Reactions of Titanium Alkoxides with N-Methylaminoalcohols

N-methylaminoalkoxides of titanium of the type Ti(OR)_4?n(O · CHR′ · CH₂ · NR″R?)_n where R = Et and Pr¹; n = 1–4; and R′ = R″ = H, R? = Me; R′ = H, R″ = R? = Me; R′ = R″ = R? = Me, synthesized by the reactions of titanium alkoxides with aminoalcohols, show interesting variations in their properties like physical state, volatility and molecular complexity. I.r. and p.m.r. spectra of these derivatives have been recorded. A few interchange reactions with methanol and tert-butanol have also been carried out. These aminoalkoxides get cleaved with acetyl chloride and undergo insertion reactions with phenylisocyanate, thus providing the first examples of insertion reactions in such derivatives.     

Thermal analysis of lanthanide polyphosphates

Summary A study of thermal analysis of some lanthanide polyphosphates has been reported. The DTA curves of Ce, Pr and Sm polyphosphates were of similar nature. They exhibited a sharp exothermic peak indicating crystallization temperature (T _c) around 520 °C. However, no peak indicatingT _m was observed upto 800 °C. TG curves of Ce, La, Pr, Sm, Y polyphosphates indicated weight loss occurring in three stages. The integral procedural decomposition thermal analysis (ipdt) indicated that these materials had refractory nature.With 4 figures and 2 tables     

Kinetics of oxidation of some disaccharides in ammoniacal medium

Kinetics of oxidation of lactose, maltose, cellobiose and melibiose has been studied by hexacyanoferrate(III) in the presence of ammonia. A general mechanism involving the formation of intermediate enodiol anion has been suggested. The effects of dielectric constant and salts have been studied in detail. The oxidation products have been characterised by descending paper chromatography. Compensation effects have been observed.     

Effects of pH and Dye Concentration on the Optical and Structural Properties of Coumarin-4 Dye-Doped SiO2-PDMS Xerogels

Optical and structural properties of coumarin-4 dye-doped SiO₂-PDMS xerogels synthesized by acid catalyzed (one-step) and acid-base catalyzed (two-step) sol-gel routes with varying pH (0.6 to 7) and dye content ( 5 × 10^–4 to 5 × 10^–2 mole) are reported. Spectroscopic methods such as photo-luminescence, FT-IR and FT-Raman were used for characterizations. The acid catalyzed xerogels prepared with pH < 2.5 exhibited two fluorescence peaks, I at 390 nm and II at 480 nm. The acid-base catalyzed xerogels synthesized with pH < 2.5 also exhibited two peaks, I at 400 nm and II at 475 nm. Peak II was not observed for the samples with pH 2.5. This phenomenon was attributed to the existence of pH dependent different forms of coumarin-4 molecule. The concentration-quenching phenomenon was observed for the acid catalyzed xerogels prepared with different dye concentration. TheFT-IR spectra indicated the existence of hydrogen bonds between the carbonyl groups of dye molecules and the silanol groups of gel matrix. The hydrogen bonding was the highest for the samples with the extremity pH, 0.6 and 7, resulting in the highest dye/gel matrix interactions, hence, the highest fluorescence peaks. The Raman studies indicated that the samples prepared with pH < 2.5 possessed relatively more number of 3-membered siloxane rings than 4-membered siloxane rings. The ring statistics was reversed for the samples with pH > 2.5. The number of silanol groups was higher for the samples with pH > 2.5.     

Telluro- and seleno-bridged TiIV-MII (M = Ni,Pd, Pt) heterobimetallic complexes

Summary Heterobimetallic complexes of the types [Cp₂Ti(-EAr)₂-M(dppe)] (ClO₄)₂ [(1)–(4); M, E = Ni, Te (1); Ni, Se (2); Pt, Te (3); Pt, Se (4); Ar = Ph (a), C₆H₄-4-Me (b), C₆H₄-4-OMe (c), C₆H₄-4-OEt (d)] and [Cp₂Ti(-TeAr)₂-MCl ₂] [M = Pd (5), Pt (6)] were obtained by the reactions of Cp₂Ti(EAr)₂ with M(dppe)(ClO₄)₂ and M(PhCN)₂Cl₂, respectively. While (1), (5) and (6) are stable in the solid state as well as in solution, (2)–(4) undergo dissociation to M(dppe)(EAr)₂ and Cp₂Ti(ClO₄)₂ in solution, as shown by multinuclear (³¹P{¹H},¹⁹⁵Pt{¹H}, ¹²⁵Te{¹H}) n.m.r. studies. The reaction of Cp₂Ti(SeAr)₂ with M(PhCN)₂Cl₂, however, leads to the formation of Cp₂TiCl₂ and a polymeric material [M(SeAr)₂] _n .     

Melt-polymerizable bisimido-bisphthalonitriles containing silicon,fluoro, and ether groups: Synthesis,characterization, and NMR study

Various melt-polymerizable bisimido-bisphthalonitrile polymer precursors were synthesized by the reaction of 4-aminophthalonitrile (4-APN) with bis(3,4-dicarboxyphenyl) dimethylsilane dianhydride (SIDA), 4,4′-hexafluoroisopropylidene diphthalic anhydride (6FDA), bis(3,4-dicarboxyphenyl)ether dianhydride (ODPA), and 3,3′, 4,4′-tetracarboxylichenzophen+ne dianhydride (BTDA) in an aprotic solvent. The synthesized monomers showed crystalline melting at 269 and 271°C. Elemental analysis, differential thermal analysis (DTA), infrared (IR), nuclear magnetic resonance (¹H-NMR) and mass spectral studies were carried out to characterize the synthesized monomers. Thermogravimetric analysis (TGA) of the synthesized monomers showed their thermal stability at 410–400°C. A detailed study and NMR investigation of the first step of condensation reaction was carried out and indicated the formation of a transient charge transfer complex. Thermal cyclization of the formed intermediate, however, gave the required monomers. A preliminary study demonstrated that melt-polymerization of the synthesized monomers gave thermallystable, tough polymers.     

Assembly of the hexameric Escherichia coli arginine repressor investigated by nano-electrospray ionization time-of-flight mass spectrometry

The arginine repressor (ArgR) from Escherichia coli regulates genes for L-arginine metabolism and is a required recombination factor for colE1 plasmid replication. Both functions require binding of L-arginine to the protein. In this work, nano-electrospray ionization time-of-flight mass spectrometry (nano-ESI-TOFMS) is used to study conformational and oligomeric states of intact ArgR and its isolated structural domains. In agreement with X-ray diffraction studies, it is shown that ArgR oligomerizes to form hexamers in both the presence and absence of L-arginine, and the basic unit of oligomerization appears to be the trimer. Higher-order assembly into dodecamers is also detected. The isolated C-terminal domain is found to associate into trimers and hexamers whereas the N-terminal domain is detected in its monomeric form. The observed species distributions suggest a role for the N-terminal domain in hexamer stabilization.     

Removal of185W,99Mo and125Sb radioisotopes from aqueous solutions using polyamine incorporated polysaccharides

Polyamino group-containing resins act both as chelating ion exchangers and weakly basic anion exchangers depending upon the species in contact in the solution. In the present work, ion exchangers based on polyamine incorporated polysaccharides (cellulose and galactomannan or guaran) have been used for removal of radioisotopes of¹⁸⁵W as WO ₄ ^2– ,⁹⁹Mo as MoO ₄ ^2– and¹²⁵Sb as Sb³⁺ from their separate aqueous solutions. These chelating anion exchangers have been synthesized by reaction of polysaccharides with epichlorohydrin followed by the respective polyamines as nucleophiles in a strongly alkaline medium. WO ₄ ^2– and MoO ₄ ^2– are adsorbed from their aqueous solutions through anion exchange process by chloride form of cellulose-triethylenetetraamine (cellulose-trien), cellulose-tetraethylenepentaamine (cellulose-tetren), guaran-triethylenetetraamine (guar-trien) and guar-tetraethylenepentaamine (guar-tetren) weakly basic anion exchangers. Guar-tetren chelating polymer has been found to be highly selective for¹²⁵Sb isotopes presumably due to the presence of chelating cis-hydroxy and tetren groups in the galactomannan matrix.     

Enantioselective synthesis of tarchonanthuslactone via iterative hydrolytic kinetic resolution

A short and practical enantioselective synthesis of tarchonanthuslactone has been achieved in high diastereomeric excess using iterative Jacobsen’s hydrolytic kinetic resolution and ring closing metathesis as the key steps.     

A boxmodel development to study the relationships between the photo-oxidants and the particles formation in the troposphere

The model BAGS (Boxmodel for Aerosol and Gasphase Simulations) has been developed. It is composed of two major modules: the first one describes the system of the chemical reactions in the gaseous phase, the second one calculates the aerosol chemical composition and the dimensional distribution of the particles. The boxmodel has been developed with the introduction of new chemical and physical processes, not previously included, in particular the formation of Secondary Organic Aerosol. The other implemented processes are a module for the dynamic of the particle population, nucleation, coagulation and dry deposition. The last phase of the work has been a check of the BAGS capabilities by a series of tests, that have permitted to compare it with other models (MAPS and MADM). The tests in particular have concerned the aerosol water content prediction, the photochemistry, the condensation of the inorganic compounds and the formation of Secondary Organic Aerosol.