Preparation and physical properties of flame retardant acrylic resin containing nano-sized aluminum hydroxide

Poly(methylmethacrylate) (PMMA) shows high strength and transparency but is a flammable material. In this study, the surface of aluminum hydroxide was modified with methacrylate containing phosphoric acid moieties before dispersion in MMA, and organic-inorganic nano-hybrid materials were obtained by bulk polymerization in the presence of the surface-modified aluminum hydroxide. The resulting hybrid materials retained the high transparency of PMMA, with transparency values similar to that of pure PMMA. Moreover, the flame resistance of the hybrid materials was improved in comparison with that of pure PMMA, with depression of the horizontal burning rate becoming a maximum at an inorganic content of 3 wt%. These results suggest that the use of aluminum hydroxide surface-modified with phosphoric acid groups is an efficient method for obtaining good performance fire-resistant polymer materials.     

Inorganic speciation of As(III, V), Se(IV, VI) and Sb(III, V) in natural water with GF-AAS using solid phase extraction technology

The paper presents a procedure for the multi-element inorganic speciation of As(III, V), Se(IV, VI) and Sb(III, V) in natural water with GF-AAS using solid phase extraction technology. Total As(III, V), Se(IV, VI) and Sb(III, V) were determined according to the following procedure: titanium dioxide (TiO₂) was used to adsorb inorganic species of As, Se and Sb in sample solution; after filtration, the solid phase was prepared to be slurry for determination. For As(III), Se(IV) and Sb(III), their inorganic species were coprecipitated with Pb-PDC, dissolved in dilute nitric acid, and then determined. The concentrations of As(V), Se(VI) and Sb(V) can be calculated by the difference of the concentrations obtained by the above determinations. For the determination of As(III), Se(IV) and Sb(III), palladium was chosen as a modifier and pyrolysis temperature was 800 °C. Optimum conditions for the coprecipitation were listed for 100 ml of sample solution: pH 3.0, 15 min of stirring time, 40.0 μg l⁻¹ Pb(NO₃)₂ and 150.0 μg l⁻¹ APDC. The proposed method was applied to the determination of trace amounts of As(III, V), Se(IV, VI) and Sb(III, V) in river water and seawater.     

Synthesis of 5-heteroarylazulenes: first selective electrophilic substitution at the 5-position of azulene

1,3-Di-tert-butylazulene reacted with highly electrophilic trifluoromethanesulfonate of N-containing heterocycles to give 5-(dihydroheteroaryl)azulene derivatives in good yield and treatment of the 5-(dihydroheteroaryl)azulene derivatives with KOH afforded 5-(heteroaryl)azulenes in excellent yield.     

Synthesis and Applications of (ONO Pincer)Ruthenium‐Complex‐Bound Norvalines

Two (ONO pincer)ruthenium‐complex‐bound norvalines, Boc?[Ru(pydc)(terpy)]Nva?OMe ( 1 ; Boc=tert‐butyloxycarbonyl, terpy=terpyridyl, Nva=norvaline) and Boc?[Ru(pydc)(tBu‐terpy)]Nva?OMe ( 5 ), were successfully synthesized and their molecular structures and absolute configurations were unequivocally determined by single‐crystal X‐ray diffraction. The robustness of the pincer Ru complexes and norvaline scaffolds against acidic/basic, oxidizing, and high‐temperature conditions enabled us to perform selective transformations of the N‐Boc and C?OMe termini into various functional groups, such as alkyl amide, alkyl urea, and polyether groups, without the loss of the Ru center or enantiomeric purity. The resulting dialkylated Ru‐bound norvaline, n‐C₁₁H₂₃CO?l ‐[Ru(pydc)(terpy)]Nva?NH‐n‐C₁₁H₂₃ (l ‐ 4 ) was found to have excellent self‐assembly properties in organic solvents, thereby affording the corresponding supramolecular gels. Ru‐bound norvaline l ‐ 1 exhibited a higher catalytic activity for the oxidation of alcohols by H₂O₂ than parent complex [Ru(pydc)(terpy)] ( 11 a ).     

Synthesis of multisubstituted 1,3-butadienes using the ruthenium-catalysed double addition of trimethylsilyldiazomethane to alkynylboronates

The ruthenium-catalysed double addition of trimethylsilyldiazomethane to alkynes developed by Dixneuf and co-workers was applied to the synthesis of 2-alkyl- or 2-aryl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,4-bis(trimethylsilyl)-1,3-butadienes by use of alkynylboronates instead of alkynes. Di- and tetrasubstituted 1,3-butadienes were prepared from a 2-boryl-1,4-disilyl-1,3-butadiene, using the Suzuki-Miyaura coupling reaction, iodolysis of the alkenylsilane moieties with N-iodosuccinimide and hydrolysis of the carbon-silicon bonds with trifluoroacetic acid. The same compound was converted also to a bicyclic compound, a trisubstituted 1,3-butadiene and a dienone through the Diels-Alder reaction, oxidation of the alkenylboronate moiety and the Mukaiyama aldol reaction.     

Hydrogen-bonded networks in organic conductors: crystal structures and electronic properties of charge-transfer salts of tetracyanoquinodimethane with 4,4'-biimidazolium having multiprotonated States

[structure: see text] Novel hydrogen-bonded charge-transfer salts of TCNQ with mono- and diprotonated 4,4'-biimidazolium were synthesized in order to demonstrate the high potential of the 4,4'-biimidazole system in a molecular conductor from the viewpoint of crystal engineering and electronic modulation. Crystal structure analyses of neutral 4,4'-biimidazole and TCNQ salts revealed the formation of two types of hydrogen-bonding modes of the 4,4'-biimidazole moiety depending on the protonated states. Neutral 4,4'-biimidazole possessed a linear chain mode of hydrogen-bonding to construct two-dimensional network. In the TCNQ salt of monoprotonated 4,4'-biimidazolium, the 4,4'-biimidazole moiety formed a dimer by a complementary mode of hydrogen-bonding. In contrast, the salt of diprotonated 4,4'-biimidazolium showed a double linear chain mode of hydrogen-bonding to construct a three-dimensional network. The formation of two types of hydrogen-bonding modes made the difference in the stacking patterns of TCNQ columns and in their transport properties. The TCNQ salt of diprotonated 4,4'-biimidazolium exhibited high electrical conductivity (sigma(rt) = 1.1 x 10(-1) S cm(-1)).     

Effects of dipole moment, linkers, and chromophores at side chains on long-range electron transfer through helical peptides

Octadecapeptides carrying a ferrocene moiety at the molecular terminal were self-assembled on gold, and long-range electron transfer from the ferrocene moiety to gold was investigated by electrochemical methods. Effects on electron transfer of dipole moment of helical peptides, linkers connecting the peptide to gold, and chromophores introduced into the side chains were discussed. Cyclic voltammetry of the monolayers in an aqueous solution revealed that long-range electron transfer over 40 A occurred along the peptide molecule. Chronoamperometry showed that the long-range electron transfer should be ascribed to a hopping mechanism with use of amide groups as hopping sites. Electron transfer through the long peptide was not significantly accelerated by the dipole moment. However, the linker remarkably affected electron transfer depending on whether it was a methylene chain or a phenylene group, suggesting that local electron transfer between gold and the peptides should be the slowest step to determine the overall rate. Pyrenyl groups introduced into the side chains in the middle of the peptide molecule did not noticeably change electron transfer, probably because pyrenyl groups were too distant to allow direct electron transfer between them. Electrostatic potential profiles across the peptide monolayers were also calculated to explain reasonably the several interesting features in the present peptide systems.     

Structure,Properties and Biodegradation of Some Bacterial Copoly(hydroxyalkanoate)s

This article describes the relationships between not only comonomer-unit compositions but also their distributions and structures as well as properties for bacterial copoly(hydroxyalkanoate)s, including poly(3-hydroxybutyrate-co-3-hydroxyvalerate), poly(3-hydroxybutyrate-co-3-hydroxy-propionate), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), poly(3-hydroxy-butyrate-co-4-hydroxybutyrate) and poly(3-hydroxybutyrate-co-3-mercapto-propionate). It was found that as-produced copoly(hydroxy-alkanoate)s have broad comonomer-unit compositional distributions, which we can control to some degree. The structure and properties of copoly(hydroxy-alkanoate)s depend not only on the chemical structure and the comonomer-unit composition but also on the comonomer-unit compositional distribution.     

Analysis to obtain precise density fluctuation of supercritical fluids by small-angle X-ray scattering

A procedure of analysis for small-angle X-ray scattering (SAXS) data has been established to obtain density fluctuation of supercritical fluids near the critical point. It is indispensable for the certain analysis to utilize both of high-quality SAXS data measured under stable thermodynamic condition and accurate P–ρ–T data in supercritical region. As a standard example, SAXS measurements have been performed for supercritical CO₂, which is a suitable sample satisfying the condition for both experiment and analysis. The measurements were carried out along four isothermal conditions at reduced temperature of T_r = T/T_c = 1.020, 1.022, 1.043 and 1.064. Comparing the experimental density fluctuation with calculated one from the most reliable equation of state, the differences are within 8% at most.