Functional materials synthesized from bio-based building blocks are fascinating and challenging in the fields of chemistry and materials science.Herein,we present a versatile strategy for synthesizing bio-based stimul...Functional materials synthesized from bio-based building blocks are fascinating and challenging in the fields of chemistry and materials science.Herein,we present a versatile strategy for synthesizing bio-based stimulus-responsive polymers derived from itaconic acid(IA).Bearing an azobenzene-containing side chain,the IA-based epoxy polymer exhibited both photoresponsiveness and acid/base-stimulus responsiveness.With controllable manipulation of the stress field of the wrinkling IA-polymer film via the stress relaxation effect resulting from the reversible cis-trans isomerization of the azobenzene moieties or solvent-induced swelling of the film,various tailor-made patterned wrinkling surfaces were conveniently fabricated.More importantly,the azobenzene protonation/deprotonation yields a reversible visual color transformation between pale yellow and purple in the film,which allows these IA-based polymer-coated surfaces to be utilized as rewritable information storage media.Various elegant pattern information can be acid-printed and base-erased(within 10 s)for multiple cycles and legible for over one day under laboratory conditions.Notably,the aforementioned dual-stimulus responsiveness of the IA-based polymer film enables its surface to be applied in information encryption.This study not only paves a new avenue for the convenient fabrication of stimulus-responsive surfaces but also sheds light on the development of functional polymers through green engineering.展开更多
The most widely used bisphenol A-type epoxy resin(DGEBA)in electrical engineering demonstrates excellent mechanical and electrical properties.However,the insoluble and infusible characteristics of cured DGEBA make it ...The most widely used bisphenol A-type epoxy resin(DGEBA)in electrical engineering demonstrates excellent mechanical and electrical properties.However,the insoluble and infusible characteristics of cured DGEBA make it difficult to efficiently degrade and recycle decommissioned electrical equipment.In this study,a degradable itaconic acid-based epoxy resin incorporating dynamic covalent bonds was prepared through the integration of ester bonds and disulfide bonds,with itaconic acid as the precursor.The covalent bonding effects on the mechanical,thermal,electrical,and degradation characteristics were systematically evaluated.The experimental results revealed that the introduction of dynamic ester bonds enhanced the mechanical properties and thermal stability of the resin system,achieving a flexural strength of 141.57 MPa and an initial decomposition temperature T_(5%)of up to 344.9℃.The resin system containing dynamic disulfide bonds exhibited a dielectric breakdown strength of 41.11 k V/mm.Simultaneously,the incorporation of disulfide bonds endowed the epoxy resin with remarkable degradability,enabling complete dissolution within 1.5 h at 90℃ in a mixed solution of dithiothreitol(DTT)and N-methylpyrrolidone(NMP).This research provides a valuable reference for the application of itaconic acid-based vitrimer with dynamic covalent bonds in electrical materials,contributing to the development and utilization of environmentally friendly electrical equipment.展开更多
Methacrylic acid,an important organic chemical,is commercially manufactured starting from fossil feedstock.The decarboxylation of itaconic acid derived for biomass is a green route to the synthesis of methacrylic acid...Methacrylic acid,an important organic chemical,is commercially manufactured starting from fossil feedstock.The decarboxylation of itaconic acid derived for biomass is a green route to the synthesis of methacrylic acid.In view of the problems existing in the researches on this route such as use of noble metal catalyst,harsh reaction conditions and low desired-product yield,we prepared a series of hydroxyapatite catalysts with different Ca/P molar ratios and evaluated their catalytic performance.The results showed that the hydroxyapatite catalyst with a Ca/P molar ratio of 1.58 had the best catalytic activity.The highest yield of MAA up to 61.2%was achieved with basically complete conversion of itaconic acid under the suitable reaction conditions of 1 equivalent of NaOH,2 MPa of N_(2),250℃,and 2 h.On this basis,a reaction network for the decarboxylation of itaconic acid to methacrylic acid catalyzed by hydroxyapatite was established.With the aid of catalyst characterization using X-ray powder diffraction,NH3/CO2 temperature-programmed desorption,N_(2)physisorption,inductively coupled plasma optical emission spectrometry,and scanning electron microscopy,we found that the distribution of surface acid sites and basic sites,crystal growth orientation,texture properties and morphology of hydroxyapatite varied with the Ca/P molar ratio.Furthermore,the change of the crystal growth orientation and its influence on the surface acidity and alkalinity were clarified.展开更多
The synthesis of methacrylic acid from biomass-derived itaconic acid is a green route,for it can get rid of the dependence on fossil resource.In order to solve the problems on this route such as use of a preciousmetal...The synthesis of methacrylic acid from biomass-derived itaconic acid is a green route,for it can get rid of the dependence on fossil resource.In order to solve the problems on this route such as use of a preciousmetal catalyst and a corrosive homogeneous alkali,we prepared a series of hydroxyapatite catalysts by an ionic liquid-assisted hydrothermal method and evaluated their catalytic performance.The results showed that the ionic liquid[Bmim]BF_(4) can affect the crystal growth of hydroxyapatite,provide fluoride ion for fluorination of hydroxyapatite,and adjust the surface acidity and basicity,morphology,textural properties,crystallinity,and composition of hydroxyapatite.The[Bmim]BF4 dosage and hydrothermal temperature can affect the fluoride ion concentration in the hydrothermal system,thus changing the degree of fluoridation of hydroxyapatite.High fluoride-ion concentration can lead to the formation of CaF_(2) and thus significantly decrease the catalytic performance of hydroxyapatite.The hydrothermal time mainly affects the growth of hydroxyapatite crystals on the c axis,leading to different catalytic performance.The suitable conditions for the preparation of this fluoridized hydroxyapatite are as follows:a mass ratio of[Bmim]BF4 to calcium salt=0.2:1,a hydrothermal time of 12 h,and a hydrothermal temperature of 130℃.A maximal methacrylic acid yield of 54.7%was obtained using the fluoridized hydroxyapatite under relatively mild reaction conditions(250℃ and 2 MPa of N_(2))in the absence of a precious-metal catalyst and a corrosive homogeneous alkali.展开更多
The terpolymer of itaconic acid, acrylamide and 2-acrylamido-2-methyl-1-propane sulfonic acid was synthesized through the free-radical polymerization. The IR spectra confirmed that there was no olefinic band, while th...The terpolymer of itaconic acid, acrylamide and 2-acrylamido-2-methyl-1-propane sulfonic acid was synthesized through the free-radical polymerization. The IR spectra confirmed that there was no olefinic band, while the TGA results revealed that the terpolymer was of high thermal stability.展开更多
The reaction mechanism of IA/MA copolymer system andcotton cellulose is conjectured and verified, the two keysteps, such as the formation of cyclic anhydride interme-diates and the building of ester crosslinklng, and ...The reaction mechanism of IA/MA copolymer system andcotton cellulose is conjectured and verified, the two keysteps, such as the formation of cyclic anhydride interme-diates and the building of ester crosslinklng, and the ef-fect of sodium hypophosphite are especially emphasized,by FT - IR spectroscopy and acid- base titration anal-yses. The experiments reveal that carboxylic acids main.ly change to cyclic anhydride in the pre - drying step andSodium Hypophosphite (SHP) has effect on it, but mostester - crosslinkages are built in the curing step and SHPhas effects on both anhydride formation and ester -crosslinking formation.展开更多
Cotton fabric samples are padded with maleic acid (MA) and itaconic acid (IA) finishing bath in the presence of potassium persulfate (K 2S 2O 8), and then dried at different temperatures for different time intervals. ...Cotton fabric samples are padded with maleic acid (MA) and itaconic acid (IA) finishing bath in the presence of potassium persulfate (K 2S 2O 8), and then dried at different temperatures for different time intervals. The portion of unreacted monomers on cotton fabric samples is determined by means of measuring the double bond content. The kinetic data (rate constants, Arrhenius activation energy, frequency factor) of the in-situ polymerization have been calculated.展开更多
Poly(aspartic acid-itaconic acid) copolymer was synthesized from aspartic acid(Asp) and itaconic acid(Ita) under microwave irradiation. The effects of microwave power, microwave irradiation time, molar ratio of itacon...Poly(aspartic acid-itaconic acid) copolymer was synthesized from aspartic acid(Asp) and itaconic acid(Ita) under microwave irradiation. The effects of microwave power, microwave irradiation time, molar ratio of itaconic acid and aspartic acid, catalyst type, catalyst and organic solvent content on copolymer yield, and the performance for inhibition of CaCO_3 fouling were investigated. It was found that the product yield achieved a highest record of 95% when the amount of catalyst Na H_2PO_4 was 0.012 mol, the amount of organic solvent propylene carbonate was 16 m L, the molar ratio of Asp/Ita was 3:1, the microwave output power was 1200 W and the irradiation time was 5.5 min. And the product performance for inhibition of calcium carbonate also reached a highest value of 94.38%. Structural characterization of the product showed that the product was the aspartic acid-itaconic acid copolymer.展开更多
With N-vinyl-2-pyrrolidone (NVP) and itaconic acid(IA), poly(N-vinyl-2-pyrrolidone/itaconic acid)[P(NVP/IA)] hydrogel was synthesized by free radical solution polymerization. The structure of this (P(NVP/IA)) was char...With N-vinyl-2-pyrrolidone (NVP) and itaconic acid(IA), poly(N-vinyl-2-pyrrolidone/itaconic acid)[P(NVP/IA)] hydrogel was synthesized by free radical solution polymerization. The structure of this (P(NVP/IA)) was characterized by IR. Effects of concentration of itaconic acid, amount of cross-link agent, N,N′-methylene-bis-acrylamide, reaction temperature, and time on properties of swelling ratio(SR) of the hydrogel were investigated.The results show that the best swelling property of the hydrogel is obtained at 50 ℃ and 1.5 h. pH sensitivity increases as the concentration of itaconic acid in the hydrogel system increases. Swelling ratio of the hydrogel decreases as the amount of cross-link agent increases.展开更多
An improved process of hydrolysis of corn starch was adopted in the production of itaconic acid （IA）, the aim was to decrease the unfermentable reducing sugar （RS） in the medium from the beginning of the fermentat...An improved process of hydrolysis of corn starch was adopted in the production of itaconic acid （IA）, the aim was to decrease the unfermentable reducing sugar （RS） in the medium from the beginning of the fermentation and to increase the crystallization efficiency of IA from the fermentation broth. The glucose （GS） syrups saccharified by several combinations of glucoamylase and pullulanase were investigated and used as the carbohydrate source of the fermentation medium for the spore-initiated submerged fermentations experiments. Compared with the conventional process （with pullulanase controlled）, the improved process decreased th.e RS residue in the fermentation broth from 3.01g/L to 1.35g/L and from 4.25g/L to 3.25g/L when the original RS of the medium were 100 and 120g/L, respectively. The crystallization efficiency of IA increased from 65% to 78.8% and from 69.58% to 82.81% with the original RS being 100 and 120g/L, respectively.展开更多
Itaconic acid is commercially produced by the cultivation of Aspergillus terreus using starch hydrolysate as carbon source. The degree of hydrolysis had a great influence on itaconic acid production which was suitable...Itaconic acid is commercially produced by the cultivation of Aspergillus terreus using starch hydrolysate as carbon source. The degree of hydrolysis had a great influence on itaconic acid production which was suitable when corn starch was saccharified at 35 DE. The α-amylase was sufficient to drive the starch hydrolysis to the degree. The agar plate assay with LiCl treatment provided a rapid, simple and unequivocal method for screening large numbers of colonies for itaconic acid producing strains. It was learned by experience that the strains on the plates with thick hyphae and light-colored spores often accompanied high itaconic acid production. A strain, designated Ast165, producing itaconic acid with a high yield, was successfully obtained by directional breeding of metabolic end products resistant strains. The itaconic acid concentration produced by Ast165 was 53.8 g/l from 100 g/l of starch hydrolysate in shake flasks. The conversion rate was 61.3%, which was the highest value found in tests.展开更多
Functionalized polypropylene with acryl amide (AAm) and itaconic acid (IA) were prepared in the molten state in the presence of dicumyl peroxide. The effects of the concentration of both mono- mers on the degree of fu...Functionalized polypropylene with acryl amide (AAm) and itaconic acid (IA) were prepared in the molten state in the presence of dicumyl peroxide. The effects of the concentration of both mono- mers on the degree of functionalization and properties of the products were investigated by FT-IR, contact angle measurement and DSC analysis. It was found that the degree of functionalization depends on the initial concentration of both monomers that used in the reaction. The influence of the AAm and IA content on the melting and crystallization temperature of PP was investigated by DSC. The contact angle of water on film surfaces of the functionalized PP (PP-g-AAm and PP-g-IA) decreased with increasing modified polymer content. From FT-IR spectra of functionalized PP a calculation was made of carbonyl index on the films surfaces. It was found that the higher intensity of the carbonyl index, the lower contact angle value and the lower crystallinity confirmed the ex- istence of functionalized AAm and/or IA in PP. It was concluded from the different characteriza- tion methods that the polarity and percentage of functionalized PP were increased up to 3 phr for both monomers, and then it was decreased by increasing the amount of monomers and had a threshold value, due to nucleating agents of monomers in PP.展开更多
A phosphorus-containing bio-based epoxy resin(EADI)was synthesized from itaconic acid(IA)and 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide(DOPO).As a matrix,its cured epoxy network with methyl hexahydrophthalic a...A phosphorus-containing bio-based epoxy resin(EADI)was synthesized from itaconic acid(IA)and 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide(DOPO).As a matrix,its cured epoxy network with methyl hexahydrophthalic anhydride(MHHPA)as the curing agent showed comparable glass-transition temperature and mechanical properties to diglycidyl ether in a bisphenol A(DGEBA)system as well as good flame retardancy with UL94 V-0 grade during a vertical burning test.As a reactive flame retardant,its flame-resistant effect on DGEBA/MHHPA system as well as its influence on the curing behavior and the thermal and mechanical properties of the modified epoxy resin were investigated.Results showed that after the introduction of EADI,not only were the flame retardancy determined by vertical burning test,LOI measurement,and thermogravimetric analysis significantly improved,but also the curing reactivity,glass transition temperature(T g),initial degradation temperature for 5%weight loss(T d(5%)),and flexural modulus of the cured system improved as well.EADI has great potential to be used as a green flame retardant in epoxy resin systems.展开更多
Itaconic acid(ITA),an effective alternative fossil fuel,derives from the bypass pathway of the tricarboxylic acid(TCA)cycle.Therefore,the imbalance of metabolic flux between TCA cycle and ITA biosynthetic pathway seri...Itaconic acid(ITA),an effective alternative fossil fuel,derives from the bypass pathway of the tricarboxylic acid(TCA)cycle.Therefore,the imbalance of metabolic flux between TCA cycle and ITA biosynthetic pathway seriously limits the production of ITA.The optimization of flux distribution between biomass and production has the potential to the productivity of ITA.Based on the previously constructed strain Escherichia coli MG1655Δ1-SAS-3(ITA titer:1.87 g/L),a CRISPRi-mediated self-inducible system(CiMS),which contained a responsive module based on the ITA biosensor YpItcR/Pccl and a regulative CRISPRi-mediated interferential module,was developed to regulate the flux of the TCA cycle and to enhance the capacity of the strain to produce ITA.First,a higher ITA-yielding strain,Δ4-Prmd-SAS-3(ITA titer:3.20 g/L),derived fromΔ1-SAS-3,was constructed by replacing the promoter PJ23100,for the expression of ITA synthesis genes,with Prmd and knocking out the three bypass genes poxB,pflB,and ldhA.Subsequently,the CiMS was used to inhibit the expression of key genes icd,pykA,and sucCD to dynamically balance the metabolic flux between TCA cycle and ITA biosynthetic pathway during the ITA production stage.The constructed strainΔ4-Prmd-SAS-3 under the dynamic regulation of the CiMS,showed a 23%increase in the ITA titer,which reached 3.93 g/L.This study indicated that CiMS was a practical strategy to dynamically and precisely regulated the metabolic flux in microbial cell factories.展开更多
Itaconic acid(IA)is a precursor of various chemicals,which has been on the US Department of Energy’s list of the top 12 platform chemicals that can potentially be produced from biomass.The IA is mainly produced throu...Itaconic acid(IA)is a precursor of various chemicals,which has been on the US Department of Energy’s list of the top 12 platform chemicals that can potentially be produced from biomass.The IA is mainly produced through a bio-fermentation method with sugar as raw material.However,the high cost and low yield restrict the industrial application of the IA.This review summarized research advances in the IA production from alternative substrates.In particular,the types of substrates as well as existing problems in the IA fermentation,strain breeding,and process regulation were discussed.And it is pointed that decreasing the price of the IA through use of alternative substrates and increasing the titer of the IA through genetic engineering should be further focused on to support the industrialization of the IA.展开更多
The Crabtree effect products ethanol and acetic acid can be used for itaconic acid(IA)production in Saccharomyces cerevisiae.However,both the IA synthesis and oxidative phosphorylation pathways were hampered by glucos...The Crabtree effect products ethanol and acetic acid can be used for itaconic acid(IA)production in Saccharomyces cerevisiae.However,both the IA synthesis and oxidative phosphorylation pathways were hampered by glucose repression when glucose was used as the substrate.This study aimed to improve IA titer by increasing gene expressions related to glucose derepression without impairing yeast growth on glucose.Engineering the acetyl-CoA synthesis pathway increased the titer of IA to 257 mg/L in a urea-based medium.Instead of entire pathway overexpression,we found that some signaling pathways regulating glucose repression were effective targets to improve IA production and respiratory capacity.As a consequence of the reduced inhibition,IA titer was further increased by knocking out a negative regulator of the mitochondrial retrograde signaling MKS1.SNF1/MIG1 signaling was disturbed by deleting the hexokinase HXK2 or an endoplasmic reticulum membrane protein GSF2.The shaking results showed that XYY286(BY4741,HO::cadA,Y::Dz.ada,208a::Mt.acs,Δhxk2,pRS415-cadA,pRS423-aac2)accumulated 535 mg/L IA in 168 h in the YSCGLU medium.qRT-PCR results verified that deletion of MKS1 or HXK2 upregulated the gene expressions of the IA synthesis and respiratory pathways during the growth on glucose.展开更多
Itaconate,a macrophage-specific anti-inflammatory metabolite,has recently emerged as a critical regulator in rheumatoid arthritis pathogenesis.We found that itaconate is a TNF-αresponsive metabolite significantly ele...Itaconate,a macrophage-specific anti-inflammatory metabolite,has recently emerged as a critical regulator in rheumatoid arthritis pathogenesis.We found that itaconate is a TNF-αresponsive metabolite significantly elevated in the serum and synovial fluid of rheumatoid arthritis patients and we demonstrated that itaconate is primarily produced by inflammatory macrophages rather than osteoclasts or osteoblasts.In TNF-transgenic and Irg1−/−hybrid mice,a more severe bone destruction phenotype was observed.展开更多
Itaconate(ITA),an immunomodulatory metabolite with known anti-inflammatory properties,has underexplored therapeutic or prophylactic potential against coronavirus disease 2019(COVID-19).Using an interanimal transmissio...Itaconate(ITA),an immunomodulatory metabolite with known anti-inflammatory properties,has underexplored therapeutic or prophylactic potential against coronavirus disease 2019(COVID-19).Using an interanimal transmission golden hamster model of severe acute respiratory syndrome coronavirus 2(SARS-CoV-2)-induced acute lung injury,we first assessed ITA changes in dNS1-RBD-vaccinated hamsters via metabolomic profiling.Then,we evaluated prophylactic intranasal(20 mg/kg at 9,6,and 3 days before SARS-CoV-2 infection)and therapeutic intraperitoneal(100 mg/kg at 6,24,and 48 hours post-infection)ITA administration,assessed by histopathology,transcriptomic,and metabolomic profiling,followed by multi-omics integration,including gene expression clustering,pathway enrichment,and cytokine/chemokine–metabolites correlation analyses.Public bronchoalveolar lavage fluid(BALF)single-cell RNA-sequencing(scRNA-seq)datasets from COVID-19 patients were re-analyzed to explore macrophage heterogeneity.Intranasal dNS1-RBD vaccine upregulated ITA levels,prompting further exploration of its immunomodulatory role.Both prophylactic and therapeutic ITA treatments significantly mitigated weight loss and improved lung pathology.Correlation analyses implied a potential regulatory crosstalk between fatty acid b-oxidation(FAO)and reduced inflammatory response.Reanalysis of BALF scRNA-seq dataset highlighted transcriptional networks involving PPARG,RARA,BHLHE41,TCF7L2,and ESRRA—genes linked to macrophage self-renewal and metabolic homeostasis,which appeared to be preserved in ITA-treated hamsters.These findings underscore ITA’s role in modulating immunometabolic responses,particularly through FAO-driven macrophage reprogramming,to attenuate SARS-CoV-2-induced lung damage.Together,this study provides insights into host-directed therapies targeting metabolic reprogramming to mitigate COVID-19 severity.展开更多
Hydrocarbon-derived polymers have been utilized in various packaging applications, such as pouches, films, foamed containers, rigid containers, and multiple components for medical, food, and other uses. However, mount...Hydrocarbon-derived polymers have been utilized in various packaging applications, such as pouches, films, foamed containers, rigid containers, and multiple components for medical, food, and other uses. However, mounting environmental considerations increased knowledge of the harmful consequences of greenhouse gas emissions, landfills, and disposal difficulties. Rising oil prices are forcing researchers and businesses to produce environmentally friendly packaging. These new sustainability requirements are particularly suited to biomass-based products, instead of petroleum sources;sourced from biomass entities. More functional and performance-oriented packaging is necessary despite the widespread usage of bio-based materials like paper. As a result, the transition to eco-friendly packaging will necessitate the improvement of existing bio-derived packaging and the development of new bio-derived materials like biopolymer paper coatings. The goal of this brief study was to give a synopsis of the present status of bio-derived packaging and an insight into ongoing and prospective developments in sustainable next-generation paper coatings for the packaging industry.展开更多
基金supported by the Natural Science Foundation of Shandong Province(No.ZR2022MB034)。
文摘Functional materials synthesized from bio-based building blocks are fascinating and challenging in the fields of chemistry and materials science.Herein,we present a versatile strategy for synthesizing bio-based stimulus-responsive polymers derived from itaconic acid(IA).Bearing an azobenzene-containing side chain,the IA-based epoxy polymer exhibited both photoresponsiveness and acid/base-stimulus responsiveness.With controllable manipulation of the stress field of the wrinkling IA-polymer film via the stress relaxation effect resulting from the reversible cis-trans isomerization of the azobenzene moieties or solvent-induced swelling of the film,various tailor-made patterned wrinkling surfaces were conveniently fabricated.More importantly,the azobenzene protonation/deprotonation yields a reversible visual color transformation between pale yellow and purple in the film,which allows these IA-based polymer-coated surfaces to be utilized as rewritable information storage media.Various elegant pattern information can be acid-printed and base-erased(within 10 s)for multiple cycles and legible for over one day under laboratory conditions.Notably,the aforementioned dual-stimulus responsiveness of the IA-based polymer film enables its surface to be applied in information encryption.This study not only paves a new avenue for the convenient fabrication of stimulus-responsive surfaces but also sheds light on the development of functional polymers through green engineering.
基金financially supported by the National Natural Science Foundation of China(No.52377025)。
文摘The most widely used bisphenol A-type epoxy resin(DGEBA)in electrical engineering demonstrates excellent mechanical and electrical properties.However,the insoluble and infusible characteristics of cured DGEBA make it difficult to efficiently degrade and recycle decommissioned electrical equipment.In this study,a degradable itaconic acid-based epoxy resin incorporating dynamic covalent bonds was prepared through the integration of ester bonds and disulfide bonds,with itaconic acid as the precursor.The covalent bonding effects on the mechanical,thermal,electrical,and degradation characteristics were systematically evaluated.The experimental results revealed that the introduction of dynamic ester bonds enhanced the mechanical properties and thermal stability of the resin system,achieving a flexural strength of 141.57 MPa and an initial decomposition temperature T_(5%)of up to 344.9℃.The resin system containing dynamic disulfide bonds exhibited a dielectric breakdown strength of 41.11 k V/mm.Simultaneously,the incorporation of disulfide bonds endowed the epoxy resin with remarkable degradability,enabling complete dissolution within 1.5 h at 90℃ in a mixed solution of dithiothreitol(DTT)and N-methylpyrrolidone(NMP).This research provides a valuable reference for the application of itaconic acid-based vitrimer with dynamic covalent bonds in electrical materials,contributing to the development and utilization of environmentally friendly electrical equipment.
基金supported by the National Natural Science Foundation of China(Grant No.21978066)Basic Research Program of Hebei Province for Natural Science Foundation and Key Basic Research Project(Grant No.18964308D)the Key Program of Natural Science Foundation of Hebei Province(Grant No.B2020202048).
文摘Methacrylic acid,an important organic chemical,is commercially manufactured starting from fossil feedstock.The decarboxylation of itaconic acid derived for biomass is a green route to the synthesis of methacrylic acid.In view of the problems existing in the researches on this route such as use of noble metal catalyst,harsh reaction conditions and low desired-product yield,we prepared a series of hydroxyapatite catalysts with different Ca/P molar ratios and evaluated their catalytic performance.The results showed that the hydroxyapatite catalyst with a Ca/P molar ratio of 1.58 had the best catalytic activity.The highest yield of MAA up to 61.2%was achieved with basically complete conversion of itaconic acid under the suitable reaction conditions of 1 equivalent of NaOH,2 MPa of N_(2),250℃,and 2 h.On this basis,a reaction network for the decarboxylation of itaconic acid to methacrylic acid catalyzed by hydroxyapatite was established.With the aid of catalyst characterization using X-ray powder diffraction,NH3/CO2 temperature-programmed desorption,N_(2)physisorption,inductively coupled plasma optical emission spectrometry,and scanning electron microscopy,we found that the distribution of surface acid sites and basic sites,crystal growth orientation,texture properties and morphology of hydroxyapatite varied with the Ca/P molar ratio.Furthermore,the change of the crystal growth orientation and its influence on the surface acidity and alkalinity were clarified.
基金supported by National Natural Science Foundation of China(21978066)Basic Research Program of Hebei Province for Natural Science Foundation and Key Basic Research Project(18964308D)the Key Program of Natural Science Foundation of Hebei Province(B2020202048).
文摘The synthesis of methacrylic acid from biomass-derived itaconic acid is a green route,for it can get rid of the dependence on fossil resource.In order to solve the problems on this route such as use of a preciousmetal catalyst and a corrosive homogeneous alkali,we prepared a series of hydroxyapatite catalysts by an ionic liquid-assisted hydrothermal method and evaluated their catalytic performance.The results showed that the ionic liquid[Bmim]BF_(4) can affect the crystal growth of hydroxyapatite,provide fluoride ion for fluorination of hydroxyapatite,and adjust the surface acidity and basicity,morphology,textural properties,crystallinity,and composition of hydroxyapatite.The[Bmim]BF4 dosage and hydrothermal temperature can affect the fluoride ion concentration in the hydrothermal system,thus changing the degree of fluoridation of hydroxyapatite.High fluoride-ion concentration can lead to the formation of CaF_(2) and thus significantly decrease the catalytic performance of hydroxyapatite.The hydrothermal time mainly affects the growth of hydroxyapatite crystals on the c axis,leading to different catalytic performance.The suitable conditions for the preparation of this fluoridized hydroxyapatite are as follows:a mass ratio of[Bmim]BF4 to calcium salt=0.2:1,a hydrothermal time of 12 h,and a hydrothermal temperature of 130℃.A maximal methacrylic acid yield of 54.7%was obtained using the fluoridized hydroxyapatite under relatively mild reaction conditions(250℃ and 2 MPa of N_(2))in the absence of a precious-metal catalyst and a corrosive homogeneous alkali.
文摘The terpolymer of itaconic acid, acrylamide and 2-acrylamido-2-methyl-1-propane sulfonic acid was synthesized through the free-radical polymerization. The IR spectra confirmed that there was no olefinic band, while the TGA results revealed that the terpolymer was of high thermal stability.
文摘The reaction mechanism of IA/MA copolymer system andcotton cellulose is conjectured and verified, the two keysteps, such as the formation of cyclic anhydride interme-diates and the building of ester crosslinklng, and the ef-fect of sodium hypophosphite are especially emphasized,by FT - IR spectroscopy and acid- base titration anal-yses. The experiments reveal that carboxylic acids main.ly change to cyclic anhydride in the pre - drying step andSodium Hypophosphite (SHP) has effect on it, but mostester - crosslinkages are built in the curing step and SHPhas effects on both anhydride formation and ester -crosslinking formation.
基金Shanghaimunicipalscienceandtechnologydevelopmentfund (No .0 113110 15 )andShanghaimunicipalkeydisciplineproject
文摘Cotton fabric samples are padded with maleic acid (MA) and itaconic acid (IA) finishing bath in the presence of potassium persulfate (K 2S 2O 8), and then dried at different temperatures for different time intervals. The portion of unreacted monomers on cotton fabric samples is determined by means of measuring the double bond content. The kinetic data (rate constants, Arrhenius activation energy, frequency factor) of the in-situ polymerization have been calculated.
基金supported financially from the National Natural Science Foundation of China (Grant No. 51308211)the State Key Laboratory of Urban Water Resource and Environment (HIT) (Grant No. ES200903)the Fundamental Research Funds for the Central Universities (Grant No. 2015MS63)
文摘Poly(aspartic acid-itaconic acid) copolymer was synthesized from aspartic acid(Asp) and itaconic acid(Ita) under microwave irradiation. The effects of microwave power, microwave irradiation time, molar ratio of itaconic acid and aspartic acid, catalyst type, catalyst and organic solvent content on copolymer yield, and the performance for inhibition of CaCO_3 fouling were investigated. It was found that the product yield achieved a highest record of 95% when the amount of catalyst Na H_2PO_4 was 0.012 mol, the amount of organic solvent propylene carbonate was 16 m L, the molar ratio of Asp/Ita was 3:1, the microwave output power was 1200 W and the irradiation time was 5.5 min. And the product performance for inhibition of calcium carbonate also reached a highest value of 94.38%. Structural characterization of the product showed that the product was the aspartic acid-itaconic acid copolymer.
文摘With N-vinyl-2-pyrrolidone (NVP) and itaconic acid(IA), poly(N-vinyl-2-pyrrolidone/itaconic acid)[P(NVP/IA)] hydrogel was synthesized by free radical solution polymerization. The structure of this (P(NVP/IA)) was characterized by IR. Effects of concentration of itaconic acid, amount of cross-link agent, N,N′-methylene-bis-acrylamide, reaction temperature, and time on properties of swelling ratio(SR) of the hydrogel were investigated.The results show that the best swelling property of the hydrogel is obtained at 50 ℃ and 1.5 h. pH sensitivity increases as the concentration of itaconic acid in the hydrogel system increases. Swelling ratio of the hydrogel decreases as the amount of cross-link agent increases.
基金the National Natural Science Foundatioo of China(No.30670566)the International S&T Cooperation Program of China(No.2006DFA33150)
文摘An improved process of hydrolysis of corn starch was adopted in the production of itaconic acid （IA）, the aim was to decrease the unfermentable reducing sugar （RS） in the medium from the beginning of the fermentation and to increase the crystallization efficiency of IA from the fermentation broth. The glucose （GS） syrups saccharified by several combinations of glucoamylase and pullulanase were investigated and used as the carbohydrate source of the fermentation medium for the spore-initiated submerged fermentations experiments. Compared with the conventional process （with pullulanase controlled）, the improved process decreased th.e RS residue in the fermentation broth from 3.01g/L to 1.35g/L and from 4.25g/L to 3.25g/L when the original RS of the medium were 100 and 120g/L, respectively. The crystallization efficiency of IA increased from 65% to 78.8% and from 69.58% to 82.81% with the original RS being 100 and 120g/L, respectively.
文摘Itaconic acid is commercially produced by the cultivation of Aspergillus terreus using starch hydrolysate as carbon source. The degree of hydrolysis had a great influence on itaconic acid production which was suitable when corn starch was saccharified at 35 DE. The α-amylase was sufficient to drive the starch hydrolysis to the degree. The agar plate assay with LiCl treatment provided a rapid, simple and unequivocal method for screening large numbers of colonies for itaconic acid producing strains. It was learned by experience that the strains on the plates with thick hyphae and light-colored spores often accompanied high itaconic acid production. A strain, designated Ast165, producing itaconic acid with a high yield, was successfully obtained by directional breeding of metabolic end products resistant strains. The itaconic acid concentration produced by Ast165 was 53.8 g/l from 100 g/l of starch hydrolysate in shake flasks. The conversion rate was 61.3%, which was the highest value found in tests.
文摘Functionalized polypropylene with acryl amide (AAm) and itaconic acid (IA) were prepared in the molten state in the presence of dicumyl peroxide. The effects of the concentration of both mono- mers on the degree of functionalization and properties of the products were investigated by FT-IR, contact angle measurement and DSC analysis. It was found that the degree of functionalization depends on the initial concentration of both monomers that used in the reaction. The influence of the AAm and IA content on the melting and crystallization temperature of PP was investigated by DSC. The contact angle of water on film surfaces of the functionalized PP (PP-g-AAm and PP-g-IA) decreased with increasing modified polymer content. From FT-IR spectra of functionalized PP a calculation was made of carbonyl index on the films surfaces. It was found that the higher intensity of the carbonyl index, the lower contact angle value and the lower crystallinity confirmed the ex- istence of functionalized AAm and/or IA in PP. It was concluded from the different characteriza- tion methods that the polarity and percentage of functionalized PP were increased up to 3 phr for both monomers, and then it was decreased by increasing the amount of monomers and had a threshold value, due to nucleating agents of monomers in PP.
基金financially supported by the National Natural Science Foundation of China(51203176)the National Basic Research Program of China(2010CB631100)+3 种基金the Natural Science Foundation of Ningbo(2012A610095)the China Postdoctoral Science Foundation(2013M-540504)the Postdoctoral Science Foundation of Zhejiang Province(Bsh1201011)the Director Funds of the Ningbo Institute of Materials Technology and Engineering,Chinese Academy of Sciences(Y20224-QF06)
文摘A phosphorus-containing bio-based epoxy resin(EADI)was synthesized from itaconic acid(IA)and 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide(DOPO).As a matrix,its cured epoxy network with methyl hexahydrophthalic anhydride(MHHPA)as the curing agent showed comparable glass-transition temperature and mechanical properties to diglycidyl ether in a bisphenol A(DGEBA)system as well as good flame retardancy with UL94 V-0 grade during a vertical burning test.As a reactive flame retardant,its flame-resistant effect on DGEBA/MHHPA system as well as its influence on the curing behavior and the thermal and mechanical properties of the modified epoxy resin were investigated.Results showed that after the introduction of EADI,not only were the flame retardancy determined by vertical burning test,LOI measurement,and thermogravimetric analysis significantly improved,but also the curing reactivity,glass transition temperature(T g),initial degradation temperature for 5%weight loss(T d(5%)),and flexural modulus of the cured system improved as well.EADI has great potential to be used as a green flame retardant in epoxy resin systems.
基金supported by the National Natural Science Foundation of China(No.21778018)Research Program of State Key Laboratory of Bioreactor Engineering and the grant from the National Key Research and Development Program of China(2021YFC2100300)the Chinese Plastic Surgery Foundation(No.2020M671021).
文摘Itaconic acid(ITA),an effective alternative fossil fuel,derives from the bypass pathway of the tricarboxylic acid(TCA)cycle.Therefore,the imbalance of metabolic flux between TCA cycle and ITA biosynthetic pathway seriously limits the production of ITA.The optimization of flux distribution between biomass and production has the potential to the productivity of ITA.Based on the previously constructed strain Escherichia coli MG1655Δ1-SAS-3(ITA titer:1.87 g/L),a CRISPRi-mediated self-inducible system(CiMS),which contained a responsive module based on the ITA biosensor YpItcR/Pccl and a regulative CRISPRi-mediated interferential module,was developed to regulate the flux of the TCA cycle and to enhance the capacity of the strain to produce ITA.First,a higher ITA-yielding strain,Δ4-Prmd-SAS-3(ITA titer:3.20 g/L),derived fromΔ1-SAS-3,was constructed by replacing the promoter PJ23100,for the expression of ITA synthesis genes,with Prmd and knocking out the three bypass genes poxB,pflB,and ldhA.Subsequently,the CiMS was used to inhibit the expression of key genes icd,pykA,and sucCD to dynamically balance the metabolic flux between TCA cycle and ITA biosynthetic pathway during the ITA production stage.The constructed strainΔ4-Prmd-SAS-3 under the dynamic regulation of the CiMS,showed a 23%increase in the ITA titer,which reached 3.93 g/L.This study indicated that CiMS was a practical strategy to dynamically and precisely regulated the metabolic flux in microbial cell factories.
基金Natural Science Foundation of Jiangsu Province of China(No.BK20160150).
文摘Itaconic acid(IA)is a precursor of various chemicals,which has been on the US Department of Energy’s list of the top 12 platform chemicals that can potentially be produced from biomass.The IA is mainly produced through a bio-fermentation method with sugar as raw material.However,the high cost and low yield restrict the industrial application of the IA.This review summarized research advances in the IA production from alternative substrates.In particular,the types of substrates as well as existing problems in the IA fermentation,strain breeding,and process regulation were discussed.And it is pointed that decreasing the price of the IA through use of alternative substrates and increasing the titer of the IA through genetic engineering should be further focused on to support the industrialization of the IA.
基金Support for this study was provided by the China National Key Research and Development Program [2019YFA0904300].
文摘The Crabtree effect products ethanol and acetic acid can be used for itaconic acid(IA)production in Saccharomyces cerevisiae.However,both the IA synthesis and oxidative phosphorylation pathways were hampered by glucose repression when glucose was used as the substrate.This study aimed to improve IA titer by increasing gene expressions related to glucose derepression without impairing yeast growth on glucose.Engineering the acetyl-CoA synthesis pathway increased the titer of IA to 257 mg/L in a urea-based medium.Instead of entire pathway overexpression,we found that some signaling pathways regulating glucose repression were effective targets to improve IA production and respiratory capacity.As a consequence of the reduced inhibition,IA titer was further increased by knocking out a negative regulator of the mitochondrial retrograde signaling MKS1.SNF1/MIG1 signaling was disturbed by deleting the hexokinase HXK2 or an endoplasmic reticulum membrane protein GSF2.The shaking results showed that XYY286(BY4741,HO::cadA,Y::Dz.ada,208a::Mt.acs,Δhxk2,pRS415-cadA,pRS423-aac2)accumulated 535 mg/L IA in 168 h in the YSCGLU medium.qRT-PCR results verified that deletion of MKS1 or HXK2 upregulated the gene expressions of the IA synthesis and respiratory pathways during the growth on glucose.
基金supported by the National Natural Science Foundation of China(NSFC)(No.82130073,No.82372430,No.31871431,No.31821002,No.32101011,No.22177073)Shanghai Frontiers Science Center of Degeneration and Regeneration in Skeletal System+3 种基金Shanghai Science and Technology Committee(No.23ZR1437600,No.24410710600,No.24141901302)Shenzhen Medical Research Fund(No.B2302005)The Open Project Funding of Shanghai Key Laboratory of Orthopedics(No.KFKT202201)Biomaterials and Regenerative Medicine Institute Cooperative,Research Project,Shanghai Jiao Tong University School of Medicine(No.2022LHA01).
文摘Itaconate,a macrophage-specific anti-inflammatory metabolite,has recently emerged as a critical regulator in rheumatoid arthritis pathogenesis.We found that itaconate is a TNF-αresponsive metabolite significantly elevated in the serum and synovial fluid of rheumatoid arthritis patients and we demonstrated that itaconate is primarily produced by inflammatory macrophages rather than osteoclasts or osteoblasts.In TNF-transgenic and Irg1−/−hybrid mice,a more severe bone destruction phenotype was observed.
基金funded by the National Natural Science Foun-dation of China(grant numbers 82322027 to T.Z.,82341043 to T.Z.,and 92369108 to J.Z.)the National Key Research and Development Program of China(grant number 2023YFC2307602 to J.Z.)+1 种基金the Natural Science Foundation of Beijing Municipal(grant number L234007 to T.Z.)the Fundamental Research Funds for the Central Universities(grant number 20720220003 to N.X.).
文摘Itaconate(ITA),an immunomodulatory metabolite with known anti-inflammatory properties,has underexplored therapeutic or prophylactic potential against coronavirus disease 2019(COVID-19).Using an interanimal transmission golden hamster model of severe acute respiratory syndrome coronavirus 2(SARS-CoV-2)-induced acute lung injury,we first assessed ITA changes in dNS1-RBD-vaccinated hamsters via metabolomic profiling.Then,we evaluated prophylactic intranasal(20 mg/kg at 9,6,and 3 days before SARS-CoV-2 infection)and therapeutic intraperitoneal(100 mg/kg at 6,24,and 48 hours post-infection)ITA administration,assessed by histopathology,transcriptomic,and metabolomic profiling,followed by multi-omics integration,including gene expression clustering,pathway enrichment,and cytokine/chemokine–metabolites correlation analyses.Public bronchoalveolar lavage fluid(BALF)single-cell RNA-sequencing(scRNA-seq)datasets from COVID-19 patients were re-analyzed to explore macrophage heterogeneity.Intranasal dNS1-RBD vaccine upregulated ITA levels,prompting further exploration of its immunomodulatory role.Both prophylactic and therapeutic ITA treatments significantly mitigated weight loss and improved lung pathology.Correlation analyses implied a potential regulatory crosstalk between fatty acid b-oxidation(FAO)and reduced inflammatory response.Reanalysis of BALF scRNA-seq dataset highlighted transcriptional networks involving PPARG,RARA,BHLHE41,TCF7L2,and ESRRA—genes linked to macrophage self-renewal and metabolic homeostasis,which appeared to be preserved in ITA-treated hamsters.These findings underscore ITA’s role in modulating immunometabolic responses,particularly through FAO-driven macrophage reprogramming,to attenuate SARS-CoV-2-induced lung damage.Together,this study provides insights into host-directed therapies targeting metabolic reprogramming to mitigate COVID-19 severity.
文摘Hydrocarbon-derived polymers have been utilized in various packaging applications, such as pouches, films, foamed containers, rigid containers, and multiple components for medical, food, and other uses. However, mounting environmental considerations increased knowledge of the harmful consequences of greenhouse gas emissions, landfills, and disposal difficulties. Rising oil prices are forcing researchers and businesses to produce environmentally friendly packaging. These new sustainability requirements are particularly suited to biomass-based products, instead of petroleum sources;sourced from biomass entities. More functional and performance-oriented packaging is necessary despite the widespread usage of bio-based materials like paper. As a result, the transition to eco-friendly packaging will necessitate the improvement of existing bio-derived packaging and the development of new bio-derived materials like biopolymer paper coatings. The goal of this brief study was to give a synopsis of the present status of bio-derived packaging and an insight into ongoing and prospective developments in sustainable next-generation paper coatings for the packaging industry.
