Salt-induced acceleration of chemical reactions in cellulose nanopores

Chemical reactions in charged nanopores, such as present in cellulose fibers, can be accelerated by adding an inert salt, that does not participate in the reaction. Due to a Donnan-like equilibrium between ions inside and outside the pores, the concentration of co-ions in the nanopores (having a charge of the same sign as that of the pore wall), is lower than the concentration in the bulk. The co-ion concentration in pores can be increased by adding an inert salt, which shifts the Donnan equilibrium. The increased concentration of reactants in pores results in faster reaction kinetics. Reactions of cellulose with periodate confirm these predictions.     

Synthesis and study of N,N‐disubstituted 4‐[(4‐aminophenyl)diazenyl]benzylidene‐4′‐alkylanilines

A series of N,N‐disubstituted‐4‐[(4‐aminophenyl)diazenyl]benzylidene‐4′‐alkylanilines (azo dyes) were synthesized from the reaction of the corresponding benzaldehyde with alkylanilines. These azo dyes exhibit nematic and SmC phases on heating. Their order parameter, photo‐stability and miscibility were studied by investigation of a representative sample.     

QbD approached comparison of reaction mechanism in microwave synthesized gold nanoparticles and their superior catalytic role against hazardous nirto‐dye

Microwave irradiation (MI) process characteristically enables extremely rapid “in‐core” heating of dipoles and ions, in comparison to conventional thermal (conductance) process of heat transfer. During the process of nanoparticles synthesis, MI both modulates functionality behaviors as well as dynamic of reaction in favorable direction. So, MI providing a facile, favorable and alternative approach during nanoparticles synthesis nanoparticles with enhanced catalytic performances. Although, conventionally used reducing and capping reagents of synthetic origin, are usually environmentally hazardous and toxic for living organism. But, in absence of suitable capping agent; stability, shelf life and catalytic activity of metallic nanoparticles adversely affected. However, polymeric templates which emerged as suitable choice of agent for both reducing and capping purposes; bearing additional advantages in terms of catalyst free one step green synthesis process with high degree of biosafety and efficiency. Another aspect of current works was to understand role of process variables in growth mechanism and catalytic performances of microwave processed metallic nanoparticles, as well as comparison of these parameters with conventional heating method. However, due to poor prediction ability with previously published architect OFAT (One factor at a time) design with these nanoparticles as well as random selection of process variables with their different levels, such comparison couldn't be possible. Hence, using gum Ghatti (Anogeissus latifolia) as a model bio‐template and under simulated reaction conditions; architect of QbD design systems were integrated in microwave processed nanoparticles to establish mechanistic role these variables. Furthermore, in comparison to conventional heating; we reported well validated mathematical modeling of process variables on characteristic of nanoparticles as well as synthesized gold nanoparticles of desired and identical dimensions, in both thermal and microwave‐based processes. Interestingly, despite of identical dimension, MI processed gold nanoparticles bearing higher efficiency (kinetic rate) against remediation of hazardous nitro dye (4‐nitrophenol), into safer amino (4‐aminophenol) analogues.     

Investigating Chain Dynamics in Highly Crosslinked Polymers using Solid‐State 1H NMR Spectroscopy

Solid state ¹H NMR line‐shape analysis and (double quantum) DQ ¹H NMR experiments have been used to investigate the segmental and polymer chain dynamics as a function of temperature for a series of thermosetting epoxy resins produced using different diamine curing agents. In these thermosets, chemical crosslinks introduce topological constraints leading to residual stresses during curing. Materials containing a unique ferrocene‐based diamine (FcDA) curing agent were evaluated to address the role of the ferrocene fluxional process on the atomic‐level polymer dynamics. At temperatures above the glass transition temperature (T_g), the DQ ¹H NMR experiments provided a measure of the relative effective crosslink and entanglement densities for these materials and revealed significant polymer chain dynamic heterogeneity in the FcDA‐cured thermosets. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1143–1156     

Synthesis of fused indolines by interrupted Fischer indolization in a microfluidic reactor

This study describes our development of a microfluidic reaction scheme for the synthesis of fused indoline ring systems found in several bioactive compounds. We have utilized a continuous-flow microfluidic reactor for the reaction of hydrazines with latent aldehydes through the interrupted Fischer indolization reaction to form fused indoline and azaindoline products. We have identified optimal conditions and evaluated the scope of this microfluidic reaction using various hydrazine and latent aldehyde surrogates. This green chemistry approach can be of general utility to rapidly produce indoline scaffolds and intermediates in a continuous manner.     

Deprotection of durable benzenesulfonyl protection for phenols — efficient synthesis of polyphenols

A robust protection method for phenol was demonstrated by the use of durable benzenesulfonyl group, which survives various harsh reaction conditions using Grignard reagent, organolithium reagent, metal alkoxide, phosgene, mineral, and Lewis acids. A facile deprotection condition utilizing pulverized KOH (5 equiv) and t-BuOH (10 equiv) in hot toluene makes this protocol as a practical method, which can be applied to the multistep synthesis of biologically and medicinally important polyphenol compounds.