Development and characterization of novel DOPO based phosphorus tetraglycidyl epoxy nanocomposites for aerospace applications

A study was made in the present investigation on the development and characterization of 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) based phosphorus tetraglycidyl epoxy nanocomposites and to find its suitability for use in aerospace and high performance applications. Phosphorus-containing diamine (DOPO-NH₂) was synthesized from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and 4,4′-diaminobenzophenone (DABP), and this is utilized for the preparation of DOPO based phosphorus containing tetraglycidyl epoxy denoted as ‘D’. The synthesized resin was characterized by Fourier transform infrared spectra (FT-IR) and ¹H, ¹³C nuclear magnetic resonance (NMR) spectra. Nanoclay and polyhedral oligomeric silsesquioxane (POSS)-amine nano-reinforcements denoted as N1 and N2 were incorporated into the synthesized epoxy resin. Curing was done with diaminodiphenylmethane (DDM) and bis(3-aminophenyl) phenylphosphine oxide (BAPPO) curing agents denoted as X and Y respectively. Mechanical, thermal, flame retardant, water absorption behaviour and electrical properties of the epoxy nanocomposites were studied and the results are discussed.     

Compressive characteristics of cellular solids produced using vacuum-microwave, freeze, vacuum and hot air dehydration methods

Dried cellular solids were produced using different hydrocolloids such as locust bean gum, low methoxy pectin, methyl cellulose and tapioca starch. They were dried to less than 5% (w.b) moisture content using freeze-drying, vacuum drying, vacuum microwave drying or air-drying methods. The dry cellular solids were subjected to uniaxial compression using a Texture analyzer to study the compressive characteristics. True stress–strain relationship curves were developed for the dry cellular solids produced by different drying methods. Hencky’s strain was calculated for true strain. Comparisons of samples dried by different drying methods were done in terms of their compressive characteristics at various water activities. No matter the type of drying, the dried materials were brittle at low water activity, plastic at medium water activity and elastomeric at higher water activity levels. Due to non-uniformity in air-dried samples and more closed pores in vacuum dried samples as well as less mechanical strength, these two were considered inferior for production of strong elastomeric foams. Microwave vacuum dried foams were mechanically the strongest. All the microwave vacuum dried samples were close in their Young’s modulus. Increases in microwave power did not make any appreciable changes in pore structures although higher microwave power levels resulted in faster drying.     

Adsorption of chromium (VI) on functionalized and non-functionalized carbon nanotubes

We did a comparative study on the adsorption capacity of Cr (VI) between functionalized carbon nanotubes (CNTs) and non-functionalized CNTs. The statistical analysis reveals that the optimum conditions for the highest removal of Cr (VI) are at pH 9, with dosage 0.1 gram, agitation speed and time of 120 rpm and 120 minutes, respectively. For the initial concentration of 1.0 mg/l, the removal efficiency of Cr (VI) using functionalized CNTs was 87.6% and 83% of non-functionalized CNTs. The maximum adsorption capacities of functionalized and non-functionalized CNTs were 2.517 and 2.49 mg/g, respectively. Langmuir and Freundlich models were adopted to study the adsorption isotherm, which provided a K _L and K _F value of 1.217 L/mg and 18.14 mg^1?n L ⁿ /g functionalized CNT, while 2.365 L/mg and 2.307 mg^1?n L ⁿ /g for non-functionalized CNTs. This result proves that functionalized CNTs are a better adsorbent with a higher adsorption capacity compared with the non-functionalized CNTs.     

Amphiphilic block copolymer surface composition: Effects of spin coating versus spray coating

Spray coating is demonstrated to produce different surface compositions of block copolymer films than spin coating even after annealing above the glass transition temperatures of both blocks. An amphiphilic block copolymer derived by chemically modifying the polyisoprene block of a polystyrene-block-poly(ethylene-ran-butylene)-block-polyisoprene precursor with different molar ratios of 550 g/mol poly(ethylene glycol) monomethyl ether and a semifluorinated alcohol, 10-Perfluorodecyl-1-decanol, is used as a model system to investigate the effect. X-ray photoelectron spectroscopy demonstrated significantly higher amounts of CF₂ and CF₃ carbons at the surface for spray coated films while the overall concentration of C–O bonded carbons did not change. Near edge X-ray absorption fine structure spectroscopy shows a larger C1s → ${\sigma }_{\text{C}?\text{F}}^1$ transition partial electron yield peak for the spray coated films and a negligible amount of polystyrene populating the surface for both solution deposition techniques. Water contact angles measured by the captive air bubble technique are found to be higher for the spray coated samples upon immersion in water. Scanning force microscopy also shows significant differences in the surface morphology of both films. These results indicate that it should not be assumed that the surface composition of a spin coated polymer film is representative of the same polymer deposited by spray coating.     

Removal of metsulfuron methyl by Fenton reagent

The removal of metsulfuron methyl (MeS)—a sulfonyl urea herbicide from contaminated water was investigated by advanced oxidation process (AOP) using Fenton method. The optimum dose of Fenton reagent (Fe²⁺/H₂O₂) was 10 mg/L Fe²⁺ and 60 mg/L H₂O₂ for an initial MeS concentration ([MeS]₀) range of 0–80 mg/L. The Fenton process was effective under pH 3. The degradation efficiency of MeS decreased by more than 70% at pH > 3 (pH 4.5 and 7). The initial Fe²⁺ concentration ([Fe²⁺]₀) in the Fenton reagent affected the degradation efficiency, rate and kinetics. The degradation of MeS at optimum dose of Fenton reagent was more than 95% for [MeS] ₀ of 0–40 mg/L and the degradation time was less than 30 min. The determination of residual MeS concentration after Fenton oxidation by UV spectrophotometry was affected by the interferences from Fenton reagent. The estimation of residual MeS concentration after Fenton oxidation by high pressure/performance liquid chromatograph (HPLC) was interference free and represented the actual concentration of MeS and does not include the by-products of Fenton oxidation. The degradation kinetics of MeS was modelled by second order reactions involving 8 rate constants. The two reaction constants directly involving MeS were fitted using the experimental data and the remaining constants were selected from previously reported values. The model fit for MeS and the subsequent prediction of H₂O₂ were found to be within experimental error tolerances.     

Introduction of bifunctionality into the phosphinic acid ion-exchange resin for enhancing metal ion complexation

In nuclear industry the role of conventional strong cation exchange resins is limited as they function less in high acid media. The phosphorous group that has got more affinity towards actinide elements is chosen as a chelating group and the phosphinic acid ion exchange resin was synthesized. The extraction ability of the phosphinic acid resin for plutonium (Pu) from HNO₃ medium as well as from H₂SO₄ medium was studied. Though the resin shows better extraction for Pu than the strong cation exchanger resins at higher acidities, its kinetics is slow. In order to enhance the kinetics as well as to improve upon selectivity, a sulphonic group is introduced into the phosphinic acid resin. To verify the effect of bifunctionality extraction studies have been carried out with Pu from different acid media of varying concentrations. Sulphonated phosphinic acid resin shows a 2-fold increase in distribution coefficient (k_d) as well as it reached equilibrium very fast compared to the phosphinic acid resin. It is postulated that the sulphonic acid ligand provides an access mechanism for the metal ions into the polymer matrix while it is the phosphinic acid group that is responsible for selective coordination of metal ions. Thus bifunctionality is coupling of an access mechanism to a recognition mechanism. The experiments carried out demonstrated the applicability of sulphonated phosphinic acid resin in the nuclear industry.     

Light-Control over Casein Kinase 1δ Activity with Photopharmacology: A Clear Case for Arylazopyrazole-Based Inhibitors

Protein kinases are responsible for healthy cellular processes and signalling pathways, and their dysfunction is the basis of many pathologies. There are numerous small molecule inhibitors of protein kinases that systemically regulate dysfunctional signalling processes. However, attaining selectivity in kinase inhibition within the complex human kinome is still a challenge that inspires unconventional approaches. One of those approaches is photopharmacology, which uses light-controlled bioactive molecules to selectively activate drugs only at the intended space and time, thereby avoiding side effects outside of the irradiated area. Still, in the context of kinase inhibition, photopharmacology has thus far been rather unsuccessful in providing light-controlled drugs. Here, we present the discovery and optimisation of a photoswitchable inhibitor of casein kinase 1δ (CK1δ), important for the control of cell differentiation, circadian rhythm, DNA repair, apoptosis, and numerous other signalling processes. Varying the position at which the light-responsive azobenzene moiety has been introduced into a known CK1δ inhibitor, LH846, revealed the preferred regioisomer for efficient photo-modulation of inhibitory activity, but the photoswitchable inhibitor suffered from sub-optimal (photo)chemical properties. Replacement of the bis-phenyl azobenzene group with the arylazopyrazole moiety yielded a superior photoswitch with very high photostationary state distributions, increased solubility and a 10-fold difference in activity between irradiated and thermally adapted samples. The reasons behind those findings are explored with molecular docking and molecular dynamics simulations. Results described here show how the evaluation of privileged molecular architecture, followed by the optimisation of the photoswitchable unit, is a valuable strategy for the challenging design of the photoswitchable kinase inhibitors.