Electrophilic Addition Research Articles

Review on aqueous graphene nanoplatelet Nanofluids: Preparation, Stability, thermophysical Properties, and applications in heat exchangers and solar thermal collectors

Nanofluids of graphene nanoplatelets (GNP) have superior thermal performance characteristics and good stability, are relatively affordable, and can easily be prepared by the two-step method. This review performs an in-depth analysis of the preparation, stability, and thermophysical properties of GNP nanofluids, and their applications in heat exchangers, solar thermal collectors, and heat pipes. This study analyses in detail the performance improvements achieved with pristine, covalent functionalised, and non-covalent functionalised GNP nanofluids compared to water. Covalent functionalisation was found to be superior to non-covalent functionalisation in terms of stability and heat transfer coefficients. Functionalisation by electrophilic addition and free-radical grafting were found to be more environmentally friendly compared to acid treatment. In terms of convective heat transfer coefficient, pristine GNP outperformed functionalised GNP, but both types showed large improvements compared to water. It was found that stability and heat transfer performance improved as particle size was decreased, while thermal conduction and convection coefficients increased with nanofluid concentration and temperature. Thermal conductivity improvements of over 30% were found for both pristine and covalently functionalised GNP nanofluids at 0.1 wt% concentration. A maximum convection heat transfer coefficient increase of 200% was achieved using 0.1 wt% pristine GNP nanofluid. By comparison, a maximum improvement of 119% was achieved using covalently functionalised GNP. The convective heat transfer enhancement seemed to increase with decreasing tube diameter. In flat plate solar collector applications, efficiency improvements over 20% were obtained for covalently functionalised GNP nanofluids at 0.1 wt%, while an efficiency improvement of over 65% was obtained using pristine GNP in an evacuated tube solar collector. Applications in cooling, heat pipes, and direct absorption solar collectors were also reviewed. From this study, it could be inferred that GNP nanofluids are a viable alternative working fluid. Further research is needed to optimise their performance.

Studies on reaction mechanisms and distinct chemiluminescence from cyanoimino neonicotinoids triggered by peroxymonosulfate in advanced oxidation processes

In this study, we proposed a novel method to investigate the advanced oxidation process of neonicotinoids (NNIs) from the perspective of concomitant chemiluminescence (CL) reaction. It was found that in the presence of cobalt ions with cyanoimino NNIs, acetamiprid (ACE) and thiacloprid (THI), could promote peroxymonosulfate and Ru(bpy)32+ to produce strong CL, but no CL occurred with nitro-involved NNIs as alternatives. Experimental dada from UV absorption spectra and chemiluminescence spectra suggested that new cyclic compounds might be formed during the reaction. Based on the results of free radical scavenging experiment and mass spectra, a new degradation and reaction mechanism of cyanoimino-containing NNIs was proposed. ACE or THI were first attacked by SO4•− to form benzyl radicals, which in turn reacted with the carbon atoms of cyano group through electrophilic addition reaction in the formation of intramolecular ring. Then a redox reaction between Ru(bpy)33+ and imino group immediately took place with CL emission (610 nm). The new mechanistic knowledge would be meaningful for other contaminants for their interactions with PMS.

Floating-separation adsorbent for methylene blue and Pb(II) removal: Structure construction and adsorption mechanism

Inferior solid–liquid separation behavior and inadequate adsorption capacity are the main bottlenecks of current wastewater treatment adsorbents, especially in the purification of wastewater containing dyes and heavy metals. Accordingly, a novel floating separation adsorbent with polymeric chain structure, hollow glass sphere-g-(3-aminopropyl) triethoxysilane-g-poly(2-acrylamide-2-methyl-1-propanesulfonic acid) (APHGS-g-P(AMPS)), was fabricated through an electrophilic addition post-grafting strategy. The obtained APHGS-g-P(AMPS) exhibited satisfactory adsorption for methylene blue (MB) and lead ion (Pb(II)), as well as efficient flotation. Adsorption behavior analysis showed that the Pseudo-second-order kinetic model and Langmuir isotherm model were suitable for describing the adsorption process, and the maximum adsorption capacities for MB and Pb(II) were 249.33 and 345.93 mg·g−1 (313.15 K), respectively. Analysis of the adsorption mechanism indicated that the sulfonic acid group exhibited excellent universal adsorption for MB and Pb(II), which played a crucial role in the adsorption process. Furthermore, the efficient grafting of P(AMPS) polymerized chains onto the adsorbent was the pivotal factor to enhance adsorption. This study provided an efficient electrophilic addition post-grafting strategy for the structural design and functional modification of floating separation adsorbents. The results of this study are expected to have positive implications for the efficient purification of dyes and heavy metals wastewater.

Aqueous Chlorination of D-Limonene.

Limonene (1-methyl-4-(1-methylethenyl)-cyclohexene) is one of the most widespread monocyclic terpenes, being both a natural and industrial compound. It is widely present in the environment, including in water supplies. Therefore, it may be subjected to aqueous chlorination at water treatment stations during drinking water preparation. Besides, being a component of numerous body care and cosmetic products, it may present at high levels in swimming pool waters and could also be subjected to aqueous chlorination. Laboratory experiments with aqueous chlorination of D-limonene demonstrated the prevalence of the conjugated electrophilic addition of HOCl molecule to the double bonds of the parent molecule as the primary reaction. The reaction obeys the Markovnikov rule, as the levels of the corresponding products were higher than those of the alternative ones. Fragmentation pattern in conditions of electron ionization enabled the assigning of the structures for four primary products. The major products of the chlorination are formed by the addition of two HOCl molecules to limonene. The reactions of electrophilic addition are usually accompanied by the reactions of elimination. Thus, the loss of water molecules from the products of various generations results in the reproduction of the double bond, which immediately reacts further. Thus, a cascade of addition-elimination reactions brings the most various isomeric polychlorinated species. At a ratio of limonene/active chlorine higher than 1:10, the final products of aqueous chlorination (haloforms) start forming, while brominated haloforms represent a notable portion of these products due to the presence of bromine impurities in the used NaOCl. It is worth mentioning that the bulk products of aqueous chlorination are less toxic in the bioluminescence test on V. fischeri than the parent limonene.

Catalytic Coupling of Free Radical Oxidation and Electrophilic Chlorine Addition by Phase-Transfer Intermediates in Liquid Aerosols.

While examining the heterogeneous reaction of chlorine atoms with alkenes, in the presence of Cl2, we have observed an unexpectedly large enhancement of reactivity and the predominance of chlorinated reaction products even under high O2 conditions, where Cl atom recycling is expected to be minimal. These observations cannot be explained by known free radical oxidation or cycling mechanisms, but rather we find evidence for the multiphase catalytic coupling of free radical oxidation with electrophilic Cl2 addition. The mechanism entails the production of oxygenated reaction intermediates, which act as gas-liquid phase-transfer catalysts (gl-PTCs) by promoting the accommodation of gas-phase Cl2 by the aerosol, thereby enhancing electrophilic addition. Although the majority of PTCs typically couple chemistry between two immiscible liquid phases (aqueous/organic), there are few examples of PTCs that couple gas-liquid reactions. This work shows how multiphase reaction schemes of aerosols can be reimagined for understanding catalytic reaction mechanisms.

Gas-Phase Reactivity of Phenylcarbyne Anions.

Gas-phase reactivities of the phenylcarbyne anion and its four derivatives were studied using a linear quadrupole ion trap mass spectrometer. The phenylcarbyne anions were calculated to have a triplet ground state (singlet-triplet splittings of 4-9 kcal mol-1), with the exception of the 4-cyanophenylcarbyne anion that has a singlet ground state (singlet-triplet splitting of -1.9 kcal mol-1). Only the phenylcarbyne anions with a triplet ground state react with acetone and dimethyl disulfide via radical mechanisms. On the other hand, only the phenylcarbyne anion with a singlet ground state abstracts H2O and H2C═C═O from acetic acid via electrophilic addition of the reagents to the anion. Finally, two hydroxy-substituted phenylcarbyne anions (with triplet ground states) partially tautomerize with the assistance of reagent molecules to the more stable distonic phenylcarbene anions. This occurs via abstraction of a proton from the reagent by the phenylcarbyne anion to generate a neutral (triplet) phenylcarbene and a reagent anion, which is followed by proton abstraction from the hydroxyl group of the neutral phenylcarbene by the reagent anion to generate the distonic phenylcarbene anion in an excited triplet state. Experiments performed on deuterated hydroxy-substituted phenylcarbyne anions verified the mechanism. The reactivities of the distonic phenylcarbene anions were found to be quite different from those of the phenylcarbyne anions. For example, they were found to abstract CH2 from acetonitrile, which is initiated by C-H insertion─typical singlet carbene reactivity.

Origin of metabolites diversity and selectivity of P450 catalyzed benzo[a]pyrene metabolic activation

Polycyclic Aromatic Hydrocarbon (PAHs) presents one of the most abundant class of environmental pollutants. Recent study shows a lab-synthesized PAHs derivative, helicenium, can selectively kill cancer cells rather than normal cells, calling for the in-depth understanding of the metabolic process. However, the origin of metabolites diversity and selectivity of P450 catalyzed PAHs metabolic activation is still unclear to a great extent. Here we systematically investigated P450 enzymes catalyzed activation mechanism of a representative PAHs, benzo[a]pyrene (BaP), and found the corresponding activation process mainly involves two elementary steps: electrophilic addition and epoxidation. Electrophilic addition step is evidenced to be rate determining step. Two representative binding modes of BaP with P450 were found, which enables the electrophilic addition of Heme (FeO) to almost all the carbons of BaP. This electrophilic addition was proposed to be accelerated by the P450 enzyme environment when compared with the gas phase and water solvent. To dig deeper on the origin of metabolites diversity, we built several linear regression models to explore the structural-energy relationships. The selectivity was eventually attributed to the integrated effects of structural (e.g. O-C distance and O-C-Fe angle) and electrostatic parameters (e.g. charge of C and O) from both BaP and P450.

Intermolecular Carbosilylation of α-Olefins with C(sp3 )-C(sp) Bond Formation Involving Silylium-Ion Regeneration.

A regioselective addition of alkynylsilanes across unactivated, terminal alkenes is reported. The reaction is initiated by the capture of a sterically unhindered silylium ion by a silylated phenylacetylene derivative to form a bis(silylated) ketene‐like carbocation. This in situ‐generated key intermediate is the actual catalyst that maintains the catalytic cycle by a series of electrophilic addition reactions of silylium ions and β‐silicon‐stabilized carbocations. The computed reaction mechanism is fully consistent with the experimental findings. This unprecedented two‐component carbosilylation establishes a C(sp3)−C(sp) bond and a C(sp3)−Si bond in atom‐economic fashion.

Intermolekulare Carbosilylierung von α‐Olefinen mit C(sp3)−C(sp)‐Bindungsknüpfung unter Neubildung von Silyliumionen

AbstractEs wird über eine regioselektive Addition von Alkinylsilanen an nichtaktivierte, endständige Alkene berichtet. Die Reaktion wird durch Abfangen eines sterisch ungehinderten Silyliumions von einem silylierten Phenylacetylenderivat unter Bildung eines bissilylierten ketenartigen Carbokations eingeleitet. Diese lokal erzeugte Schlüsselzwischenstufe ist der tatsächliche Katalysator, der den Katalysecyclus über eine Abfolge von elektrophilen Additionsreaktionen von Silyliumionen und durch den β‐Siliciumeffekt stabilisierten Carbokationen aufrechterhält. Der berechnete Reaktionsmechanismus steht in vollständigem Einklang mit den experimentellen Befunden. Mit dieser vormals unbekannten Zweikomponentencarbosilylierung werden eine C(sp3)−C(sp)‐ und eine C(sp3)−Si‐Bindung atomökonomisch aufgebaut.

Synthesis of Benzo[b]thiophenes via Electrophilic Sulfur Mediated Cyclization of Alkynylthioanisoles.

A stable dimethyl(thiodimethyl)sulfonium tetrafluoroborate salt was employed for the electrophilic cyclization reaction of o-alkynyl thioanisoles for the synthesis of 2,3-disubstituted benzo[b]thiophenes. The reaction described herein works well with various substituted alkynes in excellent yields, and a valuable thiomethyl group was introduced with ease. The reaction utilizes moderate reaction conditions and ambient temperature while tolerating various functionalities. To elucidate the mechanism, electrophilic addition reactions using the dimethyl(thiodimethyl)sulfonium tetrafluoroborate salt with diphenylacetylene was demonstrated.

Biomass-derived porous carbon with high drug adsorption capacity undergoes enzymatic and chemical degradation

Degradability is a key safety issue when choosing materials for biomedical applications and environmental protection. This factor greatly limits the application of porous carbon in these areas due to the inert and stable nature of carbon network. In this work, this conflict could be well-resolved by rational designing a mesoporous carbon (MC) with biomass as a carbon source. The retained oxygen-containing species simultaneously increase drug adsorption capacity and the degradability of MC. The maximum adsorption quantity for doxorubicin over MC can reach 395.3 mg/g, about 3-fold over carbon nanotubes. The detailed analysis reveals that the degradation of MC occurs via a radical mediated oxidation process. The high electron density feature of MC facilitates the electrophilic addition reaction in the presence of HO. During this process, the carbon network is gradually degraded into fragments, carbon nanodots and ultimately to CO2. This work opens up a new way to fabricate degradable porous materials and provides a promising material for the practical application in biomedical and environmental field.

Critical Computational Evidence Regarding the Long-Standing Controversy over the Main Electrophilic Species in Hypochlorous Acid Solution.

Although hypochlorous acid (HOCl) solution has become a popular electrophilic reagent for industrial uses, the question of which molecule (HOCl or Cl2) undergoes electrophilic addition with olefins remains a controversial issue in some literature and textbooks, and this problem has been largely underexplored in theoretical studies. In this work, we computationally studied the electrophilic addition mechanism of olefins using three experimentally predicted effective electrophilic chlorinating agents, i.e., HOCl, Cl2, and Cl2O molecules. Our results demonstrate that Cl2 and Cl2O are the main electrophilic agents in HOCl solution, whereas the HOCl molecule cannot be the electrophile since the energy barrier when directly adding HOCl molecule to olefins is too high to overcome and the “anti-Markovnikov” regioselectivity for tri-substituted olefin is not consistent with experiments. Notably, the HOCl molecule prefers to form oxonium ion intermediate with a double bond, rather than the generally believed chlorium ion intermediate. This work could benefit mechanistic studies of critical biological and chemical processes with HOCl solution and may be used to update textbooks.

Formation of chlorinated halobenzoquinones during chlorination of free aromatic amino acids

Chlorinated halobenzoquinones (HBQs) widely exist in drinking water as emerging disinfection byproducts (DBPs), which have attracted significant attention due to their wide occurrence and high toxicity. In this study, the formation of chlorinated HBQs from the three free aromatic amino acids, tryptophan (Trp), tyrosine (Tyr) and phenylalanine (Phe), during chlorination was investigated, the formation pathways of chlorinated HBQs were explained based on the detected intermediates and influence factors. The results revealed that four chlorinated HBQs, including 2,6-dichloro-1,4-benzoquinone (2,6-DCBQ), 2,3,5-trichloro-1,4-benzoquinone, 2,3,5,6-tetrachloro-1,4-benzoquinone and 2,6-dichloro-3-methyl-1,4-benzonquinone, were formed in chlorination of the three free aromatic amino acids, and 2,6-DCBQ was the dominant species among the formed chlorinated HBQs. Of the three free aromatic amino acids, Trp and Tyr presented relatively high yields of chlorinated HBQs than Phe. Moreover, ten intermediates were successfully detected (e.g., N,2-dichloroaniline from Trp, 2,4,6-trichlorophenol from Tyr) according to the isotope and fragment information obtained using high resolution mass spectrometry. The formation pathways of chlorinated HBQs from Trp and Tyr were proposed to include electrophilic addition, electrophilic substitution, oxidation, deacidification and dehydration reaction, and further validated using theoretical calculation. The yields of chlorinated HBQs during chlorination of the free aromatic amino acids were significantly affected by free chlorine dosage, pH and temperature.

Multistep Microwave-Assisted Synthesis of Avobenzone

Multistep synthesis is a key capstone experience in organic laboratory instruction. Here, a four-step synthesis of avobenzone, an active component in sunscreens, has been developed that can be completed in two 4 h laboratory periods. This synthesis incorporates green principles and includes an aldol condensation, electrophilic addition of bromine to an alkene, an E2 dehalogenation of a dibromide, and hydration of an alkyne. Highlights of this synthesis include the use of coupling constants to identify alkene configuration, NMR analysis to determine preferred tautomeric form, the use of microwave irradiation to reduce reaction times, a solvent-free synthesis of a chalcone, and a three-step reaction that can be completed in a single lab period.

A Reinterpretation of the Imidazolate Au(I) Cyclic Trinuclear Compounds Reactivity with Iodine and Methyl Iodide with the Perspective of the Inverted Ligand Field Theory.

Coinage metal cyclic trinuclear compounds (CTCs) are an emerging class of metal coordination compounds that are valuable for many fine optoelectronic applications, even though the reactivity dependence by the different bridging ligands remains somewhat unclear. In this work, to furnish some hints to unravel the effect of substituents on the chemistry of Au(I) CTCs made of a specific class of bridging ligand, we have considered two imidazolate Au(I) CTCs and the effect of different substituents on the pyrrolic N atoms relative to classic metal oxidations with I2 or by probing electrophilic additions. Experimental suggestions depict a thin borderline between the addition of MeI to the N-methyl or N-benzyl imidazolyl CTCs, which afford the oxidized CTC in the former and the ring opening of the CTC and the formation of carbene species in the latter. Moreover, the reactions with iodine yield to the oxidation of the metal centers for the former and just of a metal center in the latter, even in molar excess of iodine. The analysis of the bond distances in the X-ray crystal structures of the oxidized highlights that Au(III)-C and Au(III)-N bonds are longer than observed for Au(I)–C and Au(I)–N bonds, as formally not expected for Au(III) centers. Computational studies converge on the attribution of these discrepancies to an additional case of inverted ligand field (ILF), which solves the question with a new interpretation of the Au(I)–ligand bonding in the oxidized CTCs, which furnishes a new interpretation of the Au(I)-ligand bonding in the oxidized CTCs, opening a discussion about addition/oxidation reactions. Finally, the theoretical studies outputs depict energy profiles that are compatible with the experimental results obtained in the reaction of the two CTCs toward the addition of I2, MeI, and HCl.

UV/Nitrate photocatalysis for degradation of Methylene blue in wastewater: Kinetics, transformation products, and toxicity assessment

This study explored the degradation kinetics of Methylene blue (MB) and formation of nitrated/nitrosated products via UV/NO3− during wastewater treatment. The contributions of UV irradiation, hydroxyl radical (HO⋅), and reactive nitrogen species were calculated to be approximately 6.21%, 77.86%, and 15.93%, respectively. Increasing NO3− dosage or decreasing MB concentration facilitated the degradation of MB. The removal efficiency of MB was higher under acidic conditions than that under alkaline and neutral conditions, which was ascribed to the higher HO⋅ concentration under acidic conditions. Both chloride ions (Cl−) and carbonate/bicarbonate ions (CO32−/HCO3−) had a slight effect on observed pseudo-first-order rate constants (kobs). However, natural organic matters (NOM), as radical scavengers and UV-irradiation filters, notably inhibited the degradation of MB. Furthermore, the degradation intermediates/products and transformation pathway of MB in UV/NO3− were clarified. Results indicated that nitrated/nitrosated products were more likely to be produced by coupling reactions and electrophilic addition. Fortunately, no significant enhancement in acute toxicity towards Vibrio fischeri was found during the degradation of MB by UV/NO3−. MB could be degraded effectively in different real water, which indicated that UV/NO3− system should be a good alternative for the degradation of pollutants.

Computational Exploration of Anomalous Regioselectivities in Cycloadditions of Ketenes to Oxazolines.

Thermal (2 + 2) cycloadditions of several N-carboalkoxy (R)-2-tert-butyldihydrooxazoles with ketenes have been studied experimentally by the Ghosez group. Contrary to results from Seebach and co-workers that the electrophilic addition of acylating agents occurs β to dihydrooxazole nitrogen, Ghosez found major cycloadducts resulting from an attack of ketene carbonyl carbon β to oxygen. We investigate the potential energy surface for the cycloaddition of diphenyl- and phenylchloroketenes to two (R)-2-tert-butyldihydrooxazoles with ωB97X-D and mPW1PW91 density functional theory and DLPNO-CCSD(T) wave function theory. These (2 + 2) cycloadditions are concerted but highly asynchronous, and the selectivity trends in ketene addition cases are in good agreement with the experiment. We propose a model based on the buildup of charge in oxazoline to reconcile the regiochemical differences between Ghosez and Seebach's observations.

Formula Assignment Algorithm for Deuterium-Labeled Ultrahigh-Resolution Mass Spectrometry: Implications of the Formation Mechanism of Halogenated Disinfection Byproducts.

Ultrahigh-resolution mass spectrometry (UHR-MS) coupled with isotope labeling has attracted significant attention in elucidating the mechanisms of the transformation of dissolved organic matter (DOM). Herein, we developed a novel formula assignment algorithm based on deuterium (D)-labeled UHR-MS, namely, FTMSDeu, for the first time. This algorithm was employed to determine the precursor molecules of halogenated disinfection byproducts (Xn-DBPs) and to evaluate the relative contribution of electrophilic addition and substitution reactions in Xn-DBP formation according to the H/D exchange of DOM molecules. Further, tandem mass spectrometry with homologous-based network analysis was used to validate the formula assignment accuracy of FTMSDeu in the identification of iodinated disinfection byproducts. Electrophilic substitution accounted for 82-98, 71-89, and 43-45% of the formation for Cl-, Br-, and I-containing Xn-DBPs, respectively, indicating the dominant role of the electrophilic substitution in chlorinated disinfection byproducts with low Br and I concentrations. The absence of putative precursors in some Xn-DBPs also suggests that Xn-DBP formation includes secondary reactions (e.g., oxidation and hydrolysis) in addition to the electrophilic addition and/or substitution of halogens. These findings highlight the significance of isotopically labeled UHR-MS techniques in revealing the transformation of DOM in natural and engineered systems.

HFIP as Protonation Reagent and Solvent for Regioselective Alkylation of Indoles with All-Carbon Centers

The regio- and chemoselective construction of indole bearing an all-carbon center at the C3-position, a versatile bioactive building block, by C(sp2)-C(sp3) formation with olefins has been achieved through utilization of hexafluoroisopropanol (HFIP) as the protonation reagent and solvent. The catalytic reactions are operationally simple and green compared with previous reports utilizing elaborated olefins and catalysts. This protocol allows for alkylation of a variety of substituted indoles with diverse of styrene type alkenes in excellent yields and with high selectivity. Application of this protocol to the synthesis of drug was pursued and with an improved yield in contrast to previous art. Catalytic kinetics and deuterium-labeling experiments suggest that the rate-determining step involves the protonation of olefin by HFIP to generate carbocation, followed by electrophilic addition to indole derivative.

Aqueous Iron(IV)-Oxo Complex: An Emerging Powerful Reactive Oxidant Formed by Iron(II)-Based Advanced Oxidation Processes for Oxidative Water Treatment.

High-valent iron(IV)-oxo complexes are of great significance as reactive intermediates implicated in diverse chemical and biological systems. The aqueous iron(IV)-oxo complex (FeaqIVO2+) is the simplest but one of the most powerful ferryl ion species, which possesses a high-spin state, high reduction potential, and long lifetime. It has been well documented that FeaqIVO2+ reacts with organic compounds through various pathways (hydrogen-atom, hydride, oxygen-atom, and electron transfer as well as electrophilic addition) at moderate reaction rates and show selective reactivity toward inorganic ions prevailing in natural water, which single out FeaqIVO2+ as a superior candidate for oxidative water treatment. This review provides state-of-the-art knowledge on the chemical properties and oxidation mechanism and kinetics of FeaqIVO2+, with special attention to the similarities and differences to two representative free radicals (hydroxyl radical and sulfate radical). Moreover, the prospective role of FeaqIVO2+ in Feaq2+ activation-initiated advanced oxidation processes (AOPs) has been intensively investigated over the past 20 years, which has significantly challenged the conventional recognition that free radicals dominated in these AOPs. The latest progress in identifying the contribution of FeaqIVO2+ in Feaq2+-based AOPs is thereby reviewed, highlighting controversies on the nature of the reactive oxidants formed in several Feaq2+ activated peroxide and oxyacid processes. Finally, future perspectives for advancing the evaluation of FeaqIVO2+ reactivity from an engineering viewpoint are proposed.