Chemistry of “In‐Water” Reactions: Spotlights on Micellar and Phase‐Transfer Catalysis DOI
Tharique N. Ansari, Gaganpreet Kaur, Thomas J. Colacot

et al.

Published: Nov. 8, 2024

Custom-designed additives play a crucial role in achieving desired transformations under aqueous conditions modern organic synthesis. In micellar catalysis, designer amphiphilic molecules create dynamic supramolecular structures that can dissolve reactants and catalysts conditions. This enables the to occur mild without need for hazardous solvents. Additionally, such as tetra -butyl ammonium chloride or bromides facilitate reactions through efficient transfer of reactive species between non-miscible biphasic systems. method, known phase-transfer has been instrumental challenging asymmetric chapter overviews recent advancements these respective fields, outlining fundamental principles underlying their operational mechanisms.

Language: Английский

Aqueous Micelles as Solvent, Ligand, and Reaction Promoter in Catalysis DOI Creative Commons

Jagdeep K. Virdi,

Ashish Dusunge,

Sachin Handa

et al.

JACS Au, Journal Year: 2024, Volume and Issue: 4(2), P. 301 - 317

Published: Jan. 16, 2024

Water is considered to be the most sustainable and safest solvent. Micellar catalysis a significant contributor chemistry in water. It promotes pathways involving water-sensitive intermediates transient catalytic species under micelles' shielding effect while also replacing costly ligands dipolar-aprotic solvents. However, there lack of critical information about micellar catalysis. This includes why it works better than traditional organic solvents, specific rules differ from those conventional catalysis, how limitations can addressed future. Perspective aims highlight current gaps our understanding provide an analysis designer surfactants' origin essential components. will fundamental including aqueous micelles simultaneously perform multiple functions such as solvent, ligand, reaction promoter.

Language: Английский

Citations

29

Recent Highlights in Micellar Catalysis: An Industrial Outlook DOI
Tharique N. Ansari, Guolin Xu, Andrew Z. Preston

et al.

Organic Process Research & Development, Journal Year: 2024, Volume and Issue: 28(4), P. 816 - 830

Published: March 14, 2024

From the context of sustainability, contemporary synthetic organic chemistry practices require significant transformation, as indicated by various sustainability matrices like atom economy, process mass intensity (PMI), E-factor, and DOZN. These factors have evidently unveiled inherent inefficiencies intrinsic to conventional protocols identified solvents principal causative agent. In response, utilization water a primary reaction medium for transformations has emerged an appealing alternative. This approach flourished with emergence micellar catalysis, where amphiphilic molecules alter bulk aqueous medium's solvation properties promote desired chemical transformation under milder sustainable conditions. After 2010, this technology gained considerable momentum established foundational framework performing reactions conditions, consequently mitigating dependency on hazardous solvents. perspective, recent advances in field catalysis will be discussed industrial applications, along future directions challenges associated regime.

Language: Английский

Citations

10

Implementation of micelle-enabled C(sp2)–C(sp3) cross-electrophile coupling in pharmaceutical synthesis DOI
Bin Wu, Ning Ye, Kangming Zhao

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(17), P. 2349 - 2352

Published: Jan. 1, 2024

A sustainable C(sp 2 )–C(sp 3 ) cross-electrophile coupling was developed between readily available 5-bromophthalide and 1-benzyl-4-iodopiperidine under micellar conditions, leading to a key intermediate of one our development compounds.

Language: Английский

Citations

8

Decoupling of the Confused Complex in Oxidation of 3,3′,5,5′-Tetramethylbenzidine for the Reliable Chromogenic Bioassay DOI

Caixia Zhu,

Hong Yang, Xuwen Cao

et al.

Analytical Chemistry, Journal Year: 2023, Volume and Issue: 95(44), P. 16407 - 16417

Published: Oct. 26, 2023

Regulation of the reaction pathways is a perennial theme in field chemistry. As typical chromogenic substrate, 3,3′,5,5′-tetramethylbenzidine (TMB) generally undertakes one-electron oxidation, but product (TMBox1) essentially confused complex and unstable, which significantly hampers clinic bioassays for more than 50 years. Herein, we report that sodium dodecyl sulfate (SDS)-based micelles could drive direct two-electron oxidation TMB to final stable TMBox2. Rather activation H2O2 oxidant by common natural peroxidase, substrate SDS decoupled thermodynamically favorable between TMBox2 with unreacted TMB, leading an unusual pathway. Mechanism studies demonstrated complementary spatial electrostatic isolation effects, caused confined hydrophobic cavities negatively charged outer surfaces micelles, were crucial. Further cascading glucose oxidase, as proof-of-concept application, allowed be reliably measured, even broader range concentrations without any conventional strong acid termination.

Language: Английский

Citations

16

Micelle-Enabled In Situ Surface Modification of Porous Organic Polymers: Formation of Heterogeneous Microcolony for Efficient Suzuki–Miyaura Coupling in Water DOI

Rajan Yadav,

Pritesh Keshari,

Susanta Hazra

et al.

ACS Applied Materials & Interfaces, Journal Year: 2025, Volume and Issue: unknown

Published: March 24, 2025

Synthesis of water-stable and dispersible heterogeneous catalysts having high catalytic efficiency is more challenging compared with homogeneous due to their low dispersity, activity, spatial confinement active centers in bulk water. Herein, we are describing systematic studies for the development microconfinement participation aqueous micelles via temporal surface modification porous organic polymer derived from phosphine ligands. Detailed investigations using various techniques such as transmission electron microscopy (TEM), scanning (SEM), tensiometry, confocal laser (CLSM), fluorescence lifetime imaging (FLIM) have been used understand role micelles, reagents, materials generation microcolonies Two-color crossover experiments also performed exchange reagents or vice versa, materials. The surfactant-modified ligation stabilization palladium, which was evidenced by high-resolution (HR-TEM), high-angle annular dark-field (HAADF-STEM), X-ray photoelectron spectroscopy (XPS) analysis. act confined space catalysis water showcasing Suzuki-Miyaura cross-coupling reaction a ppm level Pd loading under mild conditions. catalyst found be recyclable five cycles; easy scale-up C-C couplings additional features. Moreover, these data provide an opportunity revising models micellar systems that underpin sustainable

Language: Английский

Citations

0

Micelles Enabled Nickel-Catalyzed P-Arylation of Aromatic Phosphine Oxide in Water Under Mild Conditions DOI

Pritesh Keshari,

Rajan Yadav,

Priya Mata

et al.

ACS Sustainable Chemistry & Engineering, Journal Year: 2024, Volume and Issue: 12(31), P. 11473 - 11479

Published: July 15, 2024

A nonionic surfactant has been developed from agricultural waste and its potential application for the Ni-catalyzed C–P cross-coupling reaction in water. The was fully characterized by various spectroscopic imaging techniques. size of micelles morphological changes presence catalysts/substrates were established using transmission electron microscopy (TEM), dynamic light scattering (DLS), confocal microscopy. Controlled 31P NMR, 19F mass spectrometry, X-ray photoelectron spectroscopy (XPS) analysis revealed possible reactive intermediates mechanisms. synthesis shown 20 g 1 scale, respectively.

Language: Английский

Citations

3

Development of a biphasic catalytic system for Ullmann coupling hydroxylation of 2,6-dichlorotoluene DOI
Long Zhang,

Yuran Cheng,

G XU

et al.

Surfaces and Interfaces, Journal Year: 2025, Volume and Issue: unknown, P. 106382 - 106382

Published: April 1, 2025

Language: Английский

Citations

0

Manifestation of Size Heterogeneity of Molecular Aggregates in the Distribution of Their Fluorescence Lifetimes and Diffusion Coefficients DOI
A. Kasem Chowdhury, Anindya Datta

The Journal of Physical Chemistry C, Journal Year: 2025, Volume and Issue: 129(18), P. 8708 - 8716

Published: March 5, 2025

Microscopic insights into molecular aggregation have been obtained using R1, a model solvatochromic fluorophore in DMF–water mixtures. Fluorescence quantum yield (ϕf) and lifetime (τf) of R1 decrease monotonically up to rather high molar ratio water (χH2O). Near invariance the hydrodynamic radius, estimated fluorescence correlation spectroscopy, assigns this progressive increase polarity medium not aggregation. An abrupt ϕf beyond critical χH2O marks onset R1. Concomitantly, decays become bimodal, with emergence longer component associated aggregates. Significant heterogeneity is observed distribution lifetimes, indicating existence aggregates different kinds. quenching, upon further χH2O, assigned breakdown smaller ones. A qualitative between size τf by imaging microscopy.

Language: Английский

Citations

0

Core-Labeled Reverse Micelle-Based Supramolecular Solvents for Assisted Quick and Sensitive Determination of Amitriptyline in Wastewater DOI
Arun Sharma, Gagandeep Singh, Navneet Kaur

et al.

Langmuir, Journal Year: 2024, Volume and Issue: unknown

Published: Feb. 6, 2024

In recent years, the issue of pharmaceutical contaminants in water bodies has emerged as a significant environmental concern owing to potential negative impacts on both aquatic ecosystems and human health. Consequently, development efficient eco-friendly methods for their determination removal is paramount importance. this context, surfactant ensemble sensor been explored hard-to-sense amphiphilic drug, i.e., amitriptyline. Herein, pyrene-based amphiphile chemoreceptor was synthesized characterized through various spectroscopic techniques such 1H, 13C NMR, single-crystal XRD, FTIR, ES-mass spectrometry. Then, dodecanoic acid (DA) receptor THF/water solvent system were used generate reverse micelle-based self-aggregates SUPRAS (SUPRAmolecular Solvent). The structural aspects, morphology size, along with stability aggregates unfolded microscopic insights. present investigation describes synergistic approach that combines unique properties premicellar concentration supramolecular promising enhanced amitriptyline extraction simultaneous from (LOD = 12 nM). To evaluate effectiveness developed real-world scenarios, experiments conducted determine sensing efficiency among pollutants commonly found sources. results reveal nanoensemble exhibits remarkable ability, toward (AMT) drug outperforming conventional methods.

Language: Английский

Citations

2

Refolding SDS-mediated partially-unfolded proteins: A distinguishing role of tetraalkylammonium ionic liquids via mixed micellar aggregation DOI
Rajkumar Sahoo,

Prabal Pramanik,

Mintu Halder

et al.

Journal of Photochemistry and Photobiology A Chemistry, Journal Year: 2024, Volume and Issue: 454, P. 115661 - 115661

Published: April 13, 2024

Language: Английский

Citations

2