Examining the use of oxide particles to enhance the sensitivity of polymer\carbon black nanocomposite gas sensors

This paper investigates the use of NiO particles to enhance the vapour sensing properties of polyethylene adipate (PEA)\carbon black (CB) composite materials. Four PEA\CB suspensions were prepared with 0, 10, 20 and 30 w/w% NiO, respectively. Hypermer PS3 surfactant was shear mixed into each of the suspensions for 300 s to achieve a homogenous dispersion and to prevent reagglommeration of both the CB and NiO particles. A 0.1 μl drop of each composite was deposited between Cu electrodes on a printed circuit board (PCB) substrate using a microlitre syringe. The samples were allowed to dry for 24 h in an oven at 333 K to remove any remaining solvent. After preparation, the sensors were exposed to propanol and butanol at concentrations ranging from 0 to 25 000 ppm in steps of 5000 ppm. The response of the PEA\CB sensors improved significantly as the concentration of NiO particles in the material increased and maximum relative differential responses as high as 37% and 92.8% were recorded after exposure to 25 000 ppm propanol and butanol, respectively. This high response can be explained using the Flory–Huggins interaction parameter along with structural changes in the polymer composite caused by the addition of NiO. This paper concludes that NiO particles can be used as a method to increase the sensitivity of existing conducting polymer composite gas sensing materials.     

A suite of novel allenes from Australian melolonthine scarab beetles. Structure,synthesis, and stereochemistry

A suite of allenic hydrocarbons, previously unknown as a molecular class from insects, has been characterized from several Australian melolonthine scarab beetles. The allenes are represented by the formula CH(3)(CH(2))(n)()CH=*=CH(CH(2))(7)CH(3) with n being 11-15, 17 and 19, and thus, all have Delta(9,10)-unsaturation. These structures have been confirmed by syntheses and comparisons of spectral and chromatographic properties with those of the natural components. The enantiomers of (+/-)-Delta(9.10)-tricosadiene and Delta(9,10)-pentacosadiene were separable on a modified beta-cyclodextrin column (gas chromatography), and the natural Delta(9,10)-tricosadiene (n = 11) and Delta(9,10)-pentacosadiene (n = 13) were shown to be of >85% ee. Syntheses of nonracemic allenes of known predominating chirality were acquired using both organotin chemistry and sulfonylhydrazine intermediates, and comparisons then demonstrated that the natural allenes were predominantly (R)-configured.     

Stationary phase effects on the dynamic affinity of low-molecular-mass displacers

In this paper, the selectivity of a variety of cation-exchange stationary phases was investigated using a homologous series of displacer molecules based on pentaerythritol. These displacers were derived from pentaerythritol and contained either four trimethyl ammonium groups [pentaerythrityl-(trimethylammonium chloride)4, PE(TMA)4], benzene rings [pentaerythrityl-(benzyl dimethylammonium chloride)4, PE(DMABzCl)4], heptyl groups [pentaerythrityl-(heptyl dimethylammonium iodide)4, PE(DMAHepI)4] or cyclohexyl groups [pentaerythrityl-(cyclohexyl dimethylammonium iodide)4, PE(DMACyI)4]. This series enabled us to probe the secondary interactions that can play a role in the affinity of low-molecular-mass displacers for different stationary phases. The relative affinities of these displacers were examined using a displacer ranking plot based on the steric mass action (SMA) isotherm model. While hydrophobicity and aromaticity played important roles in generating the affinity to the hydrophilized polystyrene-divinylbenzene (Source 15S) and polymethacrylate-based (Toyopearl 650M) resins, these secondary interactions had a minimal impact on the selectivity in agarose resins coated with dextran (SP Sepharose XL), "gel in a shell" (S Ceramic HyperD F), and monolithic (Bio-Rad Uno S6) cation-exchange materials. Further, the results with a tentacular stationary phase (Fractogel EMD) suggest that the alkyl chains on PE(DMAHepI)4 play an important role in increasing the affinity, possibly because of strong interactions between the alkyl moiety and the polymer matrix as well as between the charged groups and the polyelectrolyte tentacles. The results of this study provide insight into the design of high affinity, low-molecular-mass displacers for different cation-exchange stationary phase materials.     

The synthesis of some lipophilic tetra-arylborates for use in membrane electrode preparation

Synthetic methods for preparing four lipophilic tetra-arylborates considered suitable candidates for use in membrane electrodes are described. Qualitative precipitation tests were performed with several cations. The sodium salts of the four tetra-arylborates were found to have limited stability but the cesium salts were relatively stable.     

Structures of HCN-Mgn (n=2-6) complexes from rotationally resolved vibrational spectroscopy and ab initio theory

High-resolution infrared laser spectroscopy has been used to determine the structures of HCN-Mgn complexes formed in helium nanodroplets. The magnesium atoms are first added to the droplets to ensure that the magnesium complexes are preformed before the HCN molecule is added. The vibrational frequencies, structures, and dipole moments of these complexes are found to vary dramatically with cluster size, illustrating the nonadditive nature of the HCN-magnesium interactions. All of the complexes discussed here have the nitrogen end of the HCN pointing towards the magnesium clusters. For Mg3, the HCN binds to the "threefold" site, yielding a symmetric top spectrum. Although the HCN-Mg4 complex also has C3v symmetry, the HCN sits "on-top" of a single magnesium atom. These structures are confirmed by both ab initio calculations and measurements of the dipole moments. Significant charge transfer is observed in the case of HCN-Mg4, indicative of charge donation from the lone pair on the nitrogen of HCN into the lowest unoccupied molecular orbital of the Mg4.     

Patterned dual pH-responsive core-shell hydrogels with controllable swelling kinetics and volumes

Dual pH-responsive core-shell hydrogels containing both a vinyl pyridine component and a 2-dimethylaminoethyl methacrylate component were prepared using an in situ photopolymerization process. Complementary photomasks were utilized to prepare hydrogels with core/shell volume ratios of 2:1, 1:1, and 1:2. Depending on the location of each polymer component, dramatically different swelling profiles were achieved. Selective swelling of the shell followed by the core components allowed the hydrogel to expand with the usual kinetics; however, by switching the location of each polymer component and swelling the core first, swelling rates decreased by over 1 order of magnitude and were dependent on the shell component's volume. The ability to pattern core/shell volumes also provided the ability to fabricate hydrogels that possess a constant maximum diameter but different cutoff points between its first and its second transition volumes. These materials may be of interest for controlled release applications.     

Double diastereoselective intramolecular cyclopropanation to P-chiral [3.1.0]-bicyclic phosphonates

[reaction: see text] A double diastereotopic differentiation strategy on a phosphonoacetate template is described. The approach utilizes Rh(2)(OAc)(4)-catalyzed intramolecular cyclopropanation (ICP) employing the (R)-pantolactone auxiliary in the ester functionality of the phosphonoacetate. The olefinic diastereofacial selectivity is governed by inherent electronic and steric interactions in the reacting carbene intermediate, while the group selectivity is dictated by the chiral auxiliary. This approach is being developed as an effective method to access bicyclic P-chiral phosphonates.     

Rearrangements of cyclobutenones. Electrocyclic ring closure and thermal ring expansions of 3-allenyl- and 3-alkynyl-2-dienyl-4,4-dimethoxycyclobutenones

Thermal rearrangements of 2-allenyl- and 2-alkynyl-3-(2-ethenylphenyl)-4,4-dimethoxycyclobutenones were studied. At ambient temperature, the allenyl compounds undergo an electrocyclic cascade to give bicyclo[4.2.0]octadienyl-fused cyclobutenones. These unusual tetracyclic cyclobutenones were shown to be viable synthetic precursors to benzo[a]anthracene-7,12-diones, compounds representing the framework of the angucycline group of naturally occurring antibiotics. In contrast, the 2-alkynylcyclobutenones are stable at ambient temperature but undergo a facile rearrangement at 110 degrees C (toluene) to give the previously unknown naphthalene derivatives, 1,2-dihydro-2,2-dimethoxy-1-(3-alkenylidene)naphtho[2,1-b]furans.