Host-guest complexes of crown ethers with HN-proton-donor molecules

Crown ethers were reacted with HN-proton-donor molecules to obtain crystalline molecular host-guest complexes. It was found that complexes with crown ethers of different structure are formed, depending on the linear dimensions and mode of steric shielding of active centers of the proton-donor molecules.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 12, 2004, pp. 2030–2033.Original Russian Text Copyright © 2004 by Wang, Ganin.This revised version was published online in April 2005 with a corrected cover date.     

Molecular Beam Mass Spectrometry System for Characterization of Thermal Plasma Chemical Vapor Deposition

A molecular beam mass spectrometry system for in situ measurement of the concentration of gas phase species including radicals impinging on a substrate during thermal plasma chemical vapor deposition (TPCVD) has been designed and constructed. Dynamically controlled substrate temperature was achieved using a variable thermal contact resistance method via a backside flow of an argon/helium mixture. A high quality molecular beam with beamtobackground signal greater than 20 was obtained under film growth conditions by sampling through a small nozzle (75 m) in the center of the substrate. Mass discrimination effects were accounted for in order to quantify the species measurements. We demonstrate that this system has a minimum detection limit of under 100 ppb. Quantitative measurements of hydrocarbon species (H, H₂, C, CH₃, CH₄, C₂H₂, C₂H₄) using Ar/H₂/CH₄ mixtures and silicon species (Si, SiH, SiH₂, SiCl, SiCl₂, Cl, HCl) using Ar/H₂/SiCl₄ mixtures were obtained under thermal plasma chemical vapor deposition conditions.     

Polystyrene/thermoplastic starch blends with different plasticizers

Conventional plastics has a large impact in increasing the environment’s pollution. That’s why the interest has turned towards novel partially and completely biodegradable polymers. In this work, blends of polystyrene and thermoplastic starch with glycerol and Buriti (Mauritia flexuosa L.) oil as plasticizers were prepared. Samples were analyzed using TG/DTG and DSC techniques. The TG results indicated that the blends with Buriti oil are thermally more stable than those with glycerol. The DSC analysis that Buriti oil provides a higher degree of plasticization of PS, compared to the blends plasticized using glycerol under the studied conditions.     

Synthesis and structural characterization of a fully conjugated macrocyclic tetraaza(14)-membered Schiff base and its bivalent metal complexes

A novel 14-membered macrocyclic Schiff base derived from 3-cinnamalideneacetoacetanilide and o-phenylenediamine acts as a tetradentate and strongly conjugated ligand to form a cationic solid complex with CuCl₂/NiCl₂/CoCl₂/ZnCl₂. The ligand and the complexes were characterized by the usual spectral and analytical techniques. The main i.r. band of the macrocyclic Schiff base was compared to that of its metal complexes. The C=N bands are shifted to the lower wave number. The cyclic voltammogram of the copper complex shows that the macrocyclic ligand is able to stabilize the copper(III) oxidation state. The e.s.r. spectra of the copper complex in DMSO solution at room temperature and liquid N₂ temperature were recorded and their salient features thoroughly discussed. The antimicrobial screening tests were also recorded and gave good results in the presence of metal ions in the ligand system.     

On the mechanism of electroluminescence emission by porous silicon layers

The analytical treatment of a model considering the electrooxidation of p-porous silicon layers under galvanostatic conditions is able to give account of experimental facts such as the shape and location of the electroluminescence peak as well as of the spectral shift of the electroluminescence peak produced by oxidation. The proposed model considers electroluminescence to be the result of electron injection into the conduction band by an adsorbed intermediate produced by electrooxidation of the surface coverage with hydrogen or siloxene of the silicon nanocrystallites. The access of holes to the surface is made possible by low accumulation layer conditions and is the rate determining step in the electroluminescence mechanism. In this way it is possible to give a satisfactory explanation to the shift towards the blue experimented by the electroluminiscence emission maximum as a consequence of electrooxidation.     

Poly[3-(3,4-dihydroxyphenyl)glyceric acid] from Stems of <Emphasis Type="Italic">Symphytum asperum</Emphasis> and <Emphasis Type="Italic">S. caucasicum</Emphasis>

Two high-molecular-weight (>1000 kDa) water-soluble preparations were isolated from stems of Symphytum asperum and S. caucasicum. Their basic component was established as poly[hydroxy-1-carboxy-2-(3,4-dihydroxyphenyl)ethylene], analogous to that of high-molecular-weight (>1000 kDa) preparations from roots of these same plants, using IR and NMR spectral data. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 303–305, July–August, 2005. An erratum to this article is available at .     

Reaction of magnesium alkylidene carbenoids with lithium acetylides and lithium thiolates: a novel synthesis of conjugated enynes and vinyl sulfides

Magnesium alkylidene carbenoids were generated from 1-chlorovinyl p-tolyl sulfoxides with i-PrMgCl at −78 °C in THF or toluene via the sulfoxide-magnesium exchange reaction. Reaction of the generated magnesium alkylidene carbenoids with lithium acetylides or lithium thiolates gave conjugated enynes or vinyl sulfides, respectively, in moderate to good yields. The intermediate of this reaction was found to be the alkenyl anion and it could be trapped with some electrophiles to give tetra-substituted conjugated enynes and vinyl sulfides.     

Bromination by means of sodium monobromoisocyanurate (SMBI)

A variety of aromatic compounds with both activating and deactivating substituents were brominated with sodium monobromoisocyanurate (SMBI) 1, diethyl ether, diethyl ether-methanesulfonic acid, trifluoroacetic acid, or sulfuric acid were employed as solvents. Thus nitrobenzene was conveniently brominated in sulfuric acid, benzene was readily monobrominated in diethyl ether-methanesulfonic acid, and phenol was selectively brominated at the ortho position under mild conditions in refluxing diethyl ether. With substituents that are easily protonated, trifluoroacetic acid may be employed as solvent in the reaction with 1, in contrast NBS was ineffective in trifluoroacetic acid. This renders 1 a superior reagent relative to NBS. In addition to aromatics, alkenes, ketones and esters were also brominated with 1. Diethyl malonate was brominated with 1 and then subjected to a Bingel reaction with NaH to afford the desired methanofullerene in reasonable yield.     

Dioxopyrrolines. LXII. Diels-Alder reaction of 1-Aryl-4- and 5-methoxycarbonyl-1H-pyrrole-2,3-diones with various 1,3-dienes

Two new dioxopyrrolines (1-aryl-4-methoxycarbonyl-1H-pyrrole-2,3-dione 6 and the 5-methoxycarbonyl isomer 8) behaved as good dienophiles to some kind of 1,3-dienes examined. In most cases, the products were explained by the reaction where the largest lobe of HOMO of dienes reacted to the larger LUMO of dienophiles in an expected cis-endo manner. However, in the reactions of 8 with alkylbutadienes, piperylene and isoprene, abnormality in the reaction was observed, which was well explained by taking account of steric factors.