The incorporation of bio-renewable resources such as fatty acids into the polymer chain allows tailoring the properties of products, for their widespread applications. A series of methacrylate monomers with sidechain fatty acids (FAMA) were synthesized by esterification of 2-hydroxyethyl methacrylate (HEMA) and fatty acids, such as caprylic, capric, lauric, mysritic, palmitic and stearic acid. Consequent polymerization of FAMAs via reversible addition-fragmentation chain transfer (RAFT) gave side-chain fatty acidcontaining well-defined polymers (PFAMA) with targeted molecular weights, narrow molecular weight distribution and precise chain-end functionality. The PFAMAs were subsequently used as macro-chain transfer agents (macro-CTA) for the polymerization of 2-(2-methoxyethoxy)ethyl methacrylate (MEO 2 MA) to obtain block copolymers. Homopolymers with fatty acid pendants display crystalline behaviour depending on the chain length of the fatty acids, evidenced by differential scanning calorimetry (DSC), polarized optical microscopy, small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS) techniques.

Detection of nitroaromatic explosives with high sensitivity and selectivity is extremely important for civilian and military safety. Here, we report the synthesis and multimodal sensing applications of an emissive alanine based dansyl tagged copolymer P(MMA-co-Dansyl-Ala-HEMA) ( DCP ), synthesized by RAFT copolymerization. The fluorescent co-polymer exhibited high sensitivity and selectivity towards conventional nitroaromatic explosives such as DNT, TNT and TNP in solution at lower range of µM level and also with saturated vapor of NACs. The quantum yield of the co-polymer was measured to be very high (Φ f = 77%) which make it an ideal candidate for sensing in solution as well as in vapor phase. The fluorescence signal from DCP copolymer gets significantly quenched upon addition of aliquots of DNT, TNT, and TNP. The Stern-Volmer constant was calculated to be very high. The quenching mechanism was further established by fluorescence up-conversion, time-resolved fluorescence and steady state absorption spectroscopy. The energetics of sensing process was calculated by Density Functional Theory (DFT) studies. We also fabricate a thin film polymer sensor which was able to detect nitroaromatic vapors with high selectivity. This opens up the possibility of building a low-cost and light-weight nitroaromatic explosives sensor for field use.

Conspectus Nature is intrinsically able to control kinetics, conversion, and selectivity of biochemical processes by means of confined reaction environments such as enzyme pockets, bilayer membranes, micelles, vesicles, cells, or bioorganic frameworks. The main reason for this fact is the optimal molecular alignment and restricted motion of reactant molecules compared to those found in bulk solution. Under this inspiration, a number of synthetic photo-nanoreactors based on supramolecular self-assembled systems have been developed during the last decades, including mesoporous inorganic materials, microemulsions, micelles, vesicles, lipid bilayer foams, polyelectrolyte nanoparticles, etc. In a broader sense, nanoreactor technology constitutes nowadays a promising tool to enhance organic synthesis under sustainable reaction conditions. In general, nanoreactors change the essential properties of the molecules within them, thus affecting their chemical reactivity. Among the nanoreactor-like systems described in the literature to facilitate photochemical processes, the more recent use of viscoelastic supramolecular gels, typically made of low-molecular-weight (LMW) compounds self-assembled through noncovalent interactions, as compartmentalized reaction media is particularly appealing due to the versatility of these materials in terms of fabrication, properties, and processability. Furthermore, the high specific surface areas found in supramolecular gels, their stimuli-responsive reversibility, good diffusion properties enhancing the interactions between reactants and the three-dimensional (3D) porous network, functional tunability, and blocking effect of external oxygen are some of the most important features that can benefit photoinduced processes carried out in confined gel media. Not surprisingly, the efficiency of photochemical processes inside gel media is largely dependent on the type of reaction, characteristics of the gel network, solvent nature, reactant properties, and reaction conditions. Thus, the main focus of this Account is to provide a concise overview of the most relevant examples reported by us and others in order to illustrate the main advantages associated with the emerging use of gel-based materials as nonconventional reaction media to facilitate and control photochemical reactions. In particular, photodimerization, triplet–triplet annihilation upconversion (TTA-UC) coupled to single electron transfer (SET), photooxidation, photoreduction, and trifluoromethylation reactions will be illustrated during the discussion. These examples suggest that gel-based media can provide a versatile platform for the discovery of new reaction pathways and facilitate the way that photochemical reactions are traditionally carried out in academia and industry in terms of reaction conditions and required infrastructure. In addition, the use of physical or chemical gels as reaction systems may also accelerate high-throughput screening of photocatalysts. Overall, a judicious choice of gelators, reactants, solvent, and rea...

We report the synthesis and characterization of well-defined polymers from oleic acid as the bio-renewable resource. Double bonds in oleate side-chains in the polymer are further modified by thiol-ene reaction, epoxidation, and cross-linking.

Pseudomonas putida (MTCC 1194) has been used to degrade phenol in water in the concentration range 100±1000 ppm. The inhibition effects of phenol as substrate have become predominant above the concentration of 500 ppm (5.31 mmoles/dm 3 ). The optimum temperature and initial pH required for maximum phenol biodegradation were 30°C and 7.00 respectively. From the degradation data the activation energy E a was found to be equal to 13.8 kcal/g mole substrate reacted. The most suitable inoculum age and volume for highest phenol degradation were 12 hrs and 7% v/v respectively. Surfactants had negligible effect on phenol biodegradation process for this microorganism. Monod model has been used to interpret the free cell data on phenol biodegradation. The kinetic parameters have been estimated upto initial concentration of 5.31 mmoles/dm 3 . l max and K S gradually increased with higher concentration of phenol. However, beyond the phenol concentration of 5.31 mmoles/dm 3 , the inhibition became prominant. The l max has been to be a strong function of initial phenol concentration. The simulated and the experimental phenol degradation pro®les have good correspondence with each other.List of symbols E a kcal/mole Activation energy K S mmoles dm A3 Saturation constant S mmoles dm A3 Phenol concentration S 0 mmoles dm A3 Initial phenol concentration t h Time of fermentation X gm dm A3 Cell mass concentration at any time of fermentation, X 0 gm dm A3