Addition Reactions Research Articles

Mechanistic studies on the oxidation reaction of n-pentane

The oxidation reaction mechanism of n-pentane is investigated using density functional theory and transition state theory as a case study to elucidate the combustion characteristics of liquids with low boiling points. This study divides the oxidation reaction of n-pentane into four steps. First, n-pentane decomposes to form n-pentyl radicals C5H11 and H, CH3 and C4H9, and C2H5 and C3H7 radicals. Second, n-pentane primarily undergoes H-abstraction reactions with H, CH3, C2H5, and C3H7 radicals to form the C5H11 radicals. Subsequently, C5H11 radicals react with O2 in an addition reaction to form n-pentyl peroxy radicals ROO. Finally, ROO radical undergoes internal H-atom transfer to form hydroperoxy pentyl radicals QOOH, which then undergoes cyclization and bond scission to produce cyclic ethers, alkenes, aldehydes, OH radicals, and HO2 radicals. Results indicate that n-pentane readily decomposes into C2H5 and C3H7 radicals, with a bond dissociation energy of 367.1 KJ/mol. The H-abstraction reactions involving H and CH3 radicals have the fastest rates, which require the lowest energy barriers of 21.6 and 41.9 KJ/mol, respectively. The reaction between C5H11 and O2 is a barrierless addition reaction. The oxidation of n-pentane, which leads to the formation of 2-methyloxirane and OH radicals, exhibits the fastest reaction rate.

Fluence-Dependent Photoinduced Charge Transfer Dynamics in Polymer-Wrapped Semiconducting Single-Walled Carbon Nanotubes.

Because an individual single-walled carbon nanotube (SWNT) can absorb multiple photons, the exciton density within a single tube depends upon excitation conditions. In SWNT-based energy conversion systems, interactions between excitons and charges make it possible for multiple types of charge transfer reactions. We exploit a SWNT-molecular donor-acceptor hybrid system (R-PBN(b)-Ph6-PDI-[(6,5) SWNT]) that fixes spatial organization and stoichiometry of perylene diimide (PDI) electron acceptors on the nanotube surface, to elucidate how excitation fluence affects ultrafast charge separation (CS) and the nature of charge recombination (CR) dynamics triggered upon SWNT near-infrared excitation. Pump-probe data characterizing these photoinduced CS and thermal CR reactions were acquired over excitation fluences that produce ∼5-125 excitons per 700 nm long nanotube. These experiments show that optical excitation gives rise to CS states in which PDI radical anions (PDI-•) and SWNT hole polarons (SWNT•+) have geminate and nongeminate spatial relationships. Under low excitation fluences, the observed dynamics reflect CR reactions of these geminate and nongeminate CS states. As excitation fluence increases, persistent excitons, which have not undergone CS, undergo reaction with ([SWNT(•+)n]-(PDI-•)n) CS states to produce lower-energy CS states that are characterized by hole (SWNT•+) and electron (SWNT•-) polarons. When nongeminate SWNT•+ and SWNT•- charge carriers are generated, CR dynamics depend on the time scale required for these oppositely charged solvated SWNT polarons to encounter each other. Because SWNT excitons have substantial excited-state reduction (1E-/*) and excited-state oxidation (1E*/+) potentials, they can drive additional charge transfer reactions involving initially prepared CS states under experimental conditions where excess excitons are present.

Synthesis of α-Quaternary Amides via Cp*Co(III)-Catalyzed Sequential C-H Bond Addition to 1,3-Dienes and Isocyanates.

The synthesis of sterically congested amides was accomplished via Cp*Co(III)-catalyzed sequential C-H bond addition to 1,3-dienes followed by aminocarbonylation with isocyanates, a coupling partner that had never been utilized in sequential C-H bond addition reactions. A variety of C-H bond reactants, internally substituted dienes, and aromatic isocyanates provided secondary amide products incorporating α-all-carbon quaternary centers. The conversion of the amide products to other useful compound classes was also demonstrated.

Synthesis of 1,2,3‐Triphospholenes, 1,2‐Diphosphetes, and Unsymmetric Phospholes by Rhodium‐catalyzed Cleavage of P−P Bonds and Addition to Alkynes

AbstractThe rhodium‐catalyzed addition reaction of cyclo‐(PPh)5 to alkynes in refluxing THF efficiently provide 1,2,3‐triphospholenes, in which the –PPh–PPh–PPh– group is transferred from cyclo‐(PPh)5 by the cleavage of P−P bonds. In refluxing chlorobenzene, the reactions are accompanied by the formation of 1,2‐diphosphetes. When the triphospholenes containing P−P bonds are reacted with reactive alkynes under rhodium‐catalyzed conditions, unsymmetric phospholes are obtained. The rhodium‐catalyzed reactions can be used to synthesize various phosphorus‐containing heterocycles with different numbers of phosphorus atoms.

Polydopamine-Mediated Antimicrobial Lipopeptide Surface Coating for Medical Devices.

Biofilm formation on medical implants such as catheters is a major issue which needs to be addressed as it leads to severe health care associated infections. This study explored the design and synthesis of a polydopamine-lipopeptide based antimicrobial coating. The coating was used to modify the surface of Ultrathane Catheters. The lipopeptide SL1.15 with an N-terminal cysteine was covalently conjugated to the polydopamine modified catheters via a Michael addition reaction between the thiol moiety in the peptide and the aromatic ring in the polydopamine layer. The immobilization of the peptide on the polydopamine coated catheters was confirmed using water contact angle, X-ray photoelectron spectroscopy, atomic force microscopy, and scanning electron microscopy (SEM). The antimicrobial activity of the coated catheters investigated using drug resistant and clinical strains of Gram-positive (MRSA and S. aureus) and Gram-negative (E. coli, A. baumannii, and P. aeruginosa) bacteria revealed that lipopeptide immobilization inhibited >90% bacterial adhesion to the catheter surface. Additionally, biofilm assays against MRSA and E. coli revealed that the lipopeptide immobilized catheters inhibited >85% bacterial growth after 1 week incubation. Finally, the cytotoxicity profile of the catheters using the human dermal fibroblast, and the human embryonic kidney cell lines demonstrated that the polydopamine-lipopeptide coating was not toxic after 72 h incubation.

Copper‐Catalyzed Carboamination of Unactivated Alkenes to Synthesize β‐Lactams with Trichloroacetonitrile

ABSTRACTβ‐Lactams, as nitrogen‐containing heterocycles with distinctive biological activities, have made significant contributions to the treatment of infectious diseases. This study which used inexpensive copper salts as catalysts, trichloroacetonitrile as a radical precursor, and potassium carbonate as base offers a concise route for the synthesis of β‐lactam compounds substituted with potentially pharmacologically active dichloroacetyl moieties. Preliminary mechanistic studies indicate that unactivated alkenes undergo sequential intermolecular radical addition and intramolecular amidation reactions. The copper salts undergo catalytic cycles involving Cu(I)/Cu(II)/Cu(III) species.

Clays as Micro-Electrodes in Environmental Detoxification

AbstractIn-situ reduction of contamination in soil and groundwater is an ongoing challenge that often requires a multi-pronged approach for effective and efficient clean-up. Spontaneous or assisted electrochemical reactions that break down certain pollutants held on clay surfaces can render natural clays a unique and powerful ally in environmental mitigation of contaminated soils. Application of a low-level DC electric field (mV/cm) has been shown to facilitate transformation of some compounds and ionic species through redox reactions in addition to transporting them through the pores in wet clay soils. Results from previous tests suggest that the natural electrochemical processes that promote pollutant sloughing or chemical breakdown can be enhanced for targeted treatment by applying low-level electric field to the contaminated soil with clay content. The central idea of this hypothesis is that clay, due to its surface charge and electrostatic interaction with adjacent pore fluid, acts as a “micro-electrode” through the diffused double layer (DDL) interactions when subjected to an external electric field. This hypothesis, proven viable, may unlock potential ability of natural clays to generate beneficial reactions for detoxification of contaminated sub-surfaces. Evidence from past laboratory experiments accompanied by a proposed electrical model of clay behaving as a micro-electrode are presented in this paper. The laboratory experiment results support the proposed electrical model.

Comparison of the Reactivity for the Solvent Extraction of Gold(iii) from Concentrated HCl Solutions Among D2EHPA, PC 88A, and Cyanex 272

ABSTRACT In this study, the chemical reactivity of three organophosphorus acidic extractants (D2EHPA, PC 88A, and Cyanex 272) was compared for the extraction of the anionic gold(III) complex, AuCl4 −, from the concentrated hydrochloric acid solutions. The extraction behavior was examined by varying the hydrochloric acid concentration from 1 to 9 M. Among the three extractants, only Cyanex 272 showed significant efficiency in extracting Au(III) with the extraction percentage was proportional to hydrochloric acid concentration. In contrast, the extraction of Au(III) by D2EHPA and PC 88A was not significant. FT-IR spectra analysis indicated that the P=O bond in Cyanex 272 weakened after extraction, suggesting its involvement in the process. Based on the structural differences between the extractants and the observed dependence of gold(III) extraction on the hydrochloric acid concentration, a nucleophilic addition reaction was proposed as the extraction mechanism. Specifically, the phosphoryl oxygen of protonated Cyanex 272 likely forms a coordinate bond with the gold ion in AuCl4 −, facilitating its extraction. This mechanism was supported by both extraction and spectroscopic data, making Cyanex 272 a promising candidate for the selective extraction of Au(III) from highly acidic solutions. The findings offer insights into the extraction of metal ions using organophosphorus extractants in highly acidic environments.

Stereodivergent atom transfer radical addition of α-functionalized alkyl iodides to alkynes: a strategy for selective synthesis of both E- and Z-iodoalkenes.

The geometrical control of atom transfer radical addition (ATRA) reactions to alkynes poses significant challenges. Herein, we present a uniform solution by developing a stereodivergent synthetic method for both isomers of the resulting alkene products, starting from the same materials. The synthesis of the thermodynamically more stable isomer utilizes the strategy of uphill catalysis while the accumulation of the less stable isomer is facilitated by a manganese-catalyzed iodo-abstraction/radical rebound process, taking advantage of its reversibility. Various substituted alkyl iodides can be used to provide easy access to both isomers of iodoalkene products with valuable functional groups such as CF3, CF2H, CN, ester, or amide at the allylic position.

Synthesis of Multifunctional Organic Molecules via Michael Addition Reaction to Manage Perovskite Crystallization and Defect

AbstractAdditive engineering plays a pivotal role in achieving high‐quality light‐absorbing layers for high‐performance and stable perovskite solar cells (PSCs). Various functional groups within the additives exert distinct regulatory effects on the perovskite layer. However, few additive molecules can synergistically fulfill the dual functions of regulating crystallization and passivating defects. Here, we custom‐synthesized 2‐ureido‐4‐pyrimidone (UPy) organic small molecules with diverse functional groups as additives to modulate crystallization and defects in perovskite films via the Michael addition reaction. Theoretical and experimental investigations demonstrate that the −OH groups in UPy exhibit significant effects in fixing uncoordinated Pb2+ ions, passivation of lead‐iodide antisite defects, alleviating hysteresis, and reducing non‐radiative recombination. Furthermore, the enhanced C=O and −NH2 motifs interact with the A‐site cation via hydrogen bonding, which relieves residual strain and adjusts crystal orientation. This strategy effectively controls perovskite crystallization and passivates defects, ultimately enhancing the quality of perovskite films. Consequently, the open‐circuit voltage of the UPy‐based p‐i‐n PSCs reaches 1.20 V, and the fill factor surpasses 84 %. The champion device delivers a power conversion efficiency of 25.75 %. Remarkably, the unencapsulated device maintained 96.9 % and 94.5 % of its initial efficiency following 3,360 hours of dark storage and 1,866 hours of 1‐sun illumination, respectively.

Single-Cell Analysis Reveals the Cellular and Molecular Changes of Liver Injury and Fibrosis in Mice During the Progression of Schistosoma japonicum Infection

Schistosomiasis is a parasitic disease that poses a serious threat to human health. However, the pathogenic mechanism during the progression of Schistosoma japonicum infection remains unclear. In order to elucidate this mechanism, we used single-cell RNA sequencing (scRNA-seq) to investigate the transcriptome characteristics of the cellular (single-cell) landscape in the livers of mice infected with Schistosoma japonicum, which were divided into three groups: uninfected mice (0 week (w)), infected mice at 6 w post-infection (the acute phase), and infected mice at 10 w post-infection (the chronic phase). A total of 31,847 liver cells were included and clustered into 21 groups. The cells and T-cells had high heterogeneity in the liver during the progression of schistosome infection. The number and intensity of the intercellular interactions significantly increased at 6 w after infection but decreased at 10 w. The inflammatory signaling pathways chemoattractant cytokine ligand (CCL)5-chemokine C-C-motif receptor (CCR)5 between macrophages and T-cells were predominant at 6 w post-infection; the CCL6-CCR2 signaling pathway between macrophages was predominant at 10 w. The CD80 signaling pathway related to T-cell activation was increased at 6 w after infection, and increased expression of its receptor CD28 on the surfaces of CD4+ and CD8+ T-cells was confirmed by flow cytometry, suggesting an increase in their activation. In addition, scRNA-seq and quantitative reverse transcription polymerase chain reaction (qRT-PCR) confirmed that the intercellular communication between secretory phosphoprotein 1 (SPP1)-cluster of differentiation (CD44), insulin-like growth factor (IGF)-1-IGF1r and visfatin-insulin receptor (Insr) associated with bone metabolism and insulin metabolism was increased and enhanced in the liver at 6 w post-infection. Overall, we provide the comprehensive single-cell transcriptome landscape of the liver in mice during the progression of schistosome infection and delineate the key cellular and molecular events involved in schistosome infection-induced liver injury and fibrosis. The elevated CCL5-CCR5 and CCL6-CCR2 signaling pathways in the liver may be a drug target for liver injury and fibrosis caused by schistosome infection, respectively.

Reactivity and philicity of phthalimide-N-oxyl and benzotriazol-N-oxyl radicals in addition reactions to vinyl compounds

Reactivity and philicity of phthalimide-N-oxyl and benzotriazol-N-oxyl radicals in addition reactions to vinyl compounds

Pyrolysis models for pressure treated wood and wood–plastic composite

AbstractPressure treated wood (PTW) and wood–plastic composites such as Trex® are popular materials for the construction of decks and other auxiliary structures, which are known to significantly contribute to spread of wildland fires into communities. In this work, representative samples of these materials were studied to determine their pyrolysis and combustion properties to enable simulation of fire growth on the surface of these building products. The pyrolysis property development process followed a well‐established hierarchical approach where thermogravimetric analysis, differential scanning calorimetry, and microscale combustion calorimetry were used to parametrize kinetics and thermodynamics of the thermal decomposition and combustion, while controlled atmosphere pyrolysis and cone calorimetry tests performed on coupon‐sized samples were used to parameterize thermal transport properties and validate performance of the fully parametrized pyrolysis models. PTW decomposition was captured using four sequential reactions with one additional reaction used to model vaporization of water. Trex® board was found to consist of two distinct layers: a thin outer layer and an internal core. The pyrolysis model for this material was constructed using some known properties of high‐density polyethylene (PE) and the properties of PTW determined in this work. The outer layer was defined in the model to consist of PE and an inert additive, while the core was defined as a blend of PE and wood particles, which kinetics and thermodynamics of the thermal decomposition and combustion were successfully captured using the model developed for PTW.

Characterization of water-soluble inorganic ions and carbonaceous aerosols in the urban atmosphere in Amman, Jordan

The urban particulate matter (PM) carbonaceous and water-soluble ions were investigated in Amman, Jordan during May 2018–March 2019. The PM2.5 total carbon (TC) annual mean was 7.6 ± 3.6 μg/m3 (organic carbon (OC) 5.9 ± 2.8 μg/m3 and elemental carbon (EC) 1.7 ± 1.1 μg/m3), which was about 16.3% of the PM2.5. The PM10 TC annual mean was 8.4 ± 3.9 μg/m3 (OC 6.5 ± 3.1 μg/m3 and elemental carbon (EC) 1.9 ± 1.1 μg/m3), about 13.3% of the PM10. The PM2.5 total water-soluble ions annual mean was 7.9 ± 1.9 μg/m3 (about 16.9%), and that of the PM10 was 10.1 ± 2.8 μg/m3 (about 16.0%). The minor ions (F−, NO2−, Br−, and PO43−) constituted less than 1% in the PM fractions. The significant fraction was for SO42− (PM2.5 4.7 ± 1.6 μg/m3 (10.0%) and PM10 5.3 ± 1.9 μg/m3 (8.3%)). The NH4+ had higher amounts of PM2.5 (1.3 ± 0.6 μg/m3; 2.7%) than that PM10 (0.9 ± 0.4 μg/m3; 1.4%). During sand and dust storm (SDS) events, TC, Cl−, and NO3− were doubled in PM, SO42− did not increase significantly, and NH4+ slightly decreased. Regression analysis revealed: (1) carbonaceous aerosols come equally from primary and secondary sources, (2) about 50% of the OC came from non-combustion sources, (3) traffic emissions dominate the PM, (4) agricultural sources have a negligible effect, (5) SO42− is completely neutralized by NH4+ in the PM2.5 but there could be additional reactions involved in the PM10, and (6) (NH4)2SO4, was the major species formed by SO42−and NH4+ instead of NH4HSO4. It is recommended to perform long-term sampling and chemical speciation for the urban atmosphere in Jordan.

N‐Oxyl Radicals in Oxidative C–O Coupling: Free‐Radical Hydrogen Substitution and Addition to C=C Bonds

N‐oxyl radicals occupy an important place in free‐radical oxidative CH‐functionalization being one of the most efficient redox‐organocatalysts for hydrogen atom abstraction (HAT). Their applications include aerobic radical chain autoxidation, CH‐functionalization with the formation of carbon‐carbon and carbon‐heteroatom bonds. The persistent nature of N‐oxyl radicals combined with their high reactivity in HAT results in their unique dual chemistry: the same radical can both propagate radical chain reaction (at low N‐oxyl concentrations) and effectively “terminate” carbon‐centered radicals (at higher N‐oxyl concentrations). The latter case opens a new synthetic application area of N‐oxyl radicals, in which they act as both hydrogen abstracting species and O‐reagents for cross‐coupling with carbon‐centered radicals thus produced. Apart from the C–H bond cleavage, reactive N‐oxyl radicals have been extensively used recently in C=C double bond functionalization via radical addition reactions. In this review, both free‐radical CH‐functionalization reactions with the introduction of N‐oxyl fragments and alkene difunctionalizations by N‐oxyls are covered with emphasis on the relationship between reaction conditions and selectivity.

Preparation and properties of polyamide elastomers by a new synthesis route of Michael addition reaction

At present, the mainstream industrial synthesis method of polyamide is still bulk fusion polymerization, which is not in line with the concept of green synthesis because of the high threshold of reaction conditions and large energy consumption. Based on this, a new synthesis route of polyamide elastomer was studied in this paper. By synthesizing the end-functionalized long carbon chain diacrylamide (DDA) containing amide bonds, the synthesis mechanism was made by the thiol double bond Michael addition reaction. A series of polyamide elastomers with different ratios of hard and soft segments were synthesized by using dimercaptan chain extenders with different molecular weights. The results showed that the new synthesis route successfully prepared DDA and polyamide elastomers. The mechanical properties of the products were excellent, and the strain rate could reach 383 %. Tensile strength up to 23.08 MPa. The synthesis route has the characteristics of simple reaction process, mild reaction conditions and high reaction conversion rate. It provides theoretical guidance for the new synthesis route of polyamide elastomer.

Electron Transfer Capability in Atomic Hydrogen Reactions for Imidazole Groups Bound to the Insulating Alkanethiolate Layer on Au(111).

The charge transfer capability associated with chemical reactions at metal-organic interfaces was studied via the atomic H addition reaction for an imidazole-terminated alkanethiolate self-assembled monolayer (Im-SAM) film on Au(111) at room temperature, using near-edge X-ray absorption fine structure spectroscopy, infrared reflection absorption spectroscopy, work function measurements, and density functional theory calculations. The imidazolium cation is a stable species in liquids; therefore, it is pertinent to determine whether the hydrogenation reactions of the imidazole groups produce imidazolium cations accompanied by electron transfer to the Au substrate, even in the absence of solvate and/or counterions on the insulating alkanethiolate layer. The experiments made it clear that the imidazolium moieties were formed during the irradiation of Im-SAM with atomic H. Theoretical model calculations also revealed that the total energies and molecular orbital levels satisfied the imidazolium cation formation associated with electron transfer. In a detailed analysis of the work function change depending on H irradiation, we confirmed that some of the imidazolium radicals became cations in Im-SAM.

Formation Mechanism and Biotransformation of Halogenated polycyclic aromatic hydrocarbons (HPAHs) from Ecological sources to Food chain sink

Halogenated polyaromatic hydrocarbons (HPAHs, H = F, Cl, Br) are a new class of PAHs derivatives that mainly originate from the incomplete combustion of halogen-laden materials and via metallurgical operations. These compounds circulate extensively in various environmental matrices. This survey provides a comprehensive review on governing synthesis routes of HPAHs, their environmental occurrence, and their health and ecological effects. The review comprehensively enlists and presents emission sources of these emerging organic pollutants into the air that serves as their main reservoir. The formation of HPAHs ensues through successive addition reactions of smally compounds accompanied by ring cyclization steps; in addition to direct unimolecular fragmentation of parents halogenated. Halogenation of parent PAHs rapidly occurs in saline ecosystems thus multiplying the availability of these notorious compounds in the environment. Certain HPAHs appear to be more carcinogenic than dioxins. Transmission routes of HPAHs from their emission sources to water bodies, soil, aquatic life, plants, terrestrial animals, and humans are well-documented. Later, the direct and indirect diffusion of HPAHs from air to the biotic (plants, animals, humans) and abiotic components (soil, water, sediments) are described in detail. The study concludes that HPAHs are permeable to the carbon matrices resulting in the alleviation of the source-to-to-sink interface. As a potential future perspective, understanding the transmission interfaces lays a foundation to intervene in the introduction of these toxicants into the food chain.

Recent Progress on NHC-Catalyzed 1,6-Conjugate Addition Reactions.

As a significant variant of the Michael reaction, the 1,6-addition reaction has undergone considerable development over the past decade. This effective strategy enables the synthesis of a variety of novel and potentially bioactive functional molecules. In this review, we summarize the recent progress in NHC-catalyzed 1,6-addition reactions, highlighting their efficiency in the rapid synthesis of complex functional molecules. We also provide our perspectives on the future development of this dynamic and highly active research area.

Fluid mediated communication among flexible micro-posts in chemically reactive solutions.

Communication in biological systems typically involves enzymatic reactions that occur within fluids confined between the soft, elastic walls of bio-channels and chambers. Through the inherent transformation of chemical to mechanical energy, the fluids can be driven to flow within the confined domains. Through fluid-structure interactions, the confining walls in turn are deformed by and affect this fluid flow. Imbuing synthetic materials with analogous feedback among chemo-mechanical, hydrodynamic and fluid-structure interactions could enable materials to perform self-driven communication and self-regulation. Herein, we develop computational models to determine how chemo-hydro-mechanical feedback affects interactions in biomimetic arrays of chemically active and passive micro-posts anchored in fluid-filled chambers. Once activated, the enzymatic reactions trigger the latter feedback, which generates a surprising variety of long-range, cooperative motion, including self-oscillations and non-reciprocal interactions, which are vital for propagating coherent, directional signals over net distances in fluids. In particular, the array propagates a distinct message; each post interprets the message; and the system responds with a specific mode of organized, collective behavior. This level of autonomous remote control is relatively rare in synthetic systems, particularly as this system operates without external electronics or power sources and only requires the addition of chemical reactants to function.