High precision refractometry based on Fresnel diffraction from phase plates

When a transparent plane-parallel plate is illuminated at a boundary region by a monochromatic parallel beam of light, Fresnel diffraction occurs because of the abrupt change in phase imposed by the finite change in refractive index at the plate boundary. The visibility of the diffraction fringes varies periodically with changes in incident angle. The visibility period depends on the plate thickness and the refractive indices of the plate and the surrounding medium. Plotting the phase change versus incident angle or counting the visibility repetition in an incident-angle interval provides, for a given plate thickness, the refractive index of the plate very accurately. It is shown here that the refractive index of a plate can be determined without knowing the plate thickness. Therefore, the technique can be utilized for measuring plate thickness with high precision. In addition, by installing a plate with known refractive index in a rectangular cell filled with a liquid and following the described procedures, the refractive index of the liquid is obtained. The technique is applied to measure the refractive indices of a glass slide, distilled water, and ethanol. The potential and merits of the technique are also discussed.     

Comparison of the role of new ethers and conventional alkoxysilanes as external donors in the polymerization of propylene using the industrial Ziegler-Natta catalyst

Two new ethers were synthesized using the Williamson reaction from related alcohols and were used as external donors in propylene polymerization in the presence of the industrial diisobutyl phthalate-based MgCl₂-supported Ziegler-Natta catalyst. For comparison the propylene polymerization was carried out in the presence of silane and in the absence of external donors. The produced polymers were characterized by differential scanning calorimetry, xylene extraction, melt flow index, scanning electron microscopy and gel permeation chromatography. The isotacticity, molecular weight and molecular weight distribution, melt flow index, crystallinity degree and thermal properties of polypropylenes were influenced by the type of external donors.     

Synthesis,crystal structural study and catalyst active of benzyloxycarbonylmethyl triphenylphosphonium hexabromopalladate (II) in amination of aryl halides and Suzuki cross-coupling reaction

In this study, palladium (II) chloride reacted with the phosphonium salt [PhCH₂COOCH₂P(Ph)₃]Br to give [PhCH₂COOCH₂P(Ph)₃]₂[Pd₂Br₆] (1). The characterization of synthesized compound was performed by elemental analysis, FT-IR, ¹H, ³¹P, ¹³C NMR and also X-ray crystallography. It was found that this compound works as an efficient catalyst for the amination of aryl halides to afford primary amines, the results of which were satisfactory. Furthermore, it was found that the catalyst showed a high activity for Suzuki carbon–carbon cross-coupling of aryl halides and phenylboronic acid. Interestingly, the catalyst can be recovered from the reaction mixture and recycled four consecutive runs without any significant loss in activity.     

Monitoring of small‐scale anionic polymerization of caprolactam; a method to be used in an additive manufacturing process

The anionic polymerization of caprolactam using small quantities of reactants was investigated as part of a project aimed at producing polyamide parts by additive manufacturing. Various methods were used to monitor the polymerization and crystallization processes. Drop on drop small‐scale polymerization was carried out on a hot surface and monitored by Fourier transform infrared, which showed that PA6 had been polymerized successfully. PA6 synthesis was carried out in a differential scanning calorimetry cell to monitor the exothermic and endothermic processes during polymerization, and the processes were also observed by hot stage microscopy. It was found that polymerization and crystallization occurred simultaneously at slow heating rates. The amount of crystallinity produced during polymerization decreased as the heating rate increased. Copyright © 2013 John Wiley & Sons, Ltd.     

A rapid and convenient synthesis of gem-bis(dithiocarbamate) derivatives from primary aliphatic amines,carbon disulfide,and aromatic aldehydes using boron trifluoride-diethyl etherate

An efficient route for the synthesis of gem-bis(dithiocarbamate) derivatives is developed using dithiocarbamic acid salts generated from primary aliphatic amines and CS₂. The method offers high yields, employs mild reaction conditions, and demonstrates excellent functional group compatibility. The structures of the products were confirmed spectroscopically and by X-ray analysis.     

Synthesis of fused hydroxy dihydropyrroles and unexpected dihydropyrazine and dihydroquinoxaline derivatives based on heterocyclic ketene aminals

The one-pot four-component synthesis of highly functionalized fused hydroxyl dihydropyrroles and dihydropyrazines from readily available diamines, 1,1-bis (methylsulfanyl)-2-nitroethene, phenylglyoxal monohydrates, and C-H acids have been developed. This strategy provides an efficient, catalyst-free approach for easy access to various new hydroxyl-dihydropyrrole and dihydropyrazine rings in good to high yields. The products were confirmed by ¹H and ¹³C NMR, IR, mass, and X-ray crystal structure analyses.     

On the asymptotic analysis of statistical multiplexers with hyper-bursty arrivals

We consider multiplexers in discrete time fed by the superposition of Ternary Markov Sources. Such sources are the natural extension of the Binary Markov Sources (BMS) recently used to model bursty arrivals in a high speed environment. Unlike BMS, we allow sources to have arbitrary (large) variance in the duration of their OFF (silence) or ON (burst) periods.This paper focuses mainly on the impact of large variability either in the ON or OFF period on the performance. Following some asymptotic analysis, simple results on the tail behavior of the number of cells queued in the multiplexer are given.Our results indicate that ignoring the variability in the ON period may grossly underestimate the cell buildup in the multiplexer queue for all levels of the utilization. Furthermore, the impact of large variability of the OFF period depends very much on the utilization of the system. For a lightly-loaded multiplexer (utilization below a given threshold), the impact of large variability of the OFF period is minimal. However, for a heavy-loaded multiplexer (utilization above the threshold) the impact of the large variability in the OFF period is similar to that of the ON period.     

Dediazoniation of Arenediazonium Ions. Part XXII. Reactions of 2, 6-Dialkyl-Substituted Benzenediazonium Ions in Super Acids,Acetonitrile and Acetone

Reactions of 2,4,6-trimethylbenzenediazonium ( 1 ), 2,6-diethylbenzenediazonium ( 2 ) and 2,6-diisopropylbenzenediazonium ( 3 ) tetrafluoroborates were studied in magic acid, SbF₅/SO₂ClF, acetonitrile and acetone by ¹H-NMR and by analysis of the dediazoniation products. The N_α-N_β rearrangement of β-N¹⁵-labelled tetrafluoroborates 1–3 was followed by ¹⁵N-NMR of the corresponding arylazonaphthols, as well as by MS analysis of the anilines obtained by reduction of the azo compounds. Diazonium salts 2 and 3 were synthesized for the first time and the steric effect of substituents at C(2) and C(6) on the reactions under study is discussed. All the results obtained can be rationalized by heterolytic dediazoniation of diazonium salts 1 – 3 and product formation from the corresponding aryl cations.