Amines play vital roles in agricultural, pharmaceutical, and food industries, but volatile amine vapors are serious threats to human health. Previously reported fluorescent sensors for amine vapor detection usually suffer from aggregation-caused quenching (ACQ) effect and need to be dispersed in solution or matrix materials. Herein, based on the fluorogen of 2-(2-hydroxyphenyl)quinazolin-4(3H)-one (HPQ) with aggregation-induced emission (AIE) properties, we have developed a fluorescent sensor HPQ-Ac for light-up detection of amine vapors through aminolysis reaction. The portable HPQ-Ac sensor can be easily prepared by directly depositing on filter paper, and it can only light up via exposure to amine vapors among various volatile organic compounds. Taking advantage of its portability and high sensitivity for amine vapors, HPQ-Ac sensor can also be used for food spoilage detection and fluorescent invisible ink.

Fluorescent Light-Up Detection of Amine Vapors Based on Aggregation-Induced Emission

Conceptual density functional theory provides a method for analyzing the chemical reactivity in terms of different global reactivity descriptors including electrophilicity and their local counterparts like philicity. These concepts’ definitions and various applications that demonstrate their interpretive power are discussed. Global and local electrophilicities are able to account for a wide variety of chemical phenomena.

Electrophilicity index within a conceptual DFT framework

The waste cooking oil (WCO) production from the catering industry and food processing industry causes serious environmental, economic and social problems. However, WCO can be used for the preparation of fine chemicals such as internal plasticizer. With this aim, this work is focused on preparing internal plasticizer by using WCO and determining technical viability of non-migration poly (vinyl chloride) (PVC) materials. The mannich base of waste cooking oil methyl ester (WCOME) was synthesized from WCO via esterification, interesterification and mannich reaction, which was used to produce self-plasticization PVC materials as an internal plasticizer. The results showed that the PVC was plasticized effectively. Self-plasticization PVC films showed no migration in n-hexane, but 15.7% of dioctyl phthalate (DOP) leached from DOP/PVC(50/50) system into n-hexane. These findings transformed the traditional plastic processing technology and obtained cleaner production of no migration plasticizer from WCO.

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A Strategy for Nonmigrating Plasticized PVC Modified with Mannich base of Waste Cooking Oil Methyl Ester.

Model reactions for the 4-dimethylaminopyridine (DMAP)-catalyzed ring-opening polymerization of lactide and the corresponding lactic O-carboxylic anhydride (lacOCA) have been studied computationally at the B3LYP/6-31G(d) level of theory. The solvent effect of dichloromethane was taken into account through PCM/SCRF single-point calculations at the B3LYP/6-31G(d) level of theory. In marked contrast with that predicted for the reaction of alcohols with acetic anhydride, the mechanism in which nucleophilic activation of the monomer involving acylpyridinium intermediates was found to be energetically less favorable than the base activation of the alcohol through hydrogen bonding. The concerted pathway for the ring-opening of lactide and lacOCA was shown to compete with the traditional stepwise mechanism involving tetrahedral intermediates. Furthermore, DMAP is proposed to act as a bifunctional catalyst through its basic nitrogen center and an acidic ortho-hydrogen atom.

Monomer versus alcohol activation in the 4-dimethylaminopyridine-catalyzed ring-opening polymerization of lactide and lactic O-carboxylic anhydride.

Substituent effects in organic chemistry are generally described in terms of experimentally derived Hammett parameters whereas a convenient theoretical tool to study these effects in π-conjugated molecular systems is molecular electrostatic potential (MESP) analysis. The present study shows that the difference between MESP at the nucleus of the para carbon of substituted benzene and a carbon atom in benzene, designated as ΔVC, is very useful to quantify and classify substituent effects. On the basis of positive and negative ΔVC values, a broad classification of around 381 substituents into electron withdrawing and donating categories is made. Each category is again sorted based on the magnitude of ΔVC into subcategories such as very strong, strong, medium, and weak electron donating/withdrawing. Furthermore, the data are used to show the transferability and additivity of substituent effects in π-conjugated organic molecules such as condensed aromatic, olefinic, acetylenic, and heterocyclic systems. The transferability properties hold good for ΔVC in all these molecular systems. The additive properties of substituent effects are strongly reflected on ΔVC and the predictive power of the data to assign the total substituent effects of multi-substituted systems is verified. The ΔVC data and the present classification of substituents are very useful to design π-conjugated organic molecular systems with desired electron rich/poor character.

Quantification and classification of substituent effects in organic chemistry: a theoretical molecular electrostatic potential study

The quality of reactivity predictions coming from alternative theoretical approaches as well as experimental reactivity constants is examined in the case of the ester aminolysis process. The aminolysis of a series of para-substituted phenyl acetates is studied. The barrier heights for the rate-determining stage of the aminolysis of 16 phenyl acetate derivatives were predicted by employing density functional theory at the B3LYP/6-31+G(d,p) level. Experimental kinetic studies were carried out for the n-butylaminolysis of seven p-substituted phenyl acetates in acetonitrile. The results show that the electrostatic potential at the carbon atom of the carbonyl reaction center provides an excellent description of reactivities with regard to both theoretical barrier heights and experimental rate constants. The performance of other reactivity indices, Mulliken and NBO atomic charges, electrophilicity index, and Hammett constants, is also assessed.

Predicting Reactivities of Organic Molecules. Theoretical and Experimental Studies on the Aminolysis of Phenyl Acetates

Density functional and ab initio methods were applied in examining the possible mechanistic pathways for the reaction of methyl benzoate with ammonia. Transition state structures and energies were determined for concerted and neutral stepwise mechanisms. The theoretical results show that the two possible pathways have similar activation energies. The general base catalysis of the process was also examined. The predictions reveal that the catalytic process results in considerable energy savings and the most favorable pathway of the reaction is through a general-base-catalyzed neutral stepwise mechanism. The structure and transition vectors of the transition states indicate that the catalytic role of ammonia is realized by facilitating the proton-transfer processes. Comparison of the energetics of the aminolysis for methyl benzoate and methyl formate shows the more favorable process to be that for the aliphatic ester. The differing reactivity of the two esters is explained in terms of the electrostatic pote...

Mechanism of the aminolysis of methyl benzoate: a computational study.

Density functional methods were applied in examining the possible mechanistic pathways for the reaction of phenyl acetate with ammonia. Transition state structures and energies were determined for concerted and neutral stepwise mechanisms. The general base catalysis of the process was also examined. The theoretical predictions reveal that the most favourable pathway of the reaction is through general base-catalysed neutral stepwise mechanism with the nucleophilic attack being the rate-determining stage. Comparisons are made with the energetics of the aminolysis for methyl formate and methyl benzoate. In the latter two esters, the energies of the first and second transition states, associated with the stepwise mechanism, are quite similar in magnitude. In contrast, in the case of phenyl acetate the transition state, associated with the nucleophilic attack (TS1), has distinctly higher energy than the elimination stage (TS2), and is the rate-determining stage of the reaction. The much lower energy of TS2 in phenyl acetate is attributed to the higher stability of the leaving group.

http://www.bcc.bas.bg/BCC_Volumes/Volume_40_Number_4_2008/Volume_40_Number_4_2008_PDF/2856-R.pdf

Yasen Atanasov

Papers

Predicting Reactivities of Organic Molecules. Theoretical and Experimental Studies on the Aminolysis of Phenyl Acetates

Mechanism of the aminolysis of methyl benzoate: a computational study.

Mechanism of the aminolysis of phenyl acetate: a computational study