Itaconic Acid Content Research Articles

PH-responsive biomass-based hydrogels for 5-fu delivery: Investigating the influential role of itaconic acid content on structural characteristic, swelling behavior, and drug loading capacity

The pH-responsive hydrogel was synthesized through an eco-friendly free radical polymerization process, utilizing ionic acid (IA), N, N-dimethyl acrylamide (DAAm), and double-bond modified vanillin (VMA). The P(DAAm-co-IA-co-VMA) hydrogel exhibited favorable compressive strength, swelling behavior, temperature sensitivity, pH sensitivity, salt solution sensitivity, and biocompatibility. Additionally, the study investigated the influence of varying IA monomer content on these properties. The evaluation of drug loading and release capabilities utilized 5-fluorouracil (5 Fu) as the model medicinal. The results showed that the P(DAAm-co-IA-co-VMA) hydrogel's cumulative release percentage was greater in the simulated intestinal fluid compared to the simulated gastric fluid, indicating its potential for oral drug delivery applications.

PAN-precursor to carbon fibre: An investigation of manufacture and material properties for varying comonomer composition

This study presents the conversion of polyacrylonitrile (PAN) co-polymers containing methyl acrylate (MA) and varying concentrations of itaconic acid (IA) comonomers, from precursor fibre into carbon fibre using pilot scale continuous processes. The impact of itaconic acid on fibre processability, thermal behaviour, energy consumption, and final mechanical properties during thermal oxidative stabilization (TOS) and carbonization are investigated. Itaconic acid concentration varies from 0.3 to 3 wt % and with increasing concentration of itaconic acid, the precursor fibre exhibited lower exothermicity and enhanced reactivity, resulting in 7 % less energy consumption during stabilization. Higher itaconic acid content led to improved carbon fibre properties. A 20 % increase in tensile strength was recorded for carbon fibres containing the highest amount of itaconic acid along with a higher amount of graphitic structure and carbon yield. Overall, this study explores the impact of precursor design on fibre properties as a route to the manufacture of carbon fibre with reduced embodied energy. The results of this study illustrate pathways to improve the efficiency and effectiveness of carbon fibre production, and to ultimately create high-performance, lightweight, and more sustainable carbon fibre-reinforced composites.

Itaconic Acid as a Comonomer in Betulin-Based Thermosets via Sequential and Bulk Preparation.

The inherent chemical functionalities of biobased monomers enable the production of renewably sourced polymers that further advance sustainable manufacturing. Itaconic acid (IA) is a nontoxic, commercially produced biobased monomer that can undergo both UV and thermal curing. Betulin is a biocompatible, structurally complex diol derived from birch tree bark that has been recently studied for materials with diverse applications. Here, betulin, IA, and biobased linear diacids, 1,12-dodecanedioic acid (C12) and 1,18-octadecanedioic acid (C18), were used to prepare thermosets using sequential and bulk curing methods. Thermoplastic polyester precursors were synthesized and formulated into polyester-methacrylate (PM) resins to produce sequential UV-curable thermosets. Bulk-cured polyester thermosets were prepared using a one-pot, solventless melt polycondensation using glycerol as a cross-linker. The structure-property relationships of the thermoplastic polyester precursors, sequentially prepared PM thermosets, and bulk-cured polyester thermosets were evaluated with varying IA content. Both types of thermosets exhibited higher storage moduli, Tgs, and thermal stabilities with greater IA comonomer content. These results demonstrate the viability of using IA as a comonomer to produce betulin-based thermosets each with tunable properties, expanding the scope of their applications and use in polymeric materials.

Synthesis and Characterization of Ibuprofen Delivery System Based on β-cyclodextrin/Itaconic Acid Copolymer

This study aims at preparation and characterization of drug delivery system based on grafted beta-cyclodextrin (β-CD) with itaconic acid (IA) using free-radical copolymerization technique, in the presence of N, N'-methylene bisacrylamide (BIS) and ammonium persulphate (APS) as a crosslinker and an initiator, respectively. The obtained copolymer (CD-PIA) was characterized using Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), X-ray diffraction patterns (XRD), transmission and scanning electron microscopes (TEM and SEM). Ibuprofen (IBU), as an anti-inflammatory drug model, was loaded during the preparation. The kinetic of the copolymerization was investigated in terms of grafting yield (GY %), grafting efficiency (GE %) and monomer conversion (%). Moreover, in vitro IBU release and kinetic of released using the different mathematical models (0-order, first-order and Higushi) were carried out in simulated gastric and intestinal fluids (SGF and SIF at pH 1.2 and 7.4, respectively) at 37 °. The results proved the successful preparation of the target copolymer with irregular spherical-like shape and particle size around 14 - 27.7 nm. After IBU loading, the copolymer exhibited thermal stability with crystalline nature. Also, the study showed that the synthesized copolymer, especially which high IA content is controlled the release of IBU after 4 h. Besides, it could be used as a potential IBU delivery system with sustained-release followed the first-order kinetic over 24 h.
 HIGHLIGHTS
 
 The nanogels drug carriers used for nonsteroidal anti-inflammatory drugs to overcome the unfavorable release in the stomach due to unforeseen pH alterations
 The polymeric grafted β-CD derivatives using IA represent a unique class of the host materials with tunable inclusion properties and high affinity for Ibuprofen release
 In vitro kinetic of IBU released showed the best fit with first-order model
 
 GRAPHICAL ABSTRACT

Starch and itaconic acid-based superabsorbent hydrogels for agricultural application

Biobased superabsorbent is considered as an interesting polymeric material with excellent water absorption capacity. It can act as an active agent carrier and soil conditioner along with others. Howsoever, extensive usage of polymeric superabsorbent derived from conventional petroleum sources is posing serious threats to sustainability of the ecosystem. In this facet, a high biobased content (63 %) superabsorbent was synthesized using starch and itaconic acid as renewable resources. The prepared superabsorbent polymer was authenticated by its high-water absorption capacity (650 g/g) due to the presence of porous morphology as supported by SEM image analysis and the presence of various polar groups in its structure as confirmed by Fourier transform infrared (FTIR) spectral analysis. The superabsorbent hydrogels with different compositions were prepared and their performance was evaluated towards water absorption with and without load, and in salt solutions. The swelling kinetic studies of the hydrogels revealed faster water absorption with higher itaconic acid content. The urea encapsulated hydrogels were used in soil to judge their abilities for water holding capacity, seed germination rate, soil porosity enhancement, etc. Moreover, the hydrogels possess good biodegradability as confirmed by the soil burial study, and thereby endowing the environmentally benign characteristic which can overcome the shortcomings of petroleum-based hydrogels. Thus, they have great potential to be used in agricultural applications, especially as environmentally friendly superabsorbent.

Synthesis and characterization of itaconic-based epoxy resin: Chemical and thermal properties of partially biobased epoxy resins

The quest for more sustainable structural epoxy resin (ER) adhesives is of major importance, environmentally and economically. A more friendly-environmental ER based on itaconic acid (IA), bisphenol A (BPA) and epichlorohydrin (ECH) was synthesized without the use of a catalyst. The obtained products were chemically characterized by means of 1H NMR and ATR-FTIR spectroscopy analysis. Thermal properties and rheological performances of the developed pre-polymer resins were also studied, and the final properties compared with a well-known commercial epoxy resin (ER-SIKA). Overall, the increase of IA content, resulted in a decrease of the glass transition temperature (Tg) of the pre-polymer resins, with values ranging between −9 °C and 31 °C. The obtained results showed that the prepared biobased ERs presented promising features for future crosslinking and can replace totally or partially BPA based ERs.

Acidic and alkaline gas sensitive and self-healing chitosan aerogel based on electrostatic interaction

Gas pollution is a serious problem. More attention has been paid to the detection and monitoring of toxic and harmful gases, and it is urgently needed for a sensor that could simultaneously identify and distinguish between acid and base gases. Based on the electrostatic interaction resulting from amidogen of chitosan (CS) and carboxylic groups of itaconic acid (IA), we successfully prepared a series of biomass aerogels (CS-IA aerogels) that could respond to acidic and alkaline gases with different concentrations. The acidic and alkaline gases could be easily detected and distinguished by changing the content of IA in CS-IA aerogels. Moreover, the electrostatic interactions could also endowed CS-IA aerogels with self-healing ability in the breaks at room temperature. After self-healing, CS-IA aerogels still sensitively answered to acidic and alkaline gases. CS-IA aerogels with sensitivity to acid-base gas and self-healing performance has been suggested to be promising candidates as application of multi-functional aerogels.

The Influence of Monomer Composition and Surface-CrossLinking Condition on Biodegradation and Gel Strength of Super Absorbent Polymer.

In this study, a superabsorbent polymer (SAP) comprising poly (IA-co-cellulose-co-VSA-co-AA; ICVA) core-SAP (CSAP) was synthesized through radical polymerization using itaconic acid (IA), acrylic acid (AA), cellulose, and vinyl sulfonic acid (VSA) as monomers. The absorption performances and relative biodegradability of various compositions prepared by adjusting the amounts of cellulose and VSA with constant IA and AA content were compared. Increasing the cellulose content in CSAP contributed to improved biodegradation of the surface-crosslinked SAP (SSAP) and gel strength, although the free absorbency (FA) and centrifuge retention capacity (CRC) decreased. Increasing the VSA content resulted in strong anionicity, which enables the absorption of large amounts of water. Surface-crosslinking technology was applied to the CSAP synthesized with the optimal composition ratio to increase its absorption performance and gel strength. Improved performance of the synthesized SSAP (a CRC of 30.4 g/g, absorbency under load (AUL) of 23.3 g/g, and permeability of 55 s) was achieved by selecting the optimal surface-crosslinking treatment time and the amount of distilled water in the surface-crosslinking solution: as the latter was increased in the surface-crosslinking solution, the AUL and permeability of the SSAP were improved, and its biodegradability was found to be 54% compared to the 100% biodegradable cellulose hydrogel in the control group.

Effect of different itaconic acid contents of poly(acrylonitrile-co-itaconic acid)s on their carbonization behaviors at elevated temperatures

The carbonization procedure is a crucial step for polyacrylonitrile (PAN)-based precursors to be transformed into carbon materials. In this study, PAN and poly(acrylonitrile-co-itaconic acid)s (PAIs) with different contents of itaconic acid (IA) were prepared through free radical polymerization, and their carbonization behaviors were investigated at different thermal treatment temperatures. As confirmed by Fourier transform infrared spectroscopy analyses, functional groups containing heteroatoms practically disappeared above 600 °C, due to crosslinking, condensation, dehydrogenation, and gas-evolution reactions of the carbonization processes. Deconvolution of the carbon, oxygen and nitrogen peaks from X-ray photoelectron spectroscopy analyses revealed the development of ordered and doped graphitic carbons at elevated thermal treatment temperatures. The total yields of PAIs with excess amounts of IA (3 ~ 6 mol%) demonstrated a large carbon loss during the carbonization procedures. PAI with 1 ~ 2 mol% IA afforded carbon materials with a relatively high graphitic carbon content at 1200 °C, which is potentially important for electrical conductivity. Meanwhile, carbon materials prepared from PAI with 2 mol% IA at 1200 °C exhibited a relatively high content of pyridinic nitrogen, suggesting potentially superior catalytic activity. This study afforded technical guidelines on the structural elements of PAN-based precursors to prepare carbon materials with predesigned characteristics.

Synthesis of Bio-Based Poly(Butylene Adipate-co-Butylene Itaconate) Copolyesters with Pentaerythritol: A Thermal, Mechanical, Rheological, and Molecular Dynamics Simulation Study.

Bio-based unsaturated poly(butylene adipate-co-butylene itaconate) (PBABI) aliphatic copolyesters were synthesized with pentaerythritol (PE) as a modifier, observing the melting point, crystallization, and glass transition temperatures were decreased from 59.5 to 19.5 °C and 28.2 to −9.1 °C as an increase of itaconate concentration, and Tg ranged from −54.6 to −48.1 °C. PBABI copolyesters tend to the amorphous state by the existence of the BI unit above 40 mol%. The yield strength, elongation, and Young’s modulus at different BA/BI ratios were valued in a range of 13.2–13.8 MPa, 575.2–838.5%, and 65.1–83.8 MPa, respectively. Shear-thinning behavior was obtained in all BA/BI ratios of PBABI copolyesters around an angular frequency range of 20–30 rad s−1. Furthermore, the thermal and mechanical properties of PBABI copolyesters can be well regulated via controlling the itaconic acid contents and adding the modifier. PBABI copolyesters can be coated on a 3D air mesh polyester fabric to reinforce the mechanical property for replacing traditional plaster applications.

Synthesis of poly(acrylic-co-itaconic acid) through precipitation photopolymerization for glass-ionomer cements: Characterization and properties of the cements

ObjectiveThe aim of this study was to synthesize poly(acrylic acid-co-itaconic acid) (PAA-co-PIA) ionomer through a novel precipitation photopolymerization technique. The ionomer was characterized and the effect of its structural parameters, such as molecular weight and copolymer composition were investigated on the mechanical properties of glass-ionomer prepared using the ionomer. MethodsDesign of experiment (DOE) was used to examine the effect of monomer ratio and the amount of chain transfer agent on the molecular weight and final conversion of the ionomers synthesized through the precipitation photopolymerization. The copolymer compositions were identified using FTIR and 1H-NMR spectroscopy. The molecular weights of the copolymers were evaluated by GPC. A series of PAA-co-PIA copolymers were then synthesized via the photopolymerization technique in three monomer ratios and two molecular weight ranges (high and low) to study the properties of the glass ionomers thereof. Experimental dental glass-ionomer cements were prepared by mixing the synthesized polymers with glass powder and their compressive properties were determined according to ISO 9917-1:2007 after storing for 0, 1, 7 and 28 days in distilled water. The scanning electron microscopy (SEM) was used to study the fracture surface morphology of the cements. ResultsThe PAA-co-PIA polymers were synthesized by the photopolymerization method in a short time and high purity. The DOE showed that by decreasing the acrylic acid/itaconic acid ratio and increasing the amount of transfer agent, the molecular weight and final conversion decreased significantly. By increasing the itaconic acid content in the copolymer composition and increasing the molecular weight in a constant copolymer composition, the compressive strength and modulus were increased. Microstructures revealed that cements made of the higher molecular weight poly acids showed lower cracks and voids. SignificanceThe precipitation photopolymerization technique provides a promising and facile method in the synthesis of ionomers which are used in dental cements and other application.

Electrospun poly(acrylonitrile-co-itaconic acid) as a porous carbon precursor for high performance supercapacitor: study of the porosity induced by in situ porogen activity of itaconic acid

An acrylonitrile based copolymer, poly(acrylonitrile-co-itaconic acid), P(AN-co-IA) was synthesized with different amounts of itaconic acid (IA) to study in situ porogen activity of IA to produce porous carbon nanofibers (CNFs) without any subsequent physical or chemical activation. The concept developed here avoids unnecessary and complex extra activation steps when fabricating CNFs which ultimately lead to lower char yields and uncontrollable pore sizes. The ability of COOH in P(AN-co-IA) to act as an in situ porogen by releasing CO2 during carbonization was verified by simultaneous thermogravimetric analysis-mass spectrometry compared to polyacrylonitrile (PAN). The specific surface area of PAN CNFs (27 m2 g−1) dramatically increases to 1427 m2 g−1 upon addition of ∼8 wt% IA without any ex situ activation. Furthermore, we confirmed that the porosity could be tuned by changing the IA content. The best electrochemical performance was obtained from the copolymer containing ∼8 wt% of IA, which gives a maximum specific capacitance of ∼93 F g−1 at a scan rate of 10 mV s−1 and energy density of ∼46 Wh kg−1 at 1 A g−1 without any subsequent physical or chemical activation.

A type of itaconic acid modified polyacrylate with good mechanical performance and biocompatibility

A type of itaconic acid (IA) modified polyacrylate (PIA) was synthesized by ethyl acrylate (EA), ethyl methacrylate (EMA) and methyl methacrylate (MMA) as co-monomers through the emulsion polymerization. The chemical structure of PIA characterized by FTIR and 1H NMR manifested the successful introduction of IA into PIA chains. The increase of IA content increased the particle size from 101.9 to 327.6 nm and lowered the ZETA potentials from −42.5 to −68.1 mV, respectively. It enhanced the tensile strength and tensile modulus of PIA films from 8.5 to 11.4 MPa and 82 to 582 MPa with the IA content ranging from 0.5 to 2.5 wt%. Also, Tg raised from 6.8 °C to 17.9 °C due to the compact structure and rigidity of the chains. Moreover, TGA indicated the increased thermal stability of PIA as the increase of IA content. Foremost, MTT colorimetric test proved PIA had higher cell viability and ALT serum activity than the common coating materials in the market. In vivo toxicity test evaluated by the physiological responses of mice through the oral administration also illustrated PIA was innoxious and had good biocompatibility. The obtained results indicated PIA would have great potential as drug coating materials in the pharmaceutical industry.

Thermal Analysis on the Stabilization Behavior of Ternary Copolymers Based on Acrylonitrile, Methyl Acrylate and Itaconic Acid

Polyacrylonitrile (PAN)-based copolymers are widely used as a precursor for manufacturing high performance carbon fibers via a series of processes of thermal stabilization, carbonization, and graphitization. We have recently synthesized a series of copolymers with various compositions of acrylonitrile (AN), methyl acrylate (MA) and itaconic acid (IA) by using an efficient aqueous suspension polymerization. In this study, the influences of MA and IA units on thermal stabilization behavior of AN/MA/IA-based terpolymers has been investigated by thermal analyses using DSC and TGA. It was found that the glass transition temperatures (Tg) of AN/MA/IA-based terpolymers with a constant AN content increased with the IA content due to a specific interaction between carboxylic acid and nitrile groups, while the MA unit played a role of lowering Tg of the copolymers owing to the interruption of AN sequence with a strong dipole-dipole interaction. The exothermic peaks of DSC curves as well as the weight loss of TGA/DTG curves under air condition revealed that the IA unit in AN/MA/IA-based terpolymers contributed to accelerate the oxidation reaction especially under air condition and also to slow down the following cyclization and dehydrogenation reactions including isomerization, unlike PAN homopolymer and AN/MA-based bipolymers. On the other hand, the MA unit in AN/MA-based bipolymers and AN/MA/IA-based terpolymers served as a delaying agent on the overall thermal stabilization reactions of oxidation, cyclization and dehydrogenation.

Synthesis of hydrogels for combinatorial delivery of 5-fluorouracil and leucovorin calcium in colon cancer: optimization, in vitro characterization and its toxicological evaluation

Chemical cross-linking of monomers methacrylic acid (MAA) and itaconic acid (IA) through ethylene glycol dimethacrylate (EGDMA) was carried out for synthesizing robust hydrogel system for oral administration and tuned for targeted release of 5-fluorouracil (5-FU) and leucovorin calcium (LV) at colonic site. Aqueous-based free radical polymerization method was optimized first, and then a series of batches were prepared. Various in vitro tests were performed to probe the characteristics of synthesized hydrogels such as the presence of functional groups, surface morphology, crystalline/amorphous properties and thermal stability which confirms the cross-linking and stability of hydrogels. Swelling, drug loading and drug release evaluations were carried out at two different pH levels of 1.2 and pH 7.4. pH responsiveness was observed in synthesized hydrogels. Co-polymeric hydrogels exhibited higher swelling and release at higher pH 7.4 as compared to lower pH 1.2. Moreover, an increased trend in swelling and drug release was observed for formulations with higher content of IA. Co-polymeric hydrogels were biocompatible and non-toxic to biological system as investigated by acute oral toxicity study on rabbits.

Identifying the role of the acidic comonomer in poly(acrylonitrile-co-itaconic acid) during stabilization process through low temperature electron beam irradiation

The stabilization behavior of poly (acrylonitrile-co-itaconic acid) (PAI) by using electron beam irradiation (EBI) was investigated to identify the role of itaconic acid (IA). EBI was employed as a tool to generate radicals, which induced a “cold” stabilization reaction at room temperature and excluded ionic and thermally induced radical-mediated stabilization reactions. Fourier transform infrared spectroscopy was employed to quantitatively track the structural evolution of the PAI during stabilization. The stabilization reactions of the PAIs successfully progressed with higher EBI dosages at room temperature. More efficient cyclization reactions were observed for the PAIs with increased amounts of IA, because of the increased amorphous regions of the PAIs with a higher level of IA. The extents of the cyclization values of the PAIs normalized to their crystallinity values were similar to each other regardless of the IA contents, indicating the absence of an ionic initiation mechanism of IA at room temperature. In addition, the incorporation of IA units in PAIs increased the polarity and oxophilicity of the PAIs, thereby inducing facilitated oxygen uptake reactions, as evidenced by the high concentrations of conjugated carbonyl groups in the stabilized structures.

Dual Responsive Poly(N-vinylcaprolactam) Based Degradable Microgels for Drug Delivery

Poly(N-vinylcaprolactam)-based biodegradable microgels are prepared for drug delivery application via precipitation polymerization using diacetone acrylamide (DAAM) and dimethyl itaconate (IADME) as comonomers. The microgel particles are subsequently crosslinked by addition of adipic acid dihydrazide, which reacts with the ketone groups of DAAM. Itaconic acid (IA) groups are generated by the hydrolysis of IADME units inside the microgels resulting into both pH and temperature sensitive microgel particles. Volume phase transition temperature of the obtained microgels is influenced by both IA content and pH of the surrounding medium. Due to the incorporation of hydrazone linkages, the microgels show degradation under acidic conditions. These microgels can effectively encapsulate doxorubicin (DOX) as a model drug and show low DOX leakage under physiological conditions while rapid DOX release is observed at low pH. The results of the cytotoxicity assay further display that the DOX-loaded microgels exhibit effective antitumor activity against HeLa cells demonstrating their great potential as drug delivery carriers for cancer therapy.

Biobased UV-curable coatings based on itaconic acid

A series of renewable unsaturated polyesters were synthesized from itaconic acid (IA), succinic acid, and 1,4-butanediol by solvent-free polycondensation. Previous studies utilizing IA to make polyesters for coating applications have shown great potential; however, the curing and material properties have not been investigated in detail. The aim of this study was to investigate how the curing is affected by the amount of unsaturations and how well itaconate-based polyesters crosslink without the addition of any other unsaturated monomers or reactive diluents. The chemical structures of the polyesters were confirmed with FTIR, 1H-NMR, and THF–SEC. The degree of curing was studied with FTIR, and the mechanical properties of the crosslinked polyesters were evaluated with DMA, pendulum hardness, and microindentation. The degree of curing was found to be up to 75%, and furthermore, it was found that the final mechanical properties of the crosslinked coatings could be tuned by modifying the IA content in the monomer composition. The results from DMA showed that there is a clear trend between mechanical properties and crosslinking density.

Study on the multiple cyclization reactions and the formed structures in poly(acrylonitrile‐co‐itaconic acid) copolymers during thermal treatment

The present work provided some in‐depth understanding on the role of itaconic acid (IA) in the structural evolution of poly(acrylonitrile‐co‐itaconic acid) (PAI) polymers and the formed cyclic structures during thermal treatment. As the increasing content of IA, the cyclization initiated by the ionic mechanism increased with the less β‐amino nitrile formed and the higher extent of cyclization. The IA comonomer initiated multiple cyclization reactions, namely, the first ionic cyclization and the second ionic cyclization, by the jump transportation of activation species between different PAI chains during thermal treatment. The times of the jump transportation of activation species was about two or three at 250°C. The presence of IA comonomer promoted the formation of long sequence cyclic structures rather than isolated cyclic structure under non‐oxidative condition. The thermal stability of PAI was improved by the more and better cyclic structures and the crosslinking structures caused by the jump transportation of activation species, which reasonably resulted in a better graphitic lattice during the carbonization. Copyright © 2017 John Wiley & Sons, Ltd.

Biodegradation of Poly(Aspartic Acid-Itaconic Acid) Copolymers by Miscellaneous Microbes from Natural Water

Poly(aspartic acid-itaconic acid) copolymers (PAI) is a new scale inhibitor for water treatment. Thus, it is necessary to investigate its biodegradability. The biodegradability of PAI was investigated through CO2 evolution tests under different conditions based on determination of carbon dioxide production. The investigation results showed that the degradation rate of PAI on day 10 and day 28 were respectively 38.7 and 79.5%, indicating that PAI was one kind of easily biodegradable scale inhibitors. With the increase in the content of itaconic acid in copolymerization process, the biodegradability of PAI was significantly reduced. In addition, the high biodegradability might be attributed to the existence of C–N bone-structure and more –COO–. Finally, Cu2+ could decrease the degradation percentage and the enzyme inhibition effect of Cu2+ was not the linear effect, but the “low-dosage effect”.