Effect of cooling rate on the crystal/mesophase polymorphism of polyamide 6

The solidification of the quiescent polyamide 6 (PA 6) melt has been analyzed as a function of the cooling rate in a wide range between 1.67 × 10⁻² and close to 2 × 10² K s⁻¹, by means of differential scanning calorimetry at a low cooling rate of up to about 1 K s⁻¹, and by the recording of continuous cooling curves and time-resolved X-ray diffraction on cooling at a higher rate. The performed experiments allowed for the first time to establish the relationship between the cooling rate, the crystallization temperature, and the X-ray structure of PA 6. The exclusive formation of monoclinic α-crystals is only detected if the crystallization temperature is higher than about 430 K or if the cooling rate is slower than about 5 K s⁻¹, respectively. The formation of α-crystals is increasingly replaced by the development of mesophase with increasing cooling rate, accompanied with a decrease of the temperature of crystallization/ordering. Finally, completely amorphous samples were obtained on cooling faster than about 10² K s⁻¹. The continuous decrease of the temperature of crystallization with increasing cooling rate, regardless of the specific structure formed, precludes a primary effect of the nucleation mechanism on the α-crystal/mesophase polymorphism of PA 6. A preliminary discussion of the effect of molar mass of PA 6 on the cooling rate-dependent polymorphism is also included.     

Synthesis and chiroptical properties of ferrocene-[4]-helicenequinones: kinetic resolution of a planar-chiral diene

Both enantiomers of ferrocene [4]-helicenequinone 6, showing planar and helical chiralities, have been synthesized with very high optical purities using, as the key step, a kinetic resolution process between planar-chiral racemic ferrocene diene 2 and enantiopure sulfinyl benzoquinone (S)-3.     

Bowman-Birk inhibitors from legumes and human gastrointestinal health: current status and perspectives

Bowman-Birk inhibitors and their variants (BBI) from legumes, such as soybean, pea, lentil and chickpea, are a class of naturally-occurring protease inhibitors which have potential health-promoting properties within the gastrointestinal tract. BBI can resist both acidic conditions and the action of proteolytic enzymes, and transit through the stomach and small intestine without major degradation, permitting significant amounts to reach the large intestine in active form to exert their reported anti-carcinogenic and anti-inflammatory properties. These potential pharmacological benefits have been linked recently to the intrinsic ability of BBI to inhibit serine proteases, and the data suggest that both trypsin- and chymotrypsin-like proteases involved in carcinogenesis should be considered as potential targets of BBI. However, the therapeutic targets and the action mechanisms of BBI remain unknown. Their elucidation will provide insights into the properties of these plant protease inhibitors as colorectal chemopreventive agents, providing a strong base for the development of legume crops and their products as pro-nutritional, health-promoting food. The deployment of modern genomic tools and genome sequence information are underpinning studies of natural and induced polymorphism in BBI. Genetic markers for BBI variants with improved properties can be exploited ultimately in legume breeding programmes to assist the introgression of such variant genes and the development of superior genotypes for human nutrition.     

Ensemble statistics of active and reactive sound intensity in reverberation rooms

This paper examines fundamental statistical properties of the active and reactive sound intensity in reverberant enclosures driven with pure tones. The existing theory for sound intensity in a diffuse sound field, which is based on Waterhouse's random wave model and therefore limited to the region of high modal overlap, is extended to the region of low modal overlap by taking account of the random fluctuations of the sound power emitted by the source that generates the sound field. The validity of the extended model is confirmed by experimental and numerical results.     

Chemical speciation of trace metals in fine airborne particles: advances in operational performance of a new sequential extraction scheme

A speciation method of inorganic metal compounds in airborne particulate matter based on selective sequential extractions is described. The sequential leaching procedure was perfected for improvement of performance at different stages of scheme. The loss of fine particles during the leaching procedure was the main source of error that was assessed and corrected. Loss of sample volume due to the heating steps and due to the absorption on filter material was also a difficulty to solve. New experimental conditions were optimized for the operational scheme to remove the different sources of loss. Microwave assistance with an optimum programme as a heating system, filtration of extractable solutions, and the use of internal standards were the main contributions.     

Synthesis and Characterization of Triazolium Iodide Ionic Liquid Electrolyte for Dye Sensitized Solar Cells

Imidazolium iodide compounds have been utilized in the electrolytes for dye sensitized solar cells (DSSC). Most of the investigations with these compounds focus on the formulation of eutectic mixtures that promote efficient dissociation and diffusion of the iodide and triiodide species. Facile alternative synthetic approaches such as click chemistry (Huisgen 3+2 dipolar cycloaddition reaction) can be utilized to broaden the scope of electrochemically stable promising materials for novel electrolyte systems. Here, we report the first example of a triazolium functionalized cyclic siloxane that can be used as an electrolyte component in solvent-based DSSCs. The devices fabricated with this new triazolium salt in the electrolyte yielded short circuit current densities (26 mA/cm²), as well as power conversion efficiencies of 8%, these values are comparable to those obtained for imidazolium salt analogues.     

Competitive Silyl–Prins Cyclization versus Tandem Sakurai–Prins Cyclization: An Interesting Substitution Effect

Two different mechanism pathways are observed for the reaction of allylsilyl alcohols 1 and aldehydes in the presence of trimethylsilyl trifluoromethanesulfonate (TMSOTf). In the case of allylsilyl alcohols without allylic substituents, the reaction gives dioxaspirodecanes, which are the products of a tandem Sakurai–Prins cyclization. In contrast, allylsilyl alcohols with an allylic substituent (R²≠H) selectively provide oxepanes, thus corresponding to a direct silyl–Prins cyclization. Both types of product are obtained with excellent stereoselectivity. Theoretical studies have been performed to obtain some rationalization for the observed stereoselectivity.     

Factors involved in the nuclearity of silver thiosemicarbazone clusters: cocrystallization of two different sized tetranuclear silver(I) clusters derived from a phosphinothiosemicarbazone ligand

The reaction of silver acetate with a phosphinothiosemicarbazone ligand, HLPPh, yielded the tetranuclear silver compound [Ag 4(LPPh) 4].2MeOH ( 1), which after recrystallization results in the cocrystallization of two different silver clusters, [Ag 4(LPPh) 4] (a)[Ag 4(LPPh) 4] (b).8MeOH ( 2). The factors involved in the assembly of tetranuclear compounds derived from thiosemicarbazone ligands and the structural differences between the two clusters are analyzed herein. Additionally, HLPPh and complex 1 exhibit photoluminescence in solution at room temperature.     

Remote aromatic stabilization in radical reactions

The rates of free radical reduction of a series of anthracene derivatives and 1-phenyl-4-bromodecane with tributyltin hydride are mediated by the remote aromatic substituent in an apparent through-space interaction. Density functional calculations suggest that this enhancement is not due to direct stabilization of the free radical intermediate, and is likely to be achieved through the interaction of the aromatic moiety with the polarized transition state leading to the intermediate.