Itaconic Anhydride Research Articles

Significantly Red-Shifted Emissions of Nonconventional AIE Polymers Containing Zwitterionic Components.

Nonconventional luminescence polymers without any aromatic structures have attracted great interest from researchers due to their special structure and excellent biocompatibility. However, these materials mostly emit in the blue or green region, in which preparation of materials with long-wavelength (especially near-infrared) emission is still a great challenge. In this work, it is found that 2-(dimethyl amino) ethyl methacrylate (DMA) and itaconic anhydride (ITA) undergo a ring-opening reaction at room temperature, and subsequently generate zwitterionic compound (IDMA). Based on the clustering-triggered emission (CTE) mechanism, ionic bond can effectively promote the isolated electron-rich chromophores to form new emissive clusters with extended electron delocalization. Herein, two oligomers (P1 and P2) with different fluorescence emissions by controlling the concentration of zwitterionic monomers before polymerization are synthesized. It is worth noting that the maximum emission wavelength of P2 at high concentration is up to 712 nm, which is very rare in previous reports. In addition, the resulting oligomer (P2) shows typical aggregation-enhanced emission (AEE), excitation-dependent fluorescence, temperature-sensitive emission, and solvatochromism. The cytotoxicity assay demonstrates that P2 was low toxic to Huh7 and LM3 cells, and suitable for cell imaging. This research provides the possibility for rational molecular design and the feasibility of luminescence regulation.

Polyesters based on aspartic acid and poly(ethylene glycol): Functional polymers for hydrogel preparation

Hydrogels are commonly used as scaffolds for the preparation of three-dimensional tissue constructs and for the encapsulation and delivery of cells in regenerative medicine. Polyesters are an attractive class of polymers for hydrogel preparation. However, most polyesters have hydrophobic backbones and lack pendent groups that can be chemically functionalized. We describe here the development of water-soluble polyesters based on aspartic acid and poly(ethylene glycol) (PEG) (600 or 1500 g/mol), having pendent reactive amines. The reactivity of these amines with methacrylic anhydride, maleic anhydride, and itaconic anhydride was explored for the introduction of crosslinkable groups. The resulting methacrylamide-functionalized polymers were successfully crosslinked to form hydrogels using a redox-initiated free radical polymerization. The use of 10% (weight/volume) of polymer, and 10 mM of potassium persulfate and tetramethylethylenediamine led to high (>97%) gel content, and compressive moduli of 13–21 kPa. Human adipose-derived stromal cells were encapsulated during the crosslinking process and exhibited greater than 80% viability in the hydrogels prepared from the polyester containing 600 g/mol PEG, with lower viability observed for the polymer containing 1500 g/mol PEG. These results support the potential for aspartic acid-based copolymers with short PEG chains in the backbone to serve as a platform for cell encapsulation, with additional opportunities for further functionalization available in the future.

Improving the adhesion-to-fibers and film properties of corn starch by starch sulfo-itaconation for a better application in warp sizing

The purpose of this work was to develop a new starch-based sizing agent [sulfo-itaconylated starch (SIS)] with high adhesion and film properties, through starch sulfo-itaconation containing itaconation of acid-hydrolyzed starch (AHS) with itaconic anhydride and subsequent sulfonation with NaHSO3 in aqueous medium. The granular SIS was characterized by Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM) techniques. The adhesion of SIS to cotton fibers was evaluated by a standard method (FZ/T 15001–2008). And its film properties were also investigated in terms of tensile strength, breaking elongation, moisture regain, bending endurance and degree of crystallinity, etc. The experimental results showed that the SIS samples had higher adhesion to cotton fibers and lower film brittleness than AHS as a control. Increasing the level of starch sulfo-itaconation could gradually enhance bonding strength to cotton fibers, and increase breaking elongation and bending endurance of SIS film, indicating that increasing the number of sulfo-itaconate substituents could play a significantly positive role in overcoming the shortcomings (insufficient adhesion and brittle film) of starch. Considering the previous results, the granular SIS with a modification level range of 0.034–0.041 showed potential for the use as a new starch-based sizing agent in paper-making and textile industry.

Anhydride Grafting on Carbon Nanotubes Using Ultrasound and its Effect on Polypropylene Nanocomposite Properties

ABSTRACT Polypropylene composites and multi-walled carbon nanotubes (MWCNTs) modified with maleic anhydride (MA) and itaconic anhydride (IA) were prepared and their effect on the performance of nanocomposite properties was studied. Modification of the MWCNT was carried out in the presence of ultrasound varying the molar ratio of anhydride and dicumyl peroxide (BPO). PP nanocomposite with anhydride grafted MWCNT showed an increase, higher than 15%, in tensile strength and elastic modulus and a displacement of crystallization temperature (Tc) to higher temperatures, 1.5°C and loss weight temperature to higher temperatures, 30°C. This behavior was attributed to the better anhydride grafting in the MWCNTs induced by ultrasound.

Modification of Starch Using Itaconic Anhydride and its Characterizations

In this study, the chemical modification of starch was conducted using itaconic anhydride as an esterifying agent. The results showed that sulphuric acid is more effective as a catalyst for esterification of starch compared to sodium hydroxide. The presence of attached itaconic anhyride in the starch affected the thermal behaviour and crystallinity of the resulting products as shown by the TGA, DSC, and the XRD data. In addition, the SEM micrographs also indicated that the modified starch exhibited a unique morphology in the form of block with different sizes ranging from 1 to 20 μm in length.

Degradable polyanhydride networks derived from itaconic acid

Tunable and degradable crosslinked-polyanhydride networks from renewably derived itaconic anhydrides and multifunctional thiols have been developed.

Carboxyl-functionalized hollow polymer microspheres for detection of trace metal elements in complex food matrixes by ICP-MS assisted with solid-phase extraction

In this work, carboxyl-functionalized hollow polymer microspheres (CHPMs) was successfully fabricated using poly (styrene-itaconic anhydride) particles as the core template and itaconic anhydride and trans-anethole cross-linked with divinylbenzene as the shell. The desirable microspheres and hollow structure of CHPMs were demonstrated by scanning and transmission electron microscopies, respectively. The characterized CHPMs as an adsorbent was packed into a solid phase extraction column to simultaneously detect the V(V), Cr(III), Cu(II), Cd(II), and Pb(II) in digested food samples by inductively coupled plasma-mass spectrometry (ICP-MS). A series of experimental parameters of solid-phase extraction (SPE) were investigated through vast experiments to improve sensitivity of the proposed method in metal ions detection. The detection limits of the method reached 0.8–3.2 ng L−1 for the target elements, and the relative standard deviations (RSDs) ranging from 1.2% to 3.5% were obtained from eleven parallel experiments using a 1.0 μg L−1 sample solution. The stability allowed the material to withstand more than 15 cycling while the recoveries remained above 88%. In food samples, the detection limits were at 0.20–0.80 μg kg−1, and satisfactory recoveries of 85–104% were obtained in spike tests of laver, fish as well as chicken.

Regio‐, enantio‐, peri‐, and stereo‐selectivities of the reactions of five‐membered cyclodiene derivatives with itaconic anhydride toward the formation of norbornene lactones

AbstractThe reactions of five‐membered cyclodiene derivatives with itaconic anhydride could proceed via four plausible pathways: two pathways involving initial Diels–Alder cycloaddition reactions followed by lactonization, and two pathways involving direct ring‐opening esterification reactions followed by intramolecular Diels–Alder cycloaddition, all to afford five‐ and six‐membered norbornene lactones, which are key intermediates in the synthesis of biologically interesting molecules as well as polymers such as polyelectrolytes. There are several regio‐, enantio‐, peri‐, and stereo‐chemical possibilities in these reactions, leading to several potential pathways, and these pathways are studied with density functional theory calculations in this work. The results reveal that the initial Diels–Alder reaction pathways have lower activation barriers than esterification reaction pathways. Generally, the activation barriers for the formation of S‐enantiomers are lower compared with the formation of R‐enantiomers. The reactions are stereo‐selective toward endo‐cycloadducts over exo‐cycloadducts, and this is as a result of steric interaction. The analysis of the electrophilic (Pk+) and nucleophilic (Pk−) Parr functions at the reactive centers shows that the cycloaddition will happen in such a way as to unite the atoms with the highest molecular orbital coefficients because this would lead to the greatest stabilization, and this is in good agreement with the energetic trends and the experimental outcome.

Investigations on the replacement of bismaleimide by the bio-based bisitaconimide for recyclable thermoset composites based on thermo-reversible Diels-Alder cross-links

Stimulated by the growing demand for more sustainable polymers, explorative experiments were performed to substitute oil-based components by “green” monomers derived from bio-based compounds to decrease the carbon footprint of the production of such thermosets. The potential of itaconimides synthesised from itaconic anhydride e.g. obtained by fermentation of carbohydrates or by pyrolysis of citric acid and as such easily accessible from inexpensive renewable raw materials for DA based epoxy materials as well as their action to achieve retro DA switching temperatures as low as 80 °C was explored. Composites were manufactured using this new resin and mechanically tested. The thermo-reversibility of the network makes the crosslinked materials re-mendable after a damaging event and ultimately recyclable. In such a way the sustainability of the material can be improved as well as by using bio-based starting materials, by elongation of the lifetime and by complete recyclability at the end of the lifetime.

Facile Fabrication of Biobased Hydrogel from Natural Resources: l-Cysteine, Itaconic Anhydride, and Chitosan

Synthesis of high-value materials from natural resources via a simple chemical route is highly desirable due to the renewability and economy of biomass. Herein, we report the facile fabrication of ...

Microwave-Assisted Synthesis of Cross-Linked Co-poly(itaconic anhydride-methyl methacrylate): The Effects of the Molar Ratio and Cross-Linking Agent on the Thermal Stability

In the present work, a new series of cross-linked copolymers based on itaconic anhydride and methyl methacrylate were prepared employing free radical copolymerization in the presence of azobisisobutyronitrile as an initiator and 2-butanone as a solvent under microwave irradiation. The copolymers containing itaconic anhydride (ITA) and methyl methacrylate (MMA) were chosen due to the formation of long-term stable anhydride moieties, which might be useful to attach enzymes covalently with numerous applications in water treatment. The copolymerization process was carried out in the presence of two types of cross-linking agent, namely, ethylene dimethacrylate (EDMA) and divinylbenzene (DVB) in a range of 0-20% (w/w) to explore their effect on the thermal and stiffness properties of the obtained cross-linked copolymers. Increasing the ratio of the cross-linking agent, the copolymers prefer to precipitate rather than form a gel during the polymerization process. While using ethylene dimethacrylate as a cross-linking agent, the copolymers change from porous to stiffness structures depending on the molar ratio of the monomers used during the polymerization. On the other hand, using divinylbenzene as a cross-linking agent, the stiffness structure was obtained in all cases and there is no effect observed for the monomer’s ratio or the percentage of cross-linking agent on the morphology of the prepared copolymers.

Probing toluene catalytic removal mechanism over supported Pt nano- and single-atom-catalyst

Commercial TiO2 supported 0.20 wt% Pt catalyst is obtained via the molten salt method, and both Pt nanoparticles and single atom Pt sites are observed. It exhibits high catalytic performance for toluene oxidation, with T50 and T90 being 173 and 183 °C, respectively. Reaction intermediates including benzene, p-xylene, o-xylene, benzaldehyde, phthalic acid, maleic anhydride, itaconic anhydride, acetone, and acetic acid, are detected during toluene oxidation. On this basis, likely toluene combustion reaction pathway is provided. Benzaldehyde is the most stable surface intermediate, and its oxidation can be rate-limiting for the entire toluene oxidation reaction. 2–10.0 vol% H2O slightly inhibits the reaction by competing surface sites with the reactant, while it does not poison the catalyst. 2.5–10.0 vol% CO2 slightly poisons the catalyst by surface carbonate formation, whereas 50 ppm SO2 severely poisons the catalyst by sulfite/sulfate formation.

Sodium itaconate grafted nanocellulose for facile elimination of lead ion from water

Nanocellulose from jute fiber was grafted with sodium itaconate through esterification with itaconic anhydride followed by replacement of surface protons with sodium ions. A tea-bag pouch containing sodium itaconate grafted nanocellulose (SINC) acted as a chemisorbant for lead ions through ion exchange when dipped in an aqueous solution. Surface morphology and surface modification of SINC were characterized by FTIR, SEM, EDX, TEM, AFM and BET N2 adsorption isotherm techniques. The effective diminution of lead ion concentration was ascertained by AAS and ICP-MS methods. The impact of operating parameters like residence time, temperature, ion concentration and pH on the chemisorption capability was evaluated. The kinetic data conformed to the intra particle diffusion model and pseudo second order reaction. The Freundlich model was found to be the best for describing isotherm equilibrium. The maximum chemisorption capacity (mg g−1) of SINC, nanocellulose itaconate and nanocellulose in aqueous solution for Pb2+ were found to be 85, 58 and 10 respectively at pH 5.5. The used SINC was easily regenerated via desorption of lead ion using NaCl. The regenerated SINC could be reused for four consecutive cycles with no loss of chemisorption efficiency. The SINC was also effective for removal of other metal ions such as chromium, cadmium and mercury. This is an easily synthesizable, adaptable and well-chemisorbing system with proven reusability. This could emerge as an economical alternative to the conventional cation exchange resins. Itaconic acid functionalization of nanocellulose resulted in a cation exchange resin with good chemisorption capability, regenerability and reusability in solution.

Sytnhesis of Organoboron Amide-Ester Branched Derivatives of Poly(Itaconic Anhydride-alt-2-Vinyl-1,3-Dioxolane) and Cancer Cells Interaction Studies

New organaboron amide-ester branched derivatives of poly(itaconic anhydride- alt -2-vinyl-1,3-dioxolane) are synthesized by amidolysis and grafting reactions, respectively. The structure and composition of the synthesized compounds are characterized by FTIR-ATR (Fourier Transform-Infrared-Attenuated Total Reflection) and 1 H ( 13 C) NMR (Nuclear Magnetic Resonance) spectroscopy. These novel functionalized boron containing biopolymers are interacted with HeLa (human cervix carcinoma cell) cancer cells and L929 Fibroblast ( normal) cells. Their anticancer properties are investigated using a combination of different biochemical analysis methods. It is found that both the values of the cytotoxicity and necrotic indexes are increased due to organoboron linkage but these indexes of organoboron amide-ester derivative are visibly decreased because of a -Hydroxy- ω - methoxypoly (ethylene oxide) (PEO) biocompatibilization. The results of these studies allow us to utilize PEO branched derivatives of synthesized organoboron copolymers (up to 200 µg mL -1 ) as therapeutic potential functional copolymer drugs in cancer chemotherapy and boron-neutron capture therapy (BNCT).

A renewable dynamic covalent network based on itaconic anhydride crosslinked polyglycerol: Adaptability, UV blocking and fluorescence

An adaptive dynamic covalent network with UV blocking and fluorescence is prepared by crosslinking hyperbranched polyglycerol (HPG) with itaconic anhydride (IA) via esterification. The abundant hydroxyl groups and ester linkages in the resulting polymer (HPG/IA) afford the dynamic transesterification at elevated temperatures and enable adaptive behaviors such as stress relaxation and reparability. Because the double bonds of IA are purposely reserved in the crosslinked network, the HPG/IA exhibits excellent UV blocking due to the strong UV absorption of the double bonds. HPG/IA also exhibits strong glass adherence. With a OH/anhydride ratio of 4/1, HPG/IA displays an adhesion shear strength to glass of ~30 kPa, which is explained by the flexible structure that ensures a good contact of the polymer film with glass and the high dielectric constant that favors accumulation of electrostatic charges. Interestingly, HPG/IA exhibits strong fluorescence (FL) under UV light, and the FL of HPG/IA exhibits strong selective quenching with respect to Fe3+. These unique properties make HPG/IA a promising functional material for UV blocking glass film and fluorescent Fe3+ sensor.

Aza-Annulation of 1,2,3,4-Tetrahydro-β-carboline Derived Enaminones and Nitroenamines: Synthesis of Functionalized Indolizino[8,7-b]indoles, Pyrido[1,2-a:3,4-b']diindoles, Indolo[2,3-a]quinolizidine-4-ones and Other Tetrahydro-β-carboline Fused Heterocycles.

Aza-annulation of novel 1,2,3,4-tetrahydro-β-carboline derived enaminones and nitroenamines with various 1,2- and 1,3-bis electrophiles, such as oxalyl chloride, maleic anhydride, 1,4-benzoquinone, 3-bromopropionyl chloride, itaconic anhydride, and imines (from formaldehyde and primary amines), has been investigated. These methodologies provide simple one-step pathways for efficient construction of highly functionalized tetrahydro-β-carboline 1,2-fused, five- and six-membered heterocyclic frameworks, such as indolizino[8,7-b]indoles, pyrido[1,2-a:3,4-b′]diindoles, indolo[2,3-a]quinolizidines, and pyrimido[1′,6′:1,2]pyrido[3,4-b]indoles, which are core structures of many naturally occurring indole alkaloids with diverse bioactivity.

A facile strategy for the preparation of end-capped and cross-linkable poly(propylene carbonate) with high performance

Itaconic anhydride (IAn) was firstly used for the modification of poly(propylene carbonate) (PPC) by solution blending following with the direct heating treatment, producing end-capped and cross-linkable PPC (PECPPC) with high performance. The reaction of PPC with IAn was detailed investigated and the structure of PECPPC was identified by FTIR and 1 H NMR. A facile strategy including end-capping and cross-linking can be developed to improve the performance of PPC. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) measurements revealed that the glass transition temperature ( T g ) and thermal decomposition temperature ( T d ) of PECPPCs are all much higher than those of PPC and increased with the increasing content of IAn. Tensile tests also showed the huge enhancement on the mechanical properties of PPC with the end-capping and cross-linking techniques, and the highest tensile strength of PECPPC4 is 37.5 MPa. Furthermore, ECPPC4 exhibits high hydrolysis rate in phosphate buffer solution (PBS) than that of PPC. It is demonstrated that the strategy with the combination of end-capping and cross-linking is efficient for the perfect modification of PPC with IAn.

Enhancing Photoluminescence of Nonconventional Luminescent Polymers by Increasing Chain Flexibility

AbstractMany nonconventional luminescent polymers are found to exhibit intrinsic photoluminescence and “aggregation‐induced emission” (AIE) behavior. Strong physical interactions among polymer chains and/or a rigid molecular conformation of polymer chains are thought to be beneficial to boost stronger emissions. The purpose of this work is to prove that increasing chain flexibility is, at least in some cases, beneficial to enhance the photoluminescence of nonconventional luminescent polymers. Poly(itaconic anhydride) (PITA) and poly[(1‐octene)‐co‐(itaconic anhydride)] (POITA) synthesized in this work are highly emissive in concentrated solutions and in solid state, exhibiting typical AIE characteristics, and very interestingly, the copolymer POITA exhibits stronger and red‐shifted emissions than the homopolymer PITA in both solutions and in the solid state. These results are explained by the increase of chain flexibility, which makes the nonconventional chromophores adopt proper conformations for strong intra‐ and/or interchain n‐π* and/or π–π* interactions. This study sheds some light on designing nonconventional luminescent materials with high emission efficiency and long wavelength emission.

A bio-based hyperbranched flame retardant for epoxy resins

A novel hyperbranched flame-retardant polymer (referred to as ITA-HBP) was synthesized from itaconic anhydride as a renewable starting material. Upon the incorporation of ITA-HBP, both the toughness and flame-retarding ability of epoxy resins with low phosphorus contents increased simultaneously increased the toughness and flame retardant properties of epoxy resin with low phosphorus contents. The impact strength, fracture toughness and fracture energy of the epoxy resins are significantly enhanced by 133.2%, 78.7% and 124.7% respectively due to the in situ reinforcing and toughening effects induced by ITA-HBP. At the same time, the incorporated ITA-HBP exhibited a remarkable flame-retarding activity in the gas phase due to the production of phosphorus radicals and in the condensed phase due to the formation of a phosphorus-rich char layer of the epoxy resin. The addition of ITA-HBP considerably reduced the peak heat release rate, total heat release and smoke release of the epoxy resin. At a phosphorus content of 0.26 wt%, the ITA-HBP/epoxy thermosets scored V-0 rating in the UL-94 test and showed a limiting oxygen index of 36.3%.

Facile fabrication of glycosylated and PEGylated carbon nanotubes through the combination of mussel inspired chemistry and surface-initiated ATRP.

Surface modification of carbon nanotubes (CNTs) through controlled living polymerization has demonstrated to be a useful route for preparation of CNTs based polymer composites. However, surface oxidation of CNTs is often required to generate functional groups, which can be further utilized for immobilization of polymerization initiator and grafting polymers. The surface oxidation procedure is rather complex, high energy cost, low efficient and will destroy the structure of CNTs. Therefore, the development of simple and efficient strategies for preparation of CNTs based composites should be of great research interest and raised much attention recently. In this work, a novel mussel inspired strategy that combination of ATRP and ring-opening reaction has been developed for simultaneous preparation of glycosylated and PEGylated CNTs for the first time. CNTs were first coated with polydopamine (PDA) through self-polymerization of dopamine under alkaline aqueous solution. Then polymerization initiator was immobilized on CNT-PDA through simple esterification and amidation reaction to obtain CNT-PDA-Br. The PEGylated CNTs were synthesized through ATRP using CNT-PDA-Br as initiator and polyethylene glycol monoester acrylate and itaconic anhydride (IA) as the monomers. Finally, glucosamine was conjugated with IA via ring-opening reaction. The successful preparation of glycosylated and PEGylated CNTs (CNT-PDA-Poly(PEGMA-co-IA)-Glu) was confirmed by a number of characterization techniques in details. The obtained CNTs based composites showed improved aqueous dispersibility and desirable cytocompatibility, implying their biomedical application potential. As compared with the conventional covalent strategies, the mussel inspired method described in this work will not destroy the structure for introduction functional groups on the surface of CNTs, that can occur under rather mild experimental conditions, including room temperature, short reaction time and aqueous solution. On the other hand, the mussel inspired chemistry can also be used for surface modification of almost any materials regardless of their size, morphology and compositions. Therefore, we believe that the mussel inspired strategy should be a general method for fabrication of various polymer composites for different applications.