Computational examination of the electrophilic reaction on oxidative polymerization of phenyltrimethylsilane with sulfur chloride

Phenyltrimethylsilane possesses a higher HOMO energy (–9.34 eV) than nonsubstituted benzene (>0.41 eV). The π electron of the phenyltrimethylsilane localizes on the benzene ring at the ipso position rather than at the para position. Two center energies calculated by the MNDO-PM3 method indicate that the C? Si bond is facilitated to cleave in comparison with the C? H (para position) one of the benzene ring. Phenyltrimethylsilane and phenyl bis(trimethylsilane) were polymerized with sulfur chloride through the cationic oxidative polymerization. The product is isolated as oligo(p-phenylene sulfide), with a melting point of 150–190°C. An electrophile attacks the carbon atom linked to the Si atom in phenyltrimethylsilane. The new synthetic route of PPS can be established on the basis of the computational calculation.     

Preparation and reactions of s,s-dimethyl-n-(2,4-dinitrophenyl)sulfilimine

S,S-Dimethyl-N-(2,4-dinitrophenyl)sulfilimine(4a) has been prepared in good yield by use of DMSO, 2,4-dinitroaniline and phosphorus pentoxide in DMF and the role of DMF in this System is discussed. The method has been applied successfully to the syntheses of several sulfilimines. The reactions of 4a with protonic compounds show an interesting ylide-exchange reaction.     

Quantitative analysis of methylguanidine and guanidine in physiologic fluids by high-performance liquid chromatography-fluorescence detection method.

A rapid and sensitive high-performance liquid chromatographic method has been developed for the quantitative analysis of methylguanidine and guanidine in physiological fluids. These quanidino compounds are separated on a 6 x 0.23 cm cation-exchange column with 0.5 M sodium hydroxide solution. The guanidino compounds are detected with a fluorometer, which monitors the fluorescent guanidine derivatives produced by the reaction of the eluted constituents with 9,10-phenanthrenequinone. Sensitivity to sub-nanomole levels of methylguanidine and guanidine is demonstrated. The method was successfully applied to physiological fluids such as serum and cerebrospinal fluid from uremic patients.     

Thallium-201 chloride dynamic analysis using thallium-201 chloride and sodium iodide-131 thyroid subtraction scintigraphy

The mechanism of 201Tl chloride accumulation is unclear in thyroid gland and thyroid tumor. This report examines 108 patients that received thyroid scintigraphy examinations with both 201Tl chloride and sodium 131I. The patients were diagnosed clinically and histologically whenever possible. The ROI were obtained by subtraction imaging with both isotopes and by subtraction positive and negative areas of imaging. Dynamic curves were obtained for 201Tl chloride per square unit of each ROI. The dynamic curve in the radioiodide-accumulated area was examined. The data indicate that the clearance rate of 201Tl chloride (T15) was correlated with the sodium 131I uptake rate at 24 h (r = 0.70).     

Cationic copolymerization of phenyl propenyl ethers

Ring-substituted phenyl propenyl ethers were found to form homopolymers without any rearrangement by metal halides. Phenyl propenyl ethers were less reactive than the corresponding phenyl vinyl ethers in cationic polymerization. In order to study the electronic effect of a substituent on the reactivity, cis-p-Cl,p-CH₃, and p-CH₃O-phenyl propenyl ethers were copolymerized with phenyl propenyl ether in methylene chloride at ?78°C with stannic chloride–trichloroacetic acid, and their ¹H- and ¹³C-NMR spectra were measured. The reaction constant ρ against Hammett σ_p was ?2.1. The cis-phenyl propenyl ethers were slightly more reactive than the corresponding trans isomers. On the other hand, an o-methyl group decreased the reactivity of phenyl propenyl ether. The low reactivity of o-methyl phenyl propenyl ether was attributed to the steric hindrance between the propagating carbocation and the monomer.     

An economical approach for peptide synthesis via regioselective C–N bond cleavage of lactams

An economical, solvent-free, and metal-free method for peptide synthesis via C–N bond cleavage using lactams has been developed. The method not only eliminates the need for condensation agents and their auxiliaries, which are essential for conventional peptide synthesis, but also exhibits high atom economy. The reaction is versatile because it can tolerate side chains bearing a range of functional groups, affording up to >99% yields of the corresponding peptides without racemisation or polymerisation. Moreover, the developed strategy enables peptide segment coupling, providing access to a hexapeptide that occurs as a repeat sequence in spider silk proteins.

An economical, solvent-free, and metal-free method for peptide synthesis via C–N bond cleavage using lactams has been developed.     

Waveform control for magnetic testers using a quasi-Newton method

A nonlinear iterative learning algorithm is proposed to make a voltage waveform in the secondary coil sinusoidal in this paper. The algorithm employs a globally convergent Jacobian-free quasi-Newton type solver that has a BFGS-like structure. This method functions well, and it is demonstrated using typical soft magnetic materials.     

Surface magnetism of β-FeO(OH) by Mössbauer spectroscopy

Fine particles of -FeO(OH) were prepared using the⁵⁶Fe isotope and the surfaces of the particles were coated with extremely thin⁵⁷Fe(III) layers. Mössbauer results show that the Fe(III) ions in the top surface layer are involved in the magnetic order and occupy two kinds of surface sites. Both of the two exchange field at surface sites, estimated from the temperature dependences of the hyperfine fields, are smaller than the bulk value. The decrease of exchange fields at the surface sites corresponds to the reduced number of neighboring magnetic ions at each site.