Sustainable aerogels based on biobased poly (itaconic acid) for adsorption of cationic dyes.

This work reports the synthesis of poly (itaconic acid) by thermal polymerization mediated by 2,2'-Azobis(2-methylpropionamidine) dihydrochloride. Furthermore, physical hydrogels were prepared by using high molecular weight poly (itaconic acid) characterized by low dispersity and laponite RD. The hydrogels presented porous 3D network structures, with a high-water penetration of almost 2000 g/g of swelling ratio, which can allow the adsorption sites of both poly (itaconic acid) and laponite RD to be easily exposed and facilitate the adsorption of dyes. The water adsorption followed Schott's pseudo-second-order model. The mechanism of the adsorption process was investigated using 1H and 31P NMR. The hydrogel is able to fast adsorb by a combination of electrostatic interactions and hydrogen bonding by the synergic effect of the clay and poly (itaconic acid). Moreover, the prepared aerogels exhibited a fast removal of Basic Fuchsin, with an adsorption capacity of 67.56 mg/g and a high removal efficiency (~99 %). The adsorption followed the pseudo-second-order kinetic model and Langmuir isotherm model. Furthermore, the thermodynamic parameters showed that the BF process of adsorption was spontaneous and feasible, endothermic, and followed physisorption. These results indicated that the PIA/laponite-based aerogel can be considered a promising adsorbent material in textile wastewater treatment.

Upcycling Waste Streams from a Biorefinery Process-A Case Study on Cadmium and Lead Biosorption by Two Types of Biopolymer Post-Extraction Biomass.

This study investigated the possibility of using the spent kind of biomass of Pseudomonas putida CA-3 and Zobelella denitrificans MW1 obtained after the pilot-scale production of polyhydroxyalkanoates (PHAs) as a biosorbent for the bioremediation of aqueous solutions containing toxic cadmium and lead ions. The material was characterized by means of scanning electron microscopy, Fourier-transformed infrared spectroscopy, nuclear magnetic resonance spectroscopy and amino acid profiling. To check the sorption capacity of spent biomass against Pb and Cd ions, equilibrium studies were performed. To learn about the nature of the sorption process, kinetic modelling was carried out and the obtained results showed that the adsorption process is best described by the pseudo-second-order kinetic model (PSO), which suggests that the sorption process is connected with the chemical bonding of the ions on the sorbent surface. Information provided by the amino acid profile made it possible to predict the adsorption mechanism and FTIR analysis proved the participation of different chemical groups in the removal process. According to the equilibrium studies, the best-fitted isotherm was the Freundlich model for all used materials and metal ions considering the correlation coefficient. Summarizing the results, the spent biomass after the PHA production is an effective biosorbent and can be reused for heavy metal bioremediation.

Insight into the aqueous Laponite® nanodispersions for self-assembled poly(itaconic acid) nanocomposite hydrogels: The effect of multivalent phosphate dispersants.

HYPOTHESIS: We hypothesize, that physical network between Laponite® nanoparticles and high molecular weight polyelectrolyte formed by mixing of Laponite® nanodispersion (containing multivalent phosphate dispersant) and polyelectrolyte solution is strongly influenced by the type and content of dispersant, which forms electric double layer (EDL) closely to the Laponite® edges. Thus, optimum dispersant concentration is necessary to overcome clay-clay interactions (excellent clay delamination), but should not be exceeded, what would result in the EDL compression and weakening of attractions forming clay-polyelectrolyte network. Thus, deeper investigation of Laponite® nanodispersions is highly demanded since it would enable to better design the self-assembled clay-polyelectrolyte hydrogels. EXPERIMENTS: To study clay interparticle interactions in the presence of various multivalent phosphates, complementary methods providing wide nanodispersion characterization have been applied: zeta potential measurement and SAXS technique (electrostatic interactions), oscillatory rheology (nanodispersion physical state) and NMR experiments (ion immobilization degree). FINDINGS: It was found that multivalent phosphates induce and tune strength of clay-polyelectrolyte interactions forming hydrogel network in terms of varying EDL on the Laponite® edges. Moreover, phosphate dispersing efficiency depends on the molecular size, chemical structure, and valence of the anion; its potential as efficient dispersant for hydrogel preparation can be evaluated by estimation of anion charge density.

Recovery and Characterization Studies of Post-Production Alloy Waste from the Automotive Industry.

Superalloys provide high corrosion resistance and are widely used as high-performance materials in aerospace, automotive, chemical, and other industries. Herein, the investigation into the characteristics and properties of alloy waste; Inconel 625, Inconel 718, and Titanium Grade 5, from the automotive industry, was introduced as a result of a recovery in various processes. For this reason, the following procedures were carried as follows; the washing process to remove oil from the swarf was evaluated using several commercial agents and for the process of thermal disposal of processing fluids, a temperature of 900 °C was used in a muffle furnace without air access. The presented studies show that the commercially available series of washing agents did not modify the composition of the surface. However, the high temperatures during the calcination of oil residues are affecting the elemental composition of the alloys. According to the results of the analyses, it is not possible to remove 100% of the oil residues from alloy waste using washing agents based on light organic fractions; however, the effectiveness of this method reaches 99%. In this report, accurate SEM-EDS analyses show changes that occur on the surface after machining and removal of processing fluids. The NMR and GC/MS investigations indicate contaminants as a mixture of aliphatic and cycloaliphatic hydrocarbons with carbon numbers from C8-C30.

Cyclodextrin-modified poly(octamethylene citrate) polymers towards enhanced sorption properties.

Herein, we describe the synthesis of poly(1,8-octamethylene citrate) materials modified in the bulk with 2-hydroxypropyl-ß-cyclodextrin (cPOCCD), biodegradable elastomers with intrinsic sorption properties for drug delivery. The chemical structure, physicochemical properties, in vitro drug loading and release profiles of cPOCCD were investigated. Thus, cPOCCD polyesters absorb the studied drugs more effective and release them for a longer period of time than poly(1,8-octamethylene citrate) materials not containing cyclodextrins.

High-Molecular-Weight Polyampholytes Synthesized via Daylight-Induced, Initiator-Free Radical Polymerization of Renewable Itaconic Acid.

Herein, it is reported for the first time that when mixed with choline chloride, itaconic acid (IA), normally a low-reactive vinyl monomer, undergoes initiator-free radical polymerization under normal daylight. Furthermore, the process results in the formation of abnormally high-molecular-weight poly(itaconic acid) derivatives with Mw greater than ≈800 000 g mol-1 . Detailed 1D/2D NMR studies indicate that the polymers have two types of ionizable moieties, that is, anionic carboxylic and cationic choline ester groups in an average molar ratio of 12:1. Potentiometric titration shows polyampholyte behavior of the polymers. Tentative mechanistic studies reveal that the daylight-induced polymerization is initiated by species generated via interactions of near UV light with IA. However, EPR findings show that choline also participates in secondary radical reactions. The obtained polyampholytes are useful bio-based materials for fast and straightforward fabrication of polymer-clay nanocomposite hydrogels with excellent mechanical properties.

Luminescence phenomena of carbon dots derived from citric acid and urea - a molecular insight.

In this report, we present the results of our investigations into the elucidation of the chemical structure of moieties responsible for the blue and green luminescence of CDs derived from the microwave-assisted pyrolysis of citric acid in the presence of urea. The molecular fluorophore that forms during the synthesis of green fluorescing CDs is 4-hydroxy-1H-pyrrolo[3,4-c]pyridine-1,3,6(2H,5H)-trione (HPPT).

Luminescence phenomena of biodegradable photoluminescent poly(diol citrates).

The possible origin of luminescent properties of biodegradable photoluminescent polyesters (BPLPs) has been revealed by isolation and identification of luminescent agent from the hydrolyzate of BPLP. Elemental analysis, ESI-MS, (1)H, (13)C, 2D HSQC and COSY NMR spectra confirmed the chemical structure as 5-oxo-2,3-dihydro-5H-[1,3]thiazolo[3,2-a]pyridine-3,7-dicarboxylic acid (TPA).

Application of hydrogen peroxide encapsulated in silica xerogels to oxidation reactions.

Hydrogen peroxide was encapsulated into a silica xerogel matrix by the sol-gel technique. The composite was tested as an oxidizing agent both under conventional and microwave conditions in a few model reactions: Noyori's method of octanal and 2-octanol oxidation and cycloctene epoxidation in a 1,1,1-trifluoroethanol/Na2WO4 system. The results were compared with yields obtained for reactions with 30% H2O2 and urea-hydrogen peroxide (UHP) as oxidizing agents. It was found that the composite has activity similar to 30% H2O2 and has a several advantages over UHP such as the fact that silica and H2O are the only products of the composite decomposition or no contamination by urea or its derivatives occurs; the xerogel is easier to heated by microwave irradiation than UHP and could be used as both an oxidizing agent and as solid support for microwave assisted solvent-free oxidations.