Indeno-Polycyclic Aromatic Hydrocarbons: A Versatile New Synthetic Route

Acylation of a polycyclic aromatic hydrocarbon (PAH) adjacent to a ring junction with 2-bromobenzoyl chloride followed by Flash Vacuum Pyrolysis (FVP) of the resulting bromoketone affords the corresponding indeno-annulated PAH. The new method is illustrated by syntheses of indeno[1,2,3-cd]pyrene (1) from pyrene and indeno[1,2,3-cd]fluoranthene (2) from fluoranthene. The formation of indeno[1,2,3,4-defg]chrysene (11) from FVP of 8-(2-bromobenzoyl)-fluoranthene (10), and as a secondary product from FVP of 3-(2-bromobenzoyl)fluoranthene (9), reveals the ability of phenyl groups to migrate around the periphery of a didehydro-PAH. Mechanisms involving reversible hydrogen atom transfers are proposed. Diacylation of fluoranthene with 2-bromobenzoyl chloride followed by FVP gives the previously unknown, nonplanar, nonalternant, C₂₈H₁₄ PAH diindeno[1,2,3,4-defg: 1,2,3-rs]chrysene (21) in just two steps.     

The Identification of Cyclopenta-Fused and Ethynyl-Substituted Polycyclic Aromatic Hydrocarbons in Benzene Droplet Combustion Products

In order to investigate new aspects of polycyclic aromatic hydrocarbon (PAH) growth and soot formation, we have synthesized special reference standards of cyclopenta-fused PAH (CP-PAH) and ethynyl-substituted PAH. We have identified several of these CP-PAH and ethynyl-PAH in benzene droplet combustion products, using high pressure liquid chromatography (HPLC) and ultraviolet-visible (UV) absorption spectroscopy. Although one CP-PAH identified in these products - acenaphthylene - has previously been identified as a product of a variety of combustion systems, we have identified six additional CP-PAH and two ethynyl-PAH which have never before been unequivocally identified as the products of benzene pyrolysis or combustion: acephenanthrylene, aceanthrylene, cyclopent[hi]acephenanthrylene, cyclopenta[cd]fluoranthene, cyclopenta[cd] pyrene, dicyclopenta[cd, jk]pyrene, 2-ethynylnaphthalene, and 1-ethynylacenaphthylene. We present the corresponding UV absorption spectra obtained from the HPLC analysis of benzene droplet combustion products, and compare them to the UV absorption     

Anthraquinone Losses During Alkaline Pulping

Extensive loss of anthraquinone (AQ) or the active catalyst anthrahydroquinone (AHQ) from the AQ –- AHQ catalytic cycle has been explained in part by side reactions leading to the reaction product anthrone (anthracen-9-one), followed by subsequent formation of adducts with lignin quinone methides. Degradation of an adduct between anthrone and the quinone methide of guaiacylglycerol-β-guaiacyl ether, under soda pulping conditions, resulted in a complex mixture of products. The mixture included 3-guaiacylbenzanthrone, bianthronyl, bianthrone, guaiacol, AQ, trans-coniferyl alcohol, trans-coniferylaldehyde, cis- and trans-1-(3-methoxy-4-hydroxyphenyl)-2-(2-methoxyphenoxy)ethene, vanillin, and 2-methoxy-4-vinylphenol. C-13 NMR studies of lignins isolated from soda/AQ spent liquors indicated the presence of residual anthrone adducts and a significant content of chemically attached AQ.     

Mineral admixtures in mortars: Quantification of the physical effects of inert materials on short-term hydration

This work is the second part of an overall project, the aim of which is the development of general mix design rules for concrete containing different kinds of mineral admixtures. The first part presented the separation of the different physical effects responsible for changes in cement hydration when chemically inert quartz powders are used in mortars. This second part describes the development of an empirical model, based on semiadiabatic calorimetry measurements, which leads to the quantification of the enhancement of cement hydration due to the heterogeneous nucleation effect at short hydration times. Experimental results show that not all the admixture particles participate in the heterogeneous nucleation process. Consequently, the concept of efficient surface S_eff is introduced in the model. S_eff is the total admixture surface S (m² of mineral admixture/kg of cement) weighted by a function ξ(p). The efficiency function ξ(p) depends only on the replacement rate p and is independent of time, fineness and type of mineral admixture used. It decreases from 1 to 0: Low replacement rates give an efficiency value near 1, which means that all admixture particles enhance the hydration process. An efficiency value near 0 is obtained for high replacement rates, which indicates that, from the hydration point of view, an excess of inert powder does not lead to an increase in the amount of hydrates compared with the reference mortar without mineral admixture. The empirical model, which is mainly related to the specific surface area of the admixtures, quantifies the variation of the degree of hydration induced by the use of inert mineral admixtures. One application of the model, coupled with Powers' law, is the prediction of the short-term compressive strength of mortars.     

Mineral admixtures in mortars effect of type, amount and fineness of fine constituents on compressive strength

This work is the third part of an overall project the aim of which is the development of general mix design rules for concrete containing different kinds of mineral admixtures (also named mineral additions or mineral constituents). It deals with the compressive strength of mortars made with up to 75% of crushed quartz, limestone filler or fly ash of different fineness. The paper presents all the experimental results as a sort of database and emphasizes the effects on strength of the nature, amount and fineness of mineral admixtures. For short hydration times (1 to 2 days), the nature of mineral admixture is not a significant parameter, as mortars containing the same amount of different kinds of admixtures having equivalent fineness present similar strengths. For long hydration times (up to 6 months), the excess strength due to fly ash pozzolanic activity is quantified by the difference between the strengths of mortars containing the same proportions of inert and pozzolanic admixtures with the same fineness. In the case of inert mineral admixtures, the increase in strength with the fineness of mineral admixtures cannot be explained by the filler effect, but can be attributed to the physical effect of heterogeneous nucleation. In the next part of this work, these results will be used for the elaboration of an empirical model leading to the quantification of both physical and chemical effects. This model presents strong similarities with the previous model based on calorimetric results.     

Absorption of gas into a wavy falling film

In this work, we present results of a study of gas absorption into a falling film on a vertical substrate. The film flow is accompanied by the formation of nonlinear waves which strongly influence the diffusion layer that develops from the film surface. As a result, significant enhancement of mass transfer has been observed in experiments. We use recent advances in modelling of the hydrodynamics and solve a two-dimensional convective-diffusion equation for the solute concentration. Numerical solutions for the finite-amplitude wave regimes and associated integral absorption rates are obtained for a range of flow conditions. Our results show clearly the influence of waves on the development of the diffusion layer and, in particular, the enhancement of absorption due to the waves; the existence of optimal conditions for maximizing the absorption rate is also demonstrated.     

NGF Enhances CGRP Release Evoked by Capsaicin from Rat Trigeminal Neurons: Differential Inhibition by SNAP-25-Cleaving Proteases

Nerve growth factor (NGF) is known to intensify pain in various ways, so perturbing pertinent effects without negating its essential influences on neuronal functions could help the search for much-needed analgesics. Towards this goal, cultured neurons from neonatal rat trigeminal ganglia—a locus for craniofacial sensory nerves—were used to examine how NGF affects the Ca²⁺-dependent release of a pain mediator, calcitonin gene-related peptide (CGRP), that is triggered by activating a key signal transducer, transient receptor potential vanilloid 1 (TRPV1) with capsaicin (CAP). Measurements utilised neurons fed with or deprived of NGF for 2 days. Acute re-introduction of NGF induced Ca²⁺-dependent CGRP exocytosis that was inhibited by botulinum neurotoxin type A (BoNT/A) or a chimera of/E and/A (/EA), which truncated SNAP-25 (synaptosomal-associated protein with Mr = 25 k) at distinct sites. NGF additionally caused a Ca²⁺-independent enhancement of the neuropeptide release evoked by low concentrations (<100 nM) of CAP, but only marginally increased the peak response to ≥100 nM. Notably, BoNT/A inhibited CGRP exocytosis evoked by low but not high CAP concentrations, whereas/EA effectively reduced responses up to 1 µM CAP and inhibited to a greater extent its enhancement by NGF. In addition to establishing that sensitisation of sensory neurons to CAP by NGF is dependent on SNARE-mediated membrane fusion, insights were gleaned into the differential ability of two regions in the C-terminus of SNAP-25 (181–197 and 198–206) to support CAP-evoked Ca²⁺-dependent exocytosis at different intensities of stimulation.     

A Symmetrical Diester as the Sex Attractant Pheromone of the North American Click Beetle Parallelostethus attenuatus (Say) (Coleoptera: Elateridae)

Hexanoic acid, 1-octanol, 1,8-octanediol, octyl hexanoate, 1,8-octanediol monohexanoate, and 1,8-octanediol dihexanoate were identified in headspace volatiles collected from the crushed abdomen of a female click beetle of the species Parallelostethus attenuatus (Say) (Elaterinae, tribe Elaterini). In field trials carried out in Illinois, South Carolina, North Carolina, and Virginia, adult male beetles were strongly attracted to 1,8-octanediol dihexanoate alone. Blends of the dihexanoate with one or more of the other compounds proved to be less attractive than the dihexanoate alone, suggesting that the pheromone of this species may consist of a single compound. The symmetrical diester structure of the pheromone is a novel natural product and appears to be structurally unique among insect pheromones.