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.