Recent advancements have transformed lignin from a byproduct into a valuable raw material for polymers, dyes, adhesives, and fertilizers. However, its structural heterogeneity, variable reactive group content, impurities, and high extraction costs pose challenges to industrial-scale adoption. Efficient separation technologies and selective bond cleavage are crucial. Advanced pretreatment methods have enhanced lignin purity and reduced contamination, while novel catalytic techniques have improved depolymerization efficiency and selectivity. This review compares catalytic depolymerization methodologies, highlighting their advantages and disadvantages, and noting challenges in comparing yield values due to variations in isolation methods and lignin sources. Recognizing "technical lignin" from pulping processes, the review emphasizes its diverse applications and the necessity of understanding its structural characteristics. Emerging trends focus on bio-based functional additives and nanostructured lignin materials, promising enhanced properties and functionalities. Innovations open possibilities in sustainable agriculture, high-performance foams and composites, and advanced medical applications like drug delivery and wound healing. Leveraging lignin's biocompatibility, abundance, and potential for high-value applications, it can significantly contribute to sustainable material development across various industries. Continuous research in bio-based additives and nanostructured materials underscores lignin's potential to revolutionize material science and promote environmentally friendly industrial applications.
α-hydroxy acids (αHAs), simple and prebiotically plausible organic monomers, were likely present in various environments on and off Earth and could have played a role in directing the emergence of the first homochiral living systems. Some αHAs, which could have been of varying chirality, can undergo dehydration polymerization into polyesters, which could assemble into membraneless microdroplets upon rehydration; understanding these processes is critical for unraveling how simple prebiotic molecules transitioned into more complex systems capable of supporting selective chemical reactions, a key step toward the origin of life. Here, we focused on tartaric acid (TA), a prebiotically relevant αHA with multiple chiral forms, to probe plausible mechanisms by which primitive αHA and polyester-based systems could have participated in selective homochiral polymer synthesis. Enantiopure solutions of d-TA or l-TA polymerize efficiently via dehydration, while racemic dl-TA polymerization is inhibited due to stereochemical incompatibility. We found that Ca2+ ions influence this process in two significant ways: 1) regulating TA monomer availability through selective crystallization, removing equal amounts of both enantiomers in racemic proportion and thereby enriching the enantiomeric excess of the remaining nonracemic TA solution; and 2) modulating polymerization by suppressing enantiopure TA polymerization while enabling dl-TA polymerization. These findings suggest that the differential availability of simple inorganic ions, such as Ca2+, could have indirectly mediated the selection of simple organic chiral monomers and the emergence of homochirality in primitive protocell-forming polymers, offering a pathway from nonliving to living matter in early Earth environments.
In this paper, we review various novel/modified interfacial polymerization (IP) techniques for the fabrication of polyamide (PA) thin film composite (TFC)/thin film nanocomposite (TFN) membranes in both pressure-driven and osmotically driven separation processes. Although conventional IP technique is the dominant technology for the fabrication of commercial nanofiltration (NF) and reverse osmosis (RO) membranes, it is plagued with issues of low membrane permeability, relatively thick PA layer and susceptibility to fouling, which limit the performance. Over the past decade, we have seen a significant growth in scientific publications related to the novel/modified IP techniques used in fabricating advanced PA-TFC/TFN membranes for various water applications. Novel/modified IP lab-scale studies have consistently, so far, yielded promising results compared to membranes made by conventional IP technique, in terms of better filtration efficiency (increased permeability without compensating solute rejection), improved chemical properties (crosslinking degree), reduced surface roughness and the perfect embedment of nanomaterials within selective layers. Furthermore, several new IP techniques can precisely control the thickness of the PA layer at sub-10 nm and significantly reduce the usage of chemicals. Despite the substantial improvements, these novel IP approaches have downsides that hinder their extensive implementation both at the lab-scale and in manufacturing environments. Herein, this review offers valuable insights into the development of effective IP techniques in the fabrication of TFC/TFN membrane for enhanced water separation.
The effect of filler content and storage conditions such as drying, storing in water and thermal cycling on linear dimensional changes were investigated and evaluated. The dimensional accuracy studies were performed using a specific designed mould and a coordinate measuring machine. The findings gave support to the view that tiller content is an important factor influencing the physical and mechanical properties of the composite inlay material. The higher tiller content gave less polymerization shrinkage. The greatest linear shrinkage recorded was 0.79 %. The average linear shrinkage (in air, water and thermal cycling) for 79 % filler Prisma AP.H was 0.33 %, for 65 % tiller Prisma AP.H was 0.35 % and for 50 % filler Prisma AP.H was 0.42 %. Generally, dimensional changes was greatest when stored dry. This was followed by materials which were thermal cycled. The least dimensional change recorded was when the materials were stored in water.
The aim of the study was to evaluate post-polymerization of resin composite by measuring NanoHardness (H), Young’s Modulus (E) and Degree of Conversion (DC) using nanoindentation and Micro-Raman spectroscopy. For this purpose a computer-controlled NanoIndenter™ and a Renishaw 1000 Raman Spectrometer fitted with an Olympus microscope attachment, operated at 638 nm, were used. A light-activated resin composite was used in this study, (Z250, 3MESPE). Sub-groups (n=3) of specimens were irradiated for 20, 30, 40 s. All samples for nanoindentation were polished metallographically and typically 50 nanoindentations were performed per specimen. After curing and polishing, half of the samples were tested immediately (Group 1); the others after being stored dry at 37 °C for 7 days (Group 2) to allow scope for postpolymerization. H values ranged from 1.08 to 1.40 GPa for Group 1, and from 1.64 to1.71 GPa for Group 2. E values in Group 1 ranged from 19.60 to 19.94 GPa and for Group 2, from 21.42 to 22.05 GPa. DC values ranged from 55 to 66.39%, and 60.90 to 66.47% for Group 1 and Group 2 respectively. All values obtained shown significant different between Groups 1 and 2 (p
A molecularly imprinted polymer (MIP), with the ability to bind Pb(II) ion, was prepared using the non-covalent molecular imprinting methods and evaluated as a sorbent for the Pb(II) ion uptake. 4-vinylbenzoic acid was chosen as the complexing monomer. The imprinted polymer was synthesized by radical polymerization. The template (Pb(II) ions) was removed using 0.1 M HCl. As a result, the efficient adsorption was found to occur at pH 7. The result also showed the applicability of the Langmuir model for the sorption, with the maximum sorption capacity of 204.08 μg/mg.
Copolymerization is a cooperative polymerization that involves two or more different monomers that are incorporated into the same polymer chain. It allows the development of unlimited range of polymers, tunable properties and surface modifications. In this study, the oil-free base treated soybean waste was used as a biomass precursor and it was copolymerized with acrylamide through the free radical polymerization with potassium persulfate as initiator. The adsorption characteristic of the newly prepared acrylamide-soybean copolymer towards Pb(II) was studied by the use of Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and thermogravimetric analysis (TGA). The adsorption conditions were optimized in terms of pH, adsorbent dosage and contact time. The Freundlich isotherm model can fit well the adsorption data obtained towards Pb(II). In comparison, the pseudo-second-order is the better fit kinetic system that explained the adsorption mechanism of Pb(II) onto the acrylamide-soybean copolymer. The adsorption capacity of the acrylamide-soybean copolymer was determined to be 22.12 mg g-1, which is comparable with the absorption capacity of other grafted polymers.
Graft copolymerisation of methyl methacrylate (MMA) onto Agave angustifolia was conducted with ceric ammonium nitrate (CAN) as the redox initiator. The maximum grafting efficiency was observed at CAN and MMA concentrations of 0.91 × 10(-3) and 5.63 × 10(-2)M, respectively, at 45°C for 3h reaction time. Four characteristic peaks at 2995, 1738, 1440, and 845 cm(-1), attributed to PMMA, were found in the IR spectrum of grafted cellulose. The crystallinity index dropped from 0.74 to 0.46, while the thermal stability improved upon grafting. The water contact angle increased with grafting yield, indicating increased hydrophobicity of cellulose. SEM images showed the grafted cellulose to be enlarged and rougher. The changes in the physical nature of PMMA-grafted cellulose can be attributed to the PMMA grafting in the amorphous regions of cellulose, causing it to expand at the expense of the crystalline component.
Biosynthesis and in vivo depolymerization of intracellular medium-chain-length poly-3-hydroxyalkanoates (mcl-PHA) in Pseudomonas putida Bet001 grown on lauric acid were studied. Highest mcl-PHA fraction (>50 % of total biomass) and cell concentration (8 g L-1 ) were obtained at carbon-to-nitrogen (C/N) ratio 20, starting cell concentration 1 g L-1 , and 48 H fermentation. The mcl-PHA comprised of 3-hydroxyhexanoate (C6 ), 3-hydroxyoctanote (C8 ), 3-hydroxydecanoate (C10 ), and 3-hydroxydodecanoate (C12 ) monomers. In vivo action was studied in a mineral liquid medium without carbon source, and in different buffer solutions with varied pH, molarity, ionic strength, and temperature. The monomer liberation rate reflected the mol percentage distribution of the initial polymer subunit composition. Rate and percentage of in vivo depolymerization were highest in 0.2 M Tris-HCl buffer (pH 9, strength = 0.2 M, 30 °C) at 0.21 g L-1 H-1 and 98.6 ± 1.3 wt%, respectively. There is a congruity vis-à-vis to specific buffer type, molarity, pH, ionic strength, and temperature values for superior in vivo depolymerization activities. Direct products from in vivo depolymerization matched the individual monomeric composition of native mcl-PHA. It points to exo-type reaction for the in vivo process, and potential biological route to chiral molecules.
In this study, we present a groundbreaking approach utilizing metal-free, visible light-mediated organic photoredox catalyzed atom transfer radical polymerization (O-ATRP) to synthesize cellulose-based stimuli-responsive polymers. Our method resulted in the successful synthesis of innovative metal-free poly(N-tertiary-butylacrylamide)-graft-hydroxypropyl cellulose (PNTBAM-g-HPC) polymers with exceptional control over molecular weight and narrow dispersity index (Đ) and explored their applications in organo-photocatalytic reactions. This approach addresses the limitations of traditional atom transfer radical polymerization method, which suffer from metal contamination and toxicity related problems. O-ATRP and organic photoredox catalysts have been sought to address these difficult challenges. In this study, we synthesized organic compound; 2,4,5,6-tetrakis(diphenylamino)isophthalonitrile (4DPIPN), which served as an organic photoredox catalyst, enabling the synthesis and application study of PNTBAM-g-HPC polymers via organic photoredox catalysis. Furthermore, by employing 4DPIPN, three different types of PNTBAM-g-HPC polymers were synthesized. Through thorough characterization techniques including FTIR, NMR, UV/Visible spectroscopy, TGA, and GPC analysis, we confirmed the successful synthesis of photocatalyst and three different types of PNTBAM-g-HPC polymers under O-ATRP conditions. By adjusting the molar ratios of PNTBAM side chains, we fine-tuned the LCST of HTA-20 polymers to 37.3 °C, demonstrating their thermoresponsive behavior. This synthetic approach shows great potential for applications in biosensors, pharmaceuticals, biomedical engineering, and drug delivery systems.
Molecular imprinted polymers (MIP) are considered one of the most promising selective and novel separation methods for removal phenolic compound in wastewater treatment. MIP are crosslinked polymeric materials that exhibit high binding capacity and selectivity towards a target molecule (template), purposely present during the synthesis process. In this work MIP were prepared in a bulk polymerization method in acetonitrile using 2,4-dinitrophenol, acrylamide, ethylene glycol dimethacrylate, and benzoyl peroxide as template, functional monomer, cross-linker and initiator, respectively. An adsorption process for removal of nitrophenol using the fabricated MIP was evaluated under various pH and time conditions. The parameters studied for 2,4-dinitrophenol includes adsorption kinetics, adsorption isotherm, and selectivity. The maximum adsorption of nitrophenol by the fabricated MIP was 3.50 mg/g. The adsorption of 2,4-dinitrophenol by the fabricated MIP was found effective at pH 6.0. A kinetics study showed that nitrophenol adsorption follows a second order adsorption rate and the adsorption isotherm data is explained well by the Langmuir model.
This article demonstrates a novel nanoscale surface modification method to enhance the selectivity of porous poly(dimethylsiloxane) (PDMS) in removing oil from water. The surface modification method is simple and low cost by using sugar as a sacrificial template for temporal adhering of carbon nanotubes (CNT) before addition of PDMS prepolymer to encapsulate the CNT on its surface once polymerized. The PDMS-CNT demonstrated a tremendous increase in absorption capacity up to 3-fold compared to previously reported absorbents composed solely of PDMS. Besides showcasing excellent absorption capacity, the PDMS-CNT also shows a faster absorption rate (25 s) as compared to that of pure PDMS (40 s). The enhanced absorption rate is due to the incorporation of CNT, which roughens the surface of the polymer at the nanoscale and lowers the surface energy of porous PDMS while at the same time increasing the absorbent hydrophobicity and oleophilicity. This property makes the absorbent unique in absorbing only oil but repelling water at the same time. The PDMS-CNT is an excellent absorbent material with outstanding recyclability and selectivity for removing oil from water.
In this study, a novel multiphasic model for the calculation of the polypropylene production in a complicated hydrodynamic and the physiochemical environments has been formulated, confirmed and validated. This is a first research attempt that describes the development of the dual-phasic phenomena, the impact of the optimal process conditions on the production rate of polypropylene and the fluidized bed dynamic details which could be concurrently obtained after solving the model coupled with the CFD (computational fluid dynamics) model, the basic mathematical model and the moment equations. Furthermore, we have established the quantitative relationship between the operational condition and the dynamic gas⁻solid behavior in actual reaction environments. Our results state that the proposed model could be applied for generalizing the production rate of the polymer from a chemical procedure to pilot-scale chemical reaction engineering. However, it was assumed that the solids present in the bubble phase and the reactant gas present in the emulsion phase improved the multiphasic model, thus taking into account that the polymerization took place mutually in the emulsion besides the bubble phase. It was observed that with respect to the experimental extent of the superficial gas velocity and the Ziegler-Natta feed rate, the ratio of the polymer produced as compared to the overall rate of production was approximately in the range of 9%⁻11%. This is a significant amount and it should not be ignored. We also carried out the simulation studies for comparing the data of the CFD-dependent dual-phasic model, the emulsion phase model, the dynamic bubble model and the experimental results. It was noted that the improved dual-phasic model and the CFD model were able to predict more constricted and safer windows at similar conditions as compared to the experimental results. Our work is unique, as the integrated developed model is able to offer clearer ideas related to the dynamic bed parameters for the separate phases and is also capable of computing the chemical reaction rate for every phase in the reaction. Our improved mutiphasic model revealed similar dynamic behaviour as the conventional model in the initial stages of the polymerization reaction; however, it diverged as time progressed.
The composite polymer films of polyvinyl alcohol/polypyrrole/chloral hydrate (PVA-PPy-CH) had been prepared. Effects of γ-rays on the electrical conductivity of the composite polymer films had been investigated by using Inductance Capacitance Resistance meter (LCR) meter at a frequency ranging from 20 Hz to 1 MHz. With the incorporation of chloral hydrate in the polymer sample, the conductivity increased indicates that it is capable to be used as dopant for polymerizing conjugated polymer. The electrical conductivity obtained increased as the dose increased, which is in the order of 10-5 Scm-1 indicates that γ-rays is capable to enhance the electrical conductivity of the composite polymer films. The parameter of s is in the range of 0.31 d s d 0.49 and obeyed simple power law dispersion ωs. The Scanning Electron Microscopy (SEM) micrographs reveal the formation of polypyrrole globules in polyvinyl alcohol matrix which increased as the irradiation dose was increased.
The composite polymer films of polyvinyl alcohol/polypyrrole/chloral hydrate (PVA-PPy-CH) had been prepared. Effects of J-rays on the electrical conductivity of the composite polymer films had
been investigated by using Inductance Capacitance Resistance meter (LCR) meter at a frequency
ranging from 20 Hz to 1 MHz. With the incorporation of chloral hydrate in the polymer sample, the conductivity increased indicates that it is capable to be used as dopant for polymerizing conjugated polymer. The electrical conductivity obtained increased as the dose increased, which is in the order of 10-5Scm-1 indicates that J-rays is capable to enhance the electrical conductivity of the composite polymer films. The parameter of s is in the range of 0.31 d s d 0.49 and obeyed simple power law dispersion Zs. The Scanning Electron Microscopy (SEM) micrographs reveal the formation of polypyrrole globules in polyvinyl alcohol matrix which increased as the irradiation dose was increased.
This paper reports a rapid and in-situ electrochemical polymerization method for the fabrication of polypyrrole nanoparticles incorporated reduced graphene oxide (rGO@PPy) nanocomposites on a ITO conducting glass and its application as a counter electrode for platinum-free dye-sensitized solar cell (DSSC). The scanning electron microscopic images show the uniform distribution of PPy nanoparticles with diameter ranges between 20 and 30 nm on the rGO sheets. The electrochemical studies reveal that the rGO@PPy has smaller charge transfer resistance and similar electrocatalytic activity as that of the standard Pt counter electrode for the I₃(-)/I(-) redox reaction. The overall solar to electrical energy conversion efficiency of the DSSC with the rGO@PPy counter electrode is 2.21%, which is merely equal to the efficiency of DSSC with sputtered Pt counter electrode (2.19%). The excellent photovoltaic performance, rapid and simple fabrication method and low-cost of the rGO@PPy can be potentially exploited as a alternative counter electrode to the expensive Pt in DSSCs.
Molecularly imprinted polymers (MIPs) were prepared by bulk polymerization in acetonitrile using 2,4-dinitrophenol, acrylamide, ethylene glycol dimethacrylate, and benzoyl peroxide, as the template, functional monomer, cross-linker, and initiator, respectively. The MIP membrane was prepared by hybridization of MIP particles with cellulose acetate (CA) and polystyrene (PS) after being ground and sieved. The prepared MIP membrane was characterized using Fourier transform infrared spectroscopy and scanning electron microscopy. The parameters studied for the removal of 2,4-dinitrophenol included the effect of pH, sorption kinetics, and the selectivity of the MIP membrane. Maximum sorption of 2,4-nitrophenol by the fabricated CA membrane with MIP (CA-MIP) and the PS membrane with MIP (PS-MIP) was observed at pH 7.0 and pH 5.0, respectively. The sorption of 2,4-dinitrophenol by CA-MIP and PS-MIP followed a pseudo-second-order kinetic model. For a selectivity study, 2,4-dichlorophenol, 3-chlorophenol, and phenol were selected as potential interferences. The sorption capability of CA-MIP and PS-MIP towards 2,4-dinitrophenol was observed to be higher than that of 2,4-dichlorophenol, 3-chlorophenol, or phenol.
Poly(hydroxamic acid) chelating ion-exchange resin was prepared from crosslinked poly(methacrylate) beads. The starting polymer was prepared by a suspension polymerization of methacrylate and divinyl benzene. Conversion of the ester groups into the hydroxamic acid was carried out by treatment with hydroxylamine in an alkaline solution. Hydroxamic acid capacity of the product was 2.71 mmol/g. The resin exhibited high affinity towards Fe(III) and Pb ions and its capacities for Fe(III), Pb, Cu, Ni and Co ions were pH dependent. The ability of the resin to carry out the separation of Fe(III)CuCo/Ni and PbNi ions is also reported.
Polydopamine has been widely used as an additive to enhance membrane fouling resistance. This study reports the effects of two-step dopamine-to-polydopamine modification on the permeation, antifouling, and potential anti-UV properties of polyethersulfone (PES)-based ultrafiltration membranes. The modification was performed through a two-step mechanism: adding the dopamine additive followed by immersion into Tris-HCl solution to allow polymerization of dopamine into polydopamine (PDA). The results reveal that the step of treatment, the concentration of dopamine in the first step, and the duration of dipping in the Tris solution in the second step affect the properties of the resulting membranes. Higher dopamine loadings improve the pure water flux (PWF) by more than threefold (15 vs. 50 L/m2·h). The extended dipping period in the Tris alkaline buffer leads to an overgrowth of the PDA layer that partly covers the surface pores which lowers the PWF. The presence of dopamine or polydopamine enhances the hydrophilicity due to the enrichment of hydrophilic catechol moieties which leads to better anti-fouling. Moreover, the polydopamine film also improves the membrane resistance to UV irradiation by minimizing photodegradation's occurrence.
Biodegradable polyester polyhydroxyalkanoate (PHA) is a promising bioplastic material for industrial use as a replacement for petroleum-based plastics. PHA synthase PhaC forms an active dimer to polymerize acyl moieties from the substrate acyl-coenzyme A (CoA) into PHA polymers. Here we present the crystal structure of the catalytic domain of PhaC from Chromobacterium sp. USM2, bound to CoA. The structure reveals an asymmetric dimer, in which one protomer adopts an open conformation bound to CoA, whereas the other adopts a closed conformation in a CoA-free form. The open conformation is stabilized by the asymmetric dimerization and enables PhaC to accommodate CoA and also to create the product egress path. The bound CoA molecule has its β-mercaptoethanolamine moiety extended into the active site with the terminal SH group close to active center Cys291, enabling formation of the reaction intermediate by acylation of Cys291.