Itaconic acid

Synthesis and Application of a Phosphorous-Free and Non-Nitrogen Polymer as an Environmentally Friendly Scale Inhibition and Dispersion Agent in Simulated Cooling Water Systems.[Pubmed:32637823]

ACS Omega. 2020 Jun 18;5(25):15487-15494.

A novel phosphorus-free and non-nitrogen scale inhibition and dispersion agent was synthesized from epoxysuccinic acid (ESA), Itaconic acid (IA), and sodium methyl propylene sulfonate (SMAS). It was characterized by infrared spectroscopy (IR), nuclear magnetic resonance (NMR), and elemental analysis, and its molecular weight and distribution were determined by gel permeation chromatography (GPC). Static experimental methods were used to evaluate the scale inhibition against CaCO3, Ca3(PO4)2, and CaSO4. The dispersion ability was evaluated by measuring the dispersive property of iron oxide. By observing the morphology of the CaCO3 scale, the scale inhibition mechanism was discussed. The results showed that when the ratio of raw materials (ESA/IA/SMAS) was 10:10:5, the scale inhibition rate of CaCO3 and CaSO4 reached 100% with the dosages of 20 and 10 mg/L, respectively. In addition, the scale inhibition rate against Ca3(PO4)2 was up to 96.64% with a dosage of 100 mg/L. The property of dispersing iron oxide exhibited the best results with 50 mg/L of the agent. On the 21st day, the biodegradation rate reached 63.33%. This polymer was an environmentally friendly antiscale and dispersant with good scale inhibition and biodegradability.

Modified Starch as a Filter Controller in Water-Based Drilling Fluids.[Pubmed:32575779]

Materials (Basel). 2020 Jun 20;13(12). pii: ma13122794.

Herein, the effectiveness of an Itaconic acid (IA) graft copolymer on native corn starch (NCS) as a filter control agent in fresh water-based drilling fluids (WBDFs) was evaluated. The copolymer (S-g-IA_APS) was synthesized by conventional radical dispersion polymerization using the redox initiation system (NH4)2S2O8/NaHSO3. The modification of the starches was verified by volumetry, Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). Then, three WBDFs were formulated in which only the added polymer (NCS, S-g-IA_APS, and a commercial starch (CPS)) was varied to control the fluid losses. The physico-chemical, rheological, and filtering properties of the formulated systems were evaluated in terms of density (rho), pH, plastic viscosity (microp), apparent viscosity (microa), yield point (Yp), gel strength (Rg), and filtrated volume (VAPI). In order to evaluate the resistance to temperature and contaminants of the WBDFs, they were subjected to high pressure and high temperature filtering (VHPHT). The filter control agents were also subjected to aging and contamination with cement and salt. The S-g-IA_APS addition improved the filtering behavior at a high pressure and temperature by 38%.

Injectable thermosensitive hybrid hydrogel containing graphene oxide and chitosan as dental pulp stem cells scaffold for bone tissue engineering.[Pubmed:32561280]

Int J Biol Macromol. 2020 Jun 16. pii: S0141-8130(20)33579-0.

Here, we fabricated thermosensitive injectable hydrogel containing poly (N-isopropylacrylamide) (PNIPAAm)-based copolymer/graphene oxide (GO) composite with different feed ratio to chitosan (CS) as a natural polymer through physical and chemical crosslinking for the proliferation and differentiation of the human dental pulp stem cells (hDPSCs) to the osteoblasts. The PNIPAAm copolymer/GO composite was synthesized by free-radical copolymerization of (N-isopropylacrylamide) (NIPAAm), Itaconic acid (IA) and maleic anhydride-modified poly(ethylene glycol) (PEG) in the presence of GO and used for the preparation of the hydrogels. The formulated hydrogels were evaluated for the porous architecture, rheological behavior, compressive strength, swelling property, in vitro degradation, hemocompatibility, biocompatibility, and differentiation. The hydrogel could enhance the deposition of minerals and the activity of alkaline phosphatase (ALP), in large part attributable to the oxygen and amine-containing functional groups of GO and CS. The engineered hydrogel could also upregulate the expression of the Runt-related transcription factor 2 and osteocalcin in the hDPSCs cultivated in both the normal and osteogenic media. It seems to promote the absorption of osteogenic inducer too. Based on our findings, the engineered hydrogel demonstrated the osteogenic potential, upon which it is proposed as a constructing scaffold in bone tissue engineering for the transplantation of hDPSCs.

Biobased Poly(itaconic Acid-co-10-Hydroxyhexylitaconic Acid)s: Synthesis and Thermal Characterization.[Pubmed:32545881]

Materials (Basel). 2020 Jun 14;13(12). pii: ma13122707.

Renewable vinyl compounds Itaconic acid (IA) and its derivative 10-hydroxyhexylItaconic acid (10-HHIA) are naturally produced by fungi from biomass. This provides the opportunity to develop new biobased polyvinyls from IA and 10-HHIA monomers. In this study, we copolymerized these monomers at different ratios through free radical aqueous polymerization with potassium peroxodisulfate as an initiator, resulting in poly(IA-co-10-HHIA)s with different monomer compositions. We characterized the thermal properties of the polymers by thermogravimetric analysis (TGA) and Fourier-transform infrared spectroscopy (FT-IR). The nuclear magnetic resonance analysis and the gel permeation chromatography showed that the polymerization conversion, yield, and the molecular weights (weight-averaged Mw and number-averaged Mn) of the synthesized poly(IA-co-10-HHIA)s decreased with increasing 10-HHIA content. It is suggested that the hydroxyhexyl group of 10-HHIA inhibited the polymerization. The TGA results indicated that the poly(IA-co-10-HHIA)s continuously decomposed as temperature increased. The FT-IR analysis suggested that the formation of the hydrogen bonds between the carboxyl groups of IA and 10-HHIA in the polymer chains was promoted by heating and consequently the polymer dehydration occurred. To the best of our knowledge, this is the first time that biobased polyvinyls were synthesized using naturally occurring IA derivatives.

Valorizing a hydrothermal liquefaction aqueous phase through co-production of chemicals and lipids using the oleaginous yeast Yarrowia lipolytica.[Pubmed:32534224]

Bioresour Technol. 2020 Jun 6;313:123639.

Hydrothermal liquefaction is a promising technology to upgrade wet organic waste into a biocrude oil for diesel or jet fuel; however, this process generates an acid-rich aqueous phase which poses disposal issues. This hydrothermal liquefaction aqueous phase (HTL-AP) contains organic acids, phenol, and other toxins. This work demonstrates that Y. lipolytica as a unique host to valorize HTL-AP into a variety of co-products. Specifically, strains of Y. lipolytica can tolerate HTL-AP at 10% in defined media and 25% in rich media. The addition of HTL-AP enhances production of the polymer precursor Itaconic acid by 3-fold and the polyketide triacetic acid lactone at least 2-fold. Additional co-products (lipids and citric acid) were produced in these fermentations. Finally, bioreactor cultivation enabled 21.6 g/L triacetic acid lactone from 20% HTL-AP in mixed sugar hydrolysate. These results demonstrate the first use of Y. lipolytica in HTL-AP valorization toward production of a portfolio of value-added compounds.

Atrazine removal using chitin-cl-poly(acrylamide-co-itaconic acid) nanohydrogel: Isotherms and pH responsive nature.[Pubmed:32507180]

Carbohydr Polym. 2020 Aug 1;241:116258.

Removal of commonly used pesticide, atrazine was examined by employing chitin based nanohydrogel. Chitin-cl-poly (acrylamide-co-Itaconic acid) nanohydrogel was synthesized by microwave method. Dissolution of chitin was done by freezing thawing method in NaOH/urea solution. The morphology and functional characteristics were confirmed by FTIR, XRD, SEM, TGA, TEM, and EDX techniques. Maximum swelling capacity, isotherm study, kinetics, adsorption and desorption of atrazine pesticide were evaluated in this study. Maximum adsorption capacity of designed nanohydrogel was found to be 204.08mg/g. Langmuir and pseudo- second order models were determined to be applicable for explaining the undertaken adsorption process. Neutral pH was found to be favorable for maximum adsorption. In addition, results have specified the pH responsive nature of nanohydrogel for controlled release of atrazine.

Effect of 1,2,4,5-Benzenetetracarboxylic Acid on Unsaturated Poly(butylene adipate-co-butylene itaconate) Copolyesters: Synthesis, Non-Isothermal Crystallization Kinetics, Thermal and Mechanical Properties.[Pubmed:32438555]

Polymers (Basel). 2020 May 19;12(5). pii: polym12051160.

Unsaturated poly (butylene adipate-co-butylene itaconate) (PBABI) copolyesters were synthesized through melt polymerization composed of 1,4-butanediol (BDO), adipic acid (AA), Itaconic acid (IA) and 1,2,4,5-benzenetetracarboxylic acid (BTCA) as a cross-linking modifier. The melting point, crystallization and glass transition temperature of the PBABI copolyesters were detected around 29.8-49 degrees C, 7.2-29 degrees C and -51.1 and -58.1 degrees C, respectively. Young's modulus can be modified via partial cross-linking by BTCA in the presence of IA, ranging between 32.19-168.45 MPa. Non-isothermal crystallization kinetics were carried out to explore the crystallization behavior, revealing the highest crystallization rate was placed in the BA/BI = 90/10 at a given molecular weight. Furthermore, the thermal, mechanical properties, and crystallization rate of PBABI copolyesters can be tuned through the adjustment of BTCA and IA concentrations.

Distinct Gut Microbiota and Metabolite Profiles Induced by Different Feeding Methods in Healthy Chinese Infants.[Pubmed:32435235]

Front Microbiol. 2020 May 6;11:714.

Human milk is closely correlated with infant gut microbiota and is important for infant development. However, most infants receive exclusively insufficient breast milk, and the discordance between effects of commercial formula and human milk exists. To elucidate the differences induced by various feeding methods, we determined microbiota and metabolites composition in fecal samples from 77 healthy infants in Northeast China and identified the differences in various feeding methods. Bacterial 16S rRNA gene sequence analysis demonstrated that the fecal samples of exclusively breastfed (BF) infants were abundant in Bifidobacterium and Lactobacillus; the mixed-fed (MF) infants had the highest abundance of Veillonella and Klebsiella; the exclusively formula-fed (FF) infants were enriched in Bacteroides and Blautia; and the complementary food-fed (CF) infants were associated with higher relative abundance of Lachnoclostridium and Akkermansia. Liquid chromatography-mass spectrometry (LC-MS)-based metabolomics data revealed that the fecal samples of BF infants had the highest abundance of dl-citrulline, threonine, l-proline, l-glutamine, guanine, and l-arginine; the MF infants were abundant in d-maltose, stearidonic acid, capric acid, and myristic acid; the FF infants were enriched in Itaconic acid, 4-pyridoxic acid, prostaglandin B2, thymine, dl-alpha-hydroxybutyric acid, and orotic acid; and the CF infants were associated with higher relative abundance of taurine, l-tyrosine, adenine, and uric acid. Furthermore, compared with the BF infants, the MF and FF infants were more abundant in fatty acid biosynthesis. Collectively, these findings will provide probable explanations for some of the risks and benefits related to infant feeding methods and will support a theoretical basis for the development of infant formula.

Synthesis and application of superabsorbent polymer microspheres for rapid concentration and quantification of microbial pathogens in ambient water.[Pubmed:32421015]

Sep Purif Technol. 2020 May 15;239:116540.

Even though numerous methods have been developed for the detection and quantification of waterborne pathogens, the application of these methods is often hindered by the very low pathogen concentrations in natural waters. Therefore, rapid and efficient sample concentration methods are urgently needed. Here we present a novel method to pre-concentrate microbial pathogens in water using a portable 3D-printed system with super-absorbent polymer (SAP) microspheres, which can effectively reduce the actual volume of water in a collected sample. The SAP microspheres absorb water while excluding bacteria and viruses by size exclusion and charge repulsion. To improve the water absorption capacity of SAP in varying ionic strength waters (0-100 mM), we optimized the formulation of SAP to 180 gL(-1) Acrylamide, 75 gL(-1) Itaconic acid and 4.0 gL(-1) Bis-Acrylamide for the highest ionic strength water as a function of the extent of cross-linking and the concentration of counter ions. Fluorescence microscopy and double-layer agar plating respectively showed that the 3D-printed system with optimally-designed SAP microspheres could rapidly achieve a 10-fold increase in the concentration of Escherichia coli (E. coli) and bacteriophage MS2 within 20 min with concentration efficiencies of 87% and 96%, respectively. Fold changes between concentrated and original samples from qPCR and RT-qPCR results were found to be respectively 11.34-22.27 for E. coli with original concentrations from 10(4) to 10(6) cell.mL(-1), and 8.20-13.81 for MS2 with original concentrations from 10(4) to 10(6) PFU.mL(-1). Furthermore, SAP microspheres can be reused for 20 times without performance loss, significantly decreasing the cost of our concentration system.

Microbial Screening Based on the Mizoroki-Heck Reaction Permits Exploration of Hydroxyhexylitaconic-Acid-Producing Fungi in Soils.[Pubmed:32365722]

Microorganisms. 2020 Apr 29;8(5). pii: microorganisms8050648.

Recently, we developed a unique microbial screening method based on the Mizoroki-Heck reaction for Itaconic acid (IA)-producing fungi. This method revealed that 37 out of 240 fungal strains isolated from soils produce vinyl compounds, including IA. In this study, we further characterized these compounds in order to verify that the screening method permits the isolation of fungi that produce other vinyl compounds, excluding IA. HPLC analysis showed that 11 out of 37 isolated strains produced IA, similar to Aspergillus terreus S12-1. Surprisingly, the other 8 isolated strains produced two vinyl compounds with HPLC retention times different from that of IA. From these strains, the vinyl compounds of Aspergillus niger S17-5 were characterized. Mass spectrometric and NMR analyses showed that they were identical to 8-hydroxyhexylItaconic acid (8-HHIA) and 9-HHIA. This finding showed that 8-HHIA- and 9-HHIA-producing fungi, as well as IA-producing fungi, are ubiquitously found in soils. Neither 8-HHIA nor 9-HHIA showed antibacterial or anti-inflammatory activities. Interestingly, 8-HHIA and 9-HHIA showed cytotoxicity against the human cervical cancer cell line (HeLa) and human diploid cell line (MRC-5), and MRC-5 only, respectively, compared to IA at the same concentration. This study indicates that the screening method could easily discover fungi producing 8-HHIA and 9-HHIA in soils.

Metabolic engineering of an acid-tolerant yeast strain Pichia kudriavzevii for itaconic acid production.[Pubmed:32346511]

Metab Eng Commun. 2020 Feb 11;10:e00124.

Itaconic acid (IA), or 2-methylenesuccinic acid, has a broad spectrum of applications in the biopolymer industry owing to the presence of one vinyl bond and two acid groups in the structure. Its polymerization can follow a similar mechanism as acrylic acid but additional functionality can be incorporated into the extra beta acid group. Currently, the bio-based production of IA in industry relies on the fermentation of the filamentous fungus Aspergillus terreus. However, the difficulties associated with the fermentation undertaken by filamentous fungi together with the pathogenic potential of A. terreus pose a serious challenge for industrial-scale production. In recent years, there has been increasing interest in developing alternative production hosts for fermentation processes that are more homogenous in the production of organic acids. Pichia kudriavzevii is a non-conventional yeast with high acid tolerance to organic acids at low pH, which is a highly desirable trait by easing downstream processing. We introduced cis-aconitic acid decarboxylase gene (cad) from A. terreus (designated At_cad) into this yeast and established the initial titer of IA at 135 +/- 5 mg/L. Subsequent overexpression of a native mitochondrial tricarboxylate transporter (herein designated Pk_mttA) presumably delivered cis-aconitate efficiently to the cytosol and doubled the IA production. By introducing the newly invented CRISPR-Cas9 system into P. kudriavzevii, we successfully knocked out both copies of the gene encoding isocitrate dehydrogenase (ICD), aiming to increase the availability of cis-aconitate. The resulting P. kudriavzevii strain, devoid of ICD and overexpressing Pk_mttA and At_cad on its genome produced IA at 505 +/- 17.7 mg/L in shake flasks, and 1232 +/- 64 mg/L in fed-batch fermentation. Because the usage of an acid-tolerant species does not require pH adjustment during fermentation, this work demonstrates the great potential of engineering P. kudriavzevii as an industrial chassis for the production of organic acid.

Measurement of radiation attenuation parameters of modified defatted soy flour-soy protein isolate-based mangrove wood particleboards to be used for CT phantom production.[Pubmed:32333105]

Radiat Environ Biophys. 2020 Apr 24. pii: 10.1007/s00411-020-00844-z.

For the first time, Rhizophora spp. (Rh. spp.) particleboard phantoms were developed using defatted soy flour (DSF) and soy protein isolate (SPI) modified by sodium hydroxide and Itaconic acid polyamidoamine-epichlorohydrin (IA-PAE) adhesive. The microstructural characterization and X-ray diffraction patterns of the material revealed that the modified DSF and SPI adhesives became more compact and homogeneous when NaOH/IA-PAE was added, which prevented damage by moisture. It was confirmed that the composite is crystalline with (101), (002), and (004) orientations. Phantoms made of this material were scanned with X-ray computed tomography (CT) typically used for abdominal examinations with varying energies corresponding to 80, 120, and 135 kVp, to determine CT numbers, electron densities, and density distribution profiles. The radiation attenuation parameters were found to be not significantly different from those of water (XCOM) with p values [Formula: see text] 0.05 for DSF and SPI. The DSF- and SPI-based particleboard phantoms showed CT numbers close to those of water at the three X-ray CT energies. In addition, electron density and density distribution profiles of DSF-SPI-Rh. spp. particleboard phantoms with 15 wt% IA-PAE content were even closer to those of water and other commercial phantom materials at the three X-ray CT energies. It is concluded that DSF-SPI with NaOH/IA-PAE added can be used as a potential adhesive in Rh. spp. particleboard phantoms for radiation dosimetry.

Straightforward Synthetic Protocol to Bio-BasedUnsaturated Poly(ester amide)s from Itaconic Acidwith Thixotropic Behavior.[Pubmed:32331487]

Polymers (Basel). 2020 Apr 22;12(4). pii: polym12040980.

In the field of polymer chemistry, tremendous efforts have been made over the lastdecade to replace petrochemical monomers with building blocks from renewable resources. In thisrespect, Itaconic acid has been used as an alternative to acrylic acid or maleic acid in unsaturatedpolyesters for thermal or UV-curing applications. However, examples of poly(ester amide)s fromItaconic acid are scarce. Under standard polycondensation reactions, the presence of free aminesleads to aza-Michael addition reactions at the alpha,beta-unsaturated double bond of the Itaconic acid andisomerization reactions to mesaconic acid. Both reactions make the resulting materials useless asUV-curing polymer resins. To avoid these undesired side reactions, we herein report the use ofpreformed, well-defined diols containing internal amide bonds. The resulting unsaturatedpoly(ester amide) resins were analyzed before and after UV-induced crosslinking. Viscositymeasurements revealed a strong thixotropic behavior induced by the amide groups, which isusually not detected in structurally similar polyester resins.

Substrate profiling and tolerance testing of Halomonas TD01 suggest its potential application in sustainable manufacturing of chemicals.[Pubmed:32311394]

J Biotechnol. 2020 Jun 10;316:1-5.

Halomonas TD01, which can grow under non-sterile and continuous processes at high pH and high salt concentrations, is a robust platform for PHA production from glucose. For extending other low-cost sustainable substrates and increasing the potential application in other value-added products, a better understanding of substrates utilization and chemicals tolerance is necessary. In this study, the substrate profiling of TD01 was analyzed via Biolog. Phenotype microarray results demonstrated that TD01 has a wide-ranging substrate spectrum and can utilize 140 of the 190 test compounds. Some cheap, abundant carbon sources, such as sodium acetate, glycerol, ethanol and lactate can well support the growth of TD01 in shake-flask, and are therefore suggested to be its alternative low-cost substrates for chemicals production in future. Furthermore, the tolerance of TD01 to various chemicals was tested. The results showed that the tolerability of TD01 to high concentrations of organic acid salts is prominent. When adding 75g/L sodium acetate, 100g/L succinic acid and 100g/L Itaconic acid in the medium, the growth rate reduced 56.14%, 52.63% and 47.37%, respectively. All these results highlight TD01 as a promising, next generation industrial workhorse in chemicals biomanufacturing from cheap organic acid salts.

Synthesis of poly(acrylic-co-itaconic acid) through precipitation photopolymerization for glass-ionomer cements: Characterization and properties of the cements.[Pubmed:32307121]

Dent Mater. 2020 Jun;36(6):e169-e183.

OBJECTIVE: The 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. METHODS: Design 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 (1)H-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. RESULTS: The 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. SIGNIFICANCE: The precipitation photopolymerization technique provides a promising and facile method in the synthesis of ionomers which are used in dental cements and other application.