Chemicals with a four-carbon chain (C4 chemicals), like succinic acid, maleic acid, 1,4-butanediol, and tetrahydrofuran are extensively used as commodity chemicals and polymer precursors. Currently, these chemicals are commercially synthesized from petrochemical based feedstocks. There is a growing interest in catalytic pathways for producing these and other C4 chemicals from biomass. However, biomass is mainly composed of hexose and pentose sugars and the natural abundance of a C4 feedstock is low. This review summarizes the current development in catalytic pathways for C4 chemical synthesis from biomass derived sugars and its derivatives and suggests future direction of research.
Visible Light‐Induced [3+2] Annulation Reaction of Alkenes with Vinyl azides: Direct Synthesis of Functionalized Pyrroles
Comprehensive Summary
A photocatalytic [3+2] annulation of alkenes with vinyl azides was developed under irradiation by visible light in the presence of organic dye photocatalysts. This broad substrate scope and high functional group tolerance were demonstrated by more than 50 examples. The reaction provides a novel and efficient method for the synthesis of polyfunctionalized pyrroles under very mild metal-free conditions without other additives.
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Construction of naphthalenediimide Lanthanide (III)‐MOFs and composites incorporated electron‐rich pyrene derivative as multifunctional fluorescence sensing for nitro aromatic compounds and aldehydes
Comprehensive Summary
The development of host-guest MOF luminescent composites has attracted considerable attention. However, it is still a challenge to reasonably design large scale conjugated polycarboxylic acids metal-organic framework (MOF) and modulate donor-acceptor interaction. Herein, a series of isostructural 3D porous lanthanide MOF [Ln2(BINDI)0.5(NO3)(DMA)(H2O)]∙DMA∙2.5H2O (Ln = La (1), Ce (2), Pr (3) and Nd (4); H4BINDI (N, N’-bis(5-isophthalic acid)-1,4,5,8-naphthalenediimide) were synthesized. Considering the electron-deficient performances of Ln-BINDI MOFs, D-A type composites Ln-MOFs (1-4@H4TBAPy) were prepared via the incorporation of electron-rich H4TBAPy (1,3,6,8-Tetrakis(p-benzoic acid) pyrene), which more improved the luminescence performance of complexes 1-4 and can be used as fluorescence sensors for the detection of nitro compounds and aldehydes. High sensitivity of 1@H4TBAPy towards pNBA, pNA PNP, DNP, and TNP could be achieved through hydrogen bond interactions between MOF and analytes, as well as the π-π interaction between H4TBAPy and the naphthalene ring of BINDI, thus the fluorescence quenching efficiency of 1@H4TBAPy better than that of the complex 1. In addition, it is found that 1@H4TBAPy has high selectivity and sensitivity to aromatic aldehyde SA, 5-Mesal and HMBA. Such strategy to enhance the emission of NDI based Ln-BINDI MOFs, which will open up an avenue to obtain more fluorescent MOFs for sensing.
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Selective N‐methylation of N‐methylaniline with CO2 and H2 over Cu/In2O3 catalyst
Comprehensive Summary
N-methylation of amines with CO2 and H2 is a potential approach for CO2 utilizations because N-methylated amines can be used as solvents and organic intermediates. In2O3-supported Cu (Cu/In2O3) is acted as an effective heterogeneous catalyst for N-methylation reaction of N-methylaniline (MA) with CO2 and H2, showing higher N,N-dimethylaniline (DMA) selectivity than other supported Cu catalysts. On the one hand, the dispersion of Cu can be improved by the defective In2O3 support. On the other hand, In2O3 support is active in the dissociative adsorption of CO2 through C–O bond breaking. In addition, the H2 dissociation ability of In2O3 can also be enhanced by Cu. The combination of Cu and In2O3 is effective in the activation of CO2, the adsorption of intermediate N-Methylformanilide (MFA), the hydrogenation of MFA to DMA and the prohibition of C−N bond cleavage side reactions, thereby enhancing the reaction rate of MA conversion and the selectivity to DMA.
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Trianglimine‐Mediated Selective Sieving of Cis Isomer from the Mixture of Dihaloethenes: A Combined Molecular Dynamics and DFT Investigation
The manufacture of alkenyl halides on a larger scale often result in the formation of a mixture of isomers each having individual significant applications while their separation from each other is a strenuous task. Since most of the conventional distillation techniques are known to be intricate, energy consuming and expensive, the quest for an alternative strategy is still continuing. In this context, recently reported trianglimine macrocycle - a new class of intrinsically porous material, is promising in discerning cis isomer from a mixture of cis and trans dichloroethene. In this work, an attempt has been made to apprehend the host-guest inclusion phenomenon accountable for the selectivity of cis over the trans isomers of 1,2-dihaloethene (F, Cl and Br) using molecular dynamics simulation and DFT calculations at ω-B97xd/6-311G+(d,p) level of theory. Our results show that trianglimine can stabilise the cis isomers of the dihaloethenes inside its cavity forming complexes with high interaction energies and the rationale behind the recyclability of the host molecule has been clarified. The outcomes of the calculations bring out the potential utility of this new host architecture to produce highly pure value added chemicals in industries.
Phytochemical and pharmacological aspects of psoralen‐ A bioactive furanocoumarin from Psoralea corylifolia Linn.
Since long ago, medicinal plants have played a vital role in drug discovery. Being blessed and rich in chemovars with diverse scaffolds, they have unique characteristics of evolving based on the need. The World Health Organization also mentions that medicinal plants remain at the center for meeting primary healthcare needs as the population relies on them. The plant-derived natural products have remained an attractive choice for drug development owing to their specific biological functions relevant to human health and also the high degree of potency and specificity they offer. In this context, one such esteemed phytoconstituent with inexplicable biological potential is psoralen, a furanocoumarin. Psoralen was the first constituent isolated from the plant Psoralea corylifolia, commonly known as Bauchi. Despite being a life-saver for psoriasis, vitiligo, and leukoderma, it also showed immense anticancer, anti-inflammatory, and anti-osteoporotic potential. This review brings attention to the possible application of psoralen as an attractive target for rational drug design and medicinal chemistry. It discusses the various methods for the total synthesis of psoralen, its extraction, the pharmacological spectrum of psoralen, and the derivatization done on psoralen.
Exogenous putrescine changes biochemical (antioxidant activity, polyphenol, flavonoid, and total phenol compounds) and essential oil constituents of Salvia officinalis L.
This research is based on principal component analysis (PCA) and calculation of selection criteria (SC) to investigate the effect of foliar spraying of polyamine putrescine on essential oil yield, essential oil compounds, antioxidant activity, and biochemical compounds (polyphenol, flavonoid, and total phenol compounds) of Salvia officinalis. The treatments used included four levels of putrescine, Put (Control: 0, Put1: 500, Put2: 1000, and Put3: 1500 mg L− 1) with five replications. Based on our results, four factors had eigenvalues ≥ 1 and showed a cumulative variance percentage of 92.57% by applying different concentrations of putrescine. According to the results of this research, putrescine had significant effects on the amount of total phenolic compounds, flavonoids, and antioxidant activity. The crucial essential oil compounds of different Put treated sage were: cis- thujone (35.34%), Camphor (15.60%), trans- thujone (9.90%), 1,8- cineole (9.46%), α-Humulene (3.85%), α- pinene (3.50%) and limonene (1.23%). The results showed that the amount of total phenol, the phenolic composition of catechin, and the antioxidant activity of sage plant extract increased significantly when putrescine was used at 1000 mg/liter. Results can use the current research to optimize the production management of medicinal plants and improve the quality of their products.
Impact of dielectric constant of solvent on the formation of transition metal‐ammine complexes
Abstract
The DFT-level computational investigations into Gibbs free energies (ΔG) demonstrate that as the dielectric constant of the solvent increases, the stabilities of [M(NH3) n ]2+/3+ (n = 4, 6; M = selected 3d transition metals) complexes decrease. However, there is no observed correlation between the stability of the complex and the solvent donor number. Analysis of the charge transfer and Wiberg bond indices indicates a dative-bond character in all the complexes. The solvent effect assessed through solvation energy is determined by the change in the solvent accessible surface area (SASA) and the change in the charge distribution that occurs during complex formation. It has been observed that the SASA and charge transfer are different in the different coordination numbers, resulting in a variation in the solvent effect on complex stability in different solvents. This ultimately leads to a change between the relative stability of complexes with different coordination numbers while increasing the solvent polarity for a few complexes. Moreover, the findings indicate a direct relationship between ΔΔG (∆G solvent-∆G gas) and ΔE solv, which enables the computation of ΔG for the compounds in a particular solvent using only ΔG gas and ΔE solv. This approach is less computationally expensive.
[ASAP] Electrifying Carbon Capture by Developing Nanomaterials at the Interface of Molecular and Process Engineering
Accounts of Chemical Research
DOI: 10.1021/acs.accounts.3c00321
[ASAP] Self-Assembly via Condensation of Imine or Its N-Substituted Derivatives
Accounts of Chemical Research
DOI: 10.1021/acs.accounts.3c00475