Sharif Digital Repository

Calcineurin is an essential calcium-activated serine/threonine phosphatase. The six NMR-observable methionine methyl groups in the catalytic domain of human calcineurin Aα (CNA) were assigned and used as reporters of the presence of potential cis-trans isomers in solution. Proline 84 is found in the cis conformation in most calcineurin X-ray structures, and proline 309, which is part of a highly conserved motif in phosphoprotein phosphatases, was modeled with a cis peptide bond in one of the two molecules present in the asymmetric unit of CNA. We mutated each of the two prolines to alanine to force the trans conformation. Solution NMR shows that the P84A CNA mutant exists in two forms,... 

In this work, two important opioid antagonists, naltrexone and oxycodone, were prepared from thebaine and were characterized by IR, 1H NMR and 13C NMR spectroscopy. Moreover, computational NMR and IR parameters were obtained using density functional theory (DFT) at B3LYP/6-311++G* * level of theory. Complete NMR and vibrational assignment were carried out using the observed and calculated spectra. The IR frequencies and NMR chemical shifts, determined experimentally, were compared with those obtained theoretically from DFT calculations, showed good agreements. The RMS errors observed between experimental and calculated data for the IR absorptions are 85 and 105 cm-1, for the 1H NMR peaks are... 

The anomeric carbon chemical shifts of α-, β- and γ-cyclodextrin in solution were studied experimentally and theoretically by NMR and two-layer ONIOM2 (B3LYP/6-31G*-GIAO: HF/6-31G*-GIAO) variant. The dependence between the anomeric carbon chemical shift and the glycosidic bond φ and ψ dihedral angles in d-Glcp-d-Glcp disaccharides with and (1 → 4) linkages in α-configurations were computed by Gauge-Including Atomic Orbital (GIAO) ab initio and ONIOM in water solvent using PCM methods. Complete chemical shift surfaces versus φ and ψ for this disaccharide were computed. We also present empirical formulas of the form 13C δ = f(φ, ψ) obtained by fitting the ab initio data to trigonometric series... 

Variable-temperature 1H and 13C NMR spectroscopy are used to investigate barrier of C-N rotation in series of amides, such as N-benzoyl pyrrolidine, N-(4-chlorobenzoyl) pyrrolidine, N-(4-methoxybenzoyl) pyrrolidine, N-(4-chlorobenzoyl) piperidine, and N-(4-methoxybenzoyl) piperidine. Δ G298≠ of 65.2, 60.6, 58.8, 60.1, and 57.1 kJ mol-1are found for the above compounds, respectively. Theoretical studies were done for these compounds and the results showed good agreement with the experimental results. Theoretical and experimental results showed that substituted methoxy group on the para position of benzene ring decreases the rotational barrier. Increasing steric effect and therefore... 

The wave functions for calculating gas phase 1H chemical shifts of primary and secondary alcohols have been optimized using factorial design as multivariate technique. Gas-phase experimental 1H chemical shifts of 18 alcohols were used to establish the best levels of theory for obtaining 1H chemical shift, among them the new experimental values of 1H chemical shifts of 10 alcohols were obtained in our laboratory. HF/6-31G(d,p) wave function is proposed as the best level of theory for calculating 1H chemical shifts of primary alcohols. For secondary alcohols, ONIOM(B3LYP/6-31G(d,p): HF/6-31G(d,p)) are recommended. An additional series of primary and secondary alcohols were used as test sets... 

Solid state 13C and 15N chemical shifts of uracil and imidazole have been calculated using a 2-layer ONIOM approach at 32 levels of theory. The effect of electron correlation between two layers has been investigated by choosing two different kinds of layer selection. Factorial design has been applied as a multivariate technique to analyze the effect of wave function and layer selection on solid state 13C and 15N chemical shifts calculations. PBEPBE/6-311+G(d,p) was recommended as an optimally selected level of theory for high layer in both models. It is illustrated that considering the electron correlation of two layers of ONIOM models is important factor to calculate solid state 15N... 

The dependency of amino acid chemical shifts on φ and ψ torsion angle is, independently, studied using a five-residue fragment of ubiquitin and ONIOM(DFT:HF) approach. The variation of absolute deviation of 13Cα chemical shifts relative to φ dihedral angle is specifically dependent on secondary structure of protein not on amino acid type and fragment sequence. This dependency is observed neither on any of 13Cβ, and 1Hα chemical shifts nor on the variation of absolute deviation of 13Cα chemical shifts relative to ψ dihedral angle. The 13Cα absolute deviation chemical shifts (ADCC) plots are found as a suitable and simple tool to predict secondary structure of protein with no requirement of... 

In this work, phosphorus-31 and aluminum-27 nuclear magnetic resonance techniques were used to characterize the distribution of soluble aluminophosphate species in methanol + water and ethanol + water mixtures. The assignment of the peaks to alu-minate species was attempted, clarifying earlier work and producing information on the different aluminophosphate complexes. Nine peaks were observed at -0.41, -6.4, -7.5, -7.9, -13.1, -13.9, -16.6, -18.1 and -20.6 ppm. Four new peaks appeared in the 31P NMR spectra of the alcoholic aluminophosphate solutions and their intensities changed with changes of the alcohol:water volume ratio. These new peaks were observed in the presence of methanol or... 

27Al NMR spectroscopy is a powerful tool for the study of coordination and solvation in both aqueous and nonaqueous solutions. In this study, the complexes coexisting upon dissolution of AlCl3 in acidic acetone + methanol solutions are shown to consist essentially of mixed hexacoordinated species of the general formula [Al(CH3OH) 6-n (CH3COCH3) n ]3+ (n=1,2 and 3), all exhibiting distinctly different 27Al shielding effects. The relative populations of the various mixed species are found to be highly dependent upon the acetone:methanol mole ratio that in the more acetone-rich mixtures with aluminum become appreciably coordinated by acetone. The results demonstrate that the key factor for the... 

Multicore platforms are becoming the dominant trend in designing Mixed-Criticality Systems (MCSs), which integrate applications of different levels of criticality into the same platform. A well-known MCS is the dual-criticality system that is composed of low-criticality and high-criticality tasks. The availability of multiple cores on a single chip provides opportunities to employ fault-Tolerant techniques, such as N-Modular Redundancy (NMR), to ensure the reliability of MCSs. However, applying fault-Tolerant techniques will increase the power consumption on the chip, and thereby on-chip temperatures might increase beyond safe limits. To prevent thermal emergencies, urgent countermeasures,... 

A multicomponent polysaccharide obtained from dried tubers of certain natural terrestrial orchids was chemically modified by sulfonation using chlorosulfonic acid-dimethylformamide (HClSO3-DMF) complex as a reagent. For a structural characterization of salep sulfate 1H nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR) spectra, and Thermogravimetric analysis (TGA) curves were recorded. The sulfate content of modified salep was determined using elemental analysis. This modified biopolymer was used to prepare a new environment-friendly heavy metal ion adsorbent, salep sulfate-graft-polyacrylic acid hydrogel (SS-g-PAA). Swelling rate and equilibrium water absorbency in various... 

A new cationic flocculant was synthesized by graft copolymerization of acrylamide (AM) and 3-(methacryloylamino)propyl]trimethylammonium chloride (MAPTAC) onto salep using free radical polymerization initiated by ammonium persulfate (APS) to produce cationic salep [S-g-P(AM-co-MAPTAC)]. Reaction parameters (monomers/salep ratio, concentration of reactants, MAPTAC/AM ratio, and APS) were optimized using a full factorial experimental design to obtain the highest settling rate for cement suspensions. The best performing product was characterized by gel permeation chromatography (GPC), FTIR, 1H NMR spectroscopy, and thermogravimetric analysis (TGA). The resulted cationic flocculant may be... 

Salep phosphate modified biopolymers with different phosphate contents were prepared via reacting salep (a multi-component polysaccharide obtained from dried tubers of certain natural terrestrial orchids) with a solution of primary and secondary sodium phosphates under basic conditions in a semidry process. Structural characterization of salep phosphates were carried out by 31P NMR, FT-IR spectra and TGA curves. Determination of the phosphate content in samples was done by a standard spectrophotometric method. Then, novel (salep phosphate)-based hydrogels were synthesized by graft copolymerization of acrylic acid (AA) monomer onto salep phosphate backbones. Effect of the phosphate contents... 

Objective(s): This study aims to evaluate combined proton nuclear magnetic resonance (1H NMR) spectroscopy and gas chromatography-mass spectrometry (GC-MS) metabolic profiling approaches, for discriminating between mustard airway diseases (MADs) and healthy controls and for providing biochemical information on this disease. Materials and Methods: In the present study, analysis of serum samples collected from 17 MAD subjects and 12 healthy controls was performed using NMR. Of these subjects, 14 (8 patients and 6 controls) were analyzed by GC-MS. Then, their spectral profiles were subjected to principal component analysis (PCA) and orthogonal partial least squares regression discriminant... 

The six-coordinated silver(I) complex [Au2Ag(μ-(PPh2)2py)2(OTf)2](OTf), 4 (py = pyridine, OTf = CF3SO3), and the five-coordinated silver(I) complex [Au2Ag(acetone)(μ-(PPh2)2py)2](PF6)3, 6, were prepared by the reaction of the precursor complexes 1(OTf)2 and 1(PF6)2, in which 1 = [Au2(μ-(PPh2)2py)2]2+, with 1 equiv of Ag(OTf) in dichloromethane and excess of Ag(PF6) in a mixture of dichloromethane/acetone, respectively. Also, the five-coordinated silver(I) complex [Au2Ag(μ-(PPh2)2py)2(py)(OTf)](OTf)2, 5, was obtained by the reaction of 4 with pyridine. The clusters 4-6 were characterized using multinuclear NMR spectroscopy and elemental microanalysis. The single-crystal X-ray diffraction... 

Cementation factor greatly affects water saturation estimation. Factors such as depositional environment, diagenesis and depositional architecture make the estimation of water saturation a big challenge in carbonate reservoirs. The current study is introduced a method for calculating cementation factor in Archie formula. First, (MRGC) technique was applied on the (NMR) logging parameters along with (NDS) data to obtain the optimum number of clustering. After that, fuzzy logic method was applied on conventional log parameters obtained from the wells without any NMR log data. In the third part of the study, a novel crossplot introduced including compressional to shear-wave velocity ratio... 

In this research the radical chlorination reaction of polyethylene has been carried out in perchloroethylene solvent under atmospheric pressure, using chlorine gas and UV light. In order to characterize the structural configuration of chlorinated polymer and study the reaction rate, different samples have been taken in equal periods of time during the reaction time. The FT-IR and H NMR spectra of these samples have been recorded and interpreted. The sequences of methylene groups between two subsequent chloromethylene groups in the polymeric chains have been determined through H NMR spectra and the obtained results have been confirmed with the data of some model compounds. The relative... 

Compound 3-benzyl-2H-pyrano[3,2-c]chromene-2,5(6H)-dione(3), was prepared and fully characterized. The vibrational modes (FT-IR) and NMR data ( 1H and 13C chemical shifts) were compared with the results of Density Functional Theory (DFT) method at the B3LYP/cc-PVTZ level. The calculated vibrational frequencies and NMR chemical shifts are in good agreement with the experimental results. The electronic (UV-Vis) spectrum was calculated using the TD-DFT method in CH2Cl2 with the Polarizable Continuum Model using the integral equation formalism variant (IEFPCM) and was correlated to the experimental spectra. The assignment and analysis of the frontier HOMO and LUMO orbitals indicate that... 

The learning vector quantization (LVQ) neural network is a useful tool for pattern recognition. Based on the network weights obtained from the training set, prediction can be made for the unknown objects. In this paper, discrimination of wines based on 2D NMR spectra is performed using LVQ neural networks with orthogonal signal correction (OSC). OSC has been proposed as a data preprocessing method that removes from X information not correlated to Y. Moreover, the partial least squares discriminant analysis (PLS-DA) method has also been used to treat the same data set. It has been found that the OSC-LVQ neural networks method gives slightly better prediction results than OSC-PLS-DA © 2005...