NBT²⁺. NBT-PVA film dosimeters containing different concentrations of NBT dye from 1 to 5 mM were prepared in a solution of ethanol. The dosimeters were irradiated with ?-ray from ⁶⁰Co source at doses up to 50 kGy. UV/vis spectrophotometer was used to investigate the optical density of un-irradiated and irradiated films in terms of absorbance at 529 nm. The absorbance increases with absorbed dose up to 50 kGy for NBT-PVA film dosimeters. The dose sensitivity of NBT-PVA film increases strongly with increase of concentrations of NBT dye. The effects of irradiation temperature, humidity, dose rate and the stability of the response of the films after irradiation were investigated. A considerable increase was observed in the dose response of NBT-PVA film by adding appropriate concentration of sodium formate and Triton X-100.     

Determination of phenoxy herbicides in water samples using phase transfer microextraction with simultaneous derivatization followed by GC‐MS analysis

A sensitive and accurate method for the determination of two model phenoxy herbicides, 4‐chloro‐2‐methylphenoxy acetic acid and 4‐chloro‐2‐methylphenoxy propanoic acid, in water is explained. This method utilizes a simple phase transfer catalyst‐assisted microextraction with simultaneous derivatization. Factors affecting the performance of this method including pH of the aqueous matrix, temperature, extraction duration, type and amount of derivatization reagents, and type and amount of the phase transfer catalyst are examined. Derivatization and the use of phase transfer catalyst have proven to be especially vital for the resolution of the analytes and their sensitive determination, with an enrichment factor of 288‐fold for catalyzed over noncatalyzed procedure. Good linearity ranging from 0.1 to 80 μg L^?1 with correlation of determination (r²) between 0.9890 and 0.9945 were obtained. Previous reported detection limits are compared with our new current method. The low LOD for the two analytes (0.80 ng L^?1 for 4‐chloro‐2‐methylphenoxy propanoic acid and 3.04 ng L^?1 for 4‐chloro‐2‐methylphenoxy acetic acid) allow for the determination of low concentrations of these analytes in real samples. The absence of matrix effect was confirmed through relative recovery calculations. Application of the method to seawater and tap water samples was tested, but only 4‐chloro‐2‐methylphenoxy propanoic acid at concentrations between 0.27 ± 0.01 and 0.84 ± 0.06 μg L^?1 was detected in seawater samples.     

A new fatty ester and a new triterpene from Skimmia laureola

Aerial parts of Skimmia laureola yielded a new fatty ester, (+)-skimmilaureol (1), and a new triterpene 16-29-dihydroxy, 20-ene cyclolaudenol (2). Five known compounds, namely, O-methyl-cyclolaudenol (3), (R)-7-methoxy-6-(3'-hydroxy-2'R-methoxy-3'-methyl butyl)coumarin (4), (+)-(S)-psi-ribalinine (5), (R)-(+)-ribalinine (6) and methyl isoplatydesmine (7), previously isolated from this plant were subjected to enzymatic bioassays for the first time. Compounds 3 and 4 were found to be prolyl endopeptidase inhibitors with IC(50) 8.21 +/- 0.407 and 39.63 +/- 1.502 microM, respectively, while compounds 5-7 were found to be acetyl-cholinesterase and butyryl-cholinesterase inhibitors with IC(50) 62.46 +/- 1.58, 153.31 +/- 1.9, 74.5 +/- 1.05 and 150.04 +/- 0.45, 12.99 +/- 0.31, 78.3 +/- 1.86 microM, respectively.