Kilogram scale facile synthesis and systematic characterization of a Gd-macrochelate as T1-weighted magnetic resonance imaging contrast agent.

To overcome the problems of commercial magnetic resonance imaging (MRI) contrast agents (CAs) (i.e., small molecule Gd chelates), we have proposed a new concept of Gd macrochelates based on the coordination of Gd3+ and macromolecules, e.g., poly(acrylic acid) (PAA). To further decrease the r2/r1 ratio of the reported Gd macrochelates that is an important factor for T1 imaging, in this study, a superior macromolecule hydrolyzed polymaleic anhydride (HPMA) was found to coordinate Gd3+. The synthesis conditions were optimized and the generated Gd-HPMA macrochelate was systematically characterized. The obtained Gd-HPMA29 synthesized in a 100 L of reactor has a r1 value of 16.35 mM-1 s-1 and r2/r1 ratio of 2.05 at 7.0 T, a high Gd yield of 92.7% and a high product weight (1074 g), which demonstrates the feasibility of kilogram scale facile synthesis. After optimization of excipients and sterilization at a high temperature, the obtained Gd-HPMA30 formulation has a pH value of 7.97, osmolality of 691 mOsmol/kg water, density of 1.145 g/mL, and viscosity of 2.2 cP at 20 â„ƒ or 1.8 cP at 37 â„ƒ, which meet all specifications and physicochemical criteria for clinical injections indicating the immense potential for clinical applications.

Versatile Diphosphine Chelators for Radiolabeling Peptides with 99mTc and 64Cu.

We have developed a diphosphine (DP) platform for radiolabeling peptides with 99mTc and 64Cu for molecular SPECT and PET imaging, respectively. Two diphosphines, 2,3-bis(diphenylphosphino)maleic anhydride (DPPh) and 2,3-bis(di-p-tolylphosphino)maleic anhydride (DPTol), were each reacted with a Prostate Specific Membrane Antigen-targeted dipeptide (PSMAt) to yield the bioconjugates DPPh-PSMAt and DPTol-PSMAt, as well as an integrin-targeted cyclic peptide, RGD, to yield the bioconjugates DPPh-RGD and DPTol-RGD. Each of these DP-PSMAt conjugates formed geometric cis/trans-[MO2(DPX-PSMAt)2]+ (M = 99mTc, 99gTc, natRe; X = Ph, Tol) complexes when reacted with [MO2]+ motifs. Furthermore, both DPPh-PSMAt and DPTol-PSMAt could be formulated into kits containing reducing agent and buffer components, enabling preparation of the new radiotracers cis/trans-[99mTcO2(DPPh-PSMAt)2]+ and cis/trans-[99mTcO2(DPTol-PSMAt)2]+ from aqueous 99mTcO4- in 81% and 88% radiochemical yield (RCY), respectively, in 5 min at 100 °C. The consistently higher RCYs observed for cis/trans-[99mTcO2(DPTol-PSMAt)2]+ are attributed to the increased reactivity of DPTol-PSMAt over DPPh-PSMAt. Both cis/trans-[99mTcO2(DPPh-PSMAt)2]+ and cis/trans-[99mTcO2(DPTol-PSMAt)2]+ exhibited high metabolic stability, and in vivo SPECT imaging in healthy mice revealed that both new radiotracers cleared rapidly from circulation, via a renal pathway. These new diphosphine bioconjugates also furnished [64Cu(DPX-PSMAt)2]+ (X = Ph, Tol) complexes rapidly, in a high RCY (>95%), under mild conditions. In summary, the new DP platform is versatile: it enables straightforward functionalization of targeting peptides with a diphosphine chelator, and the resulting bioconjugates can be simply radiolabeled with both the SPECT and PET radionuclides, 99mTc and 64Cu, in high RCYs. Furthermore, the DP platform is amenable to derivatization to either increase the chelator reactivity with metallic radioisotopes or, alternatively, modify the radiotracer hydrophilicity. Functionalized diphosphine chelators thus have the potential to provide access to new molecular radiotracers for receptor-targeted imaging.

A new selective inhibitor for IMP-1 metallo-ß-lactamase, 3Z,5E-octa-3,5-diene-1,3,4-tricarboxylic acid-3,4-anhydride.

3Z,5E-Octa-3,5-diene-1,3,4-tricarboxylic acid-3,4-anhydride (ODTAA, 1) was isolated from Paecilomyces sp. FKI-6801 for its selective IMP-1 MBL inhibitory activity. The first total synthesis of 1 from the commercially available compound was achieved in 9 steps with 28% overall yield. Introduction of catechol to the maleic anhydride of 1 improved the IC50 toward IMP-1 MBL and the inhibitory activity against IMP-1 MBL-producing P. aeruginosa. Treatment of the maleic anhydride scaffold with amine showed that the ß-carbonyl-α,ß-unsaturated carboxylic acid moiety is required as a pharmacophore for IMP-1 MBL inhibition.

Dual-Dynamic Chemistries-Based Fast-Reprocessing and High-Performance Covalent Adaptable Networks.

Covalent adaptable networks (CANs) possess multiple functions including reprocessing (or recyclability), self-healing, welding, shape shifting, 3D printing, etc., due to the network rearrangement from dynamic bonds, and favorable performance from their cross-linked feature, and they are supposed to be as sustainable alternatives to thermosets. However, the thermal and mechanical properties, and stability of CANs are often sacrificed for rapid network rearrangement. In this paper, fast-reprocessing CANs with high performance are facilely constructed by in situ polymerization and dynamic cross-linking of styrene (St), maleic anhydride (MA), and acetal diol (BHAD). The rigid and hydrophobic polymer backbone endow the materials with high glass transition temperatures, mechanical performance, and water resistance. Besides, carboxylic group-catalyzed dual dynamic ester and acetal-based networks exhibit faster stress relaxation and realize extrusion reprocessing. This work provides an ingenious and simple strategy of construction of CANs combining rapid network rearrangement and excellent comprehensive performance, which is beneficial for the application of CANs.

Improve Quantum Yield of Poly(Maleic Anhydride-Alt-Vinyl Acetate) via Good Solvents.

In this study, the optical properties of poly(maleic anhydride-alt-vinyl acetate) (PMV) synthesized by different polymerization methods are studied systematically. Compared to self-stabilized precipitation polymerization (pPMV), solution polymerization produces PMV solids (sPMV) with an extraordinarily high quantum yield (QY) of 20.65%. Additionally, redissolving pPMV in good solvents (rPMV) will also help to increase QY. The rising QY of sPMV and rPMV supports the idea that good solvents will reduce the rigidity of polymer chains and promote cluster formation, which is confirmed by lower glass transition temperature (Tg ) and small angle X-ray scatterer (SAXS). The study also finds that PMV exhibits application potentials in white light-emitting diodes (WLEDs) and light conversion film.

Designing a novel poly (methyl vinyl ether maleic anhydride) based polymeric membrane with enhanced antifouling performance for removal of pentachlorophenol from aqueous solution.

In this current study, poly (methyl vinyl ether maleic anhydride) (PMVEAMA), a sustainable additive, was incorporated into poly (ether-ether sulfone) (PEES) polymer to design a novel polymeric hybrid membrane for the efficient filtration of toxic pentachlorophenol (PCP) from an aqueous medium. Hydrophilic additives significantly altered the membrane's morphology, structure, porosity, water content, and flux performance compared to the bare PEES membrane. The influence of PMVEAMA on the structural modification of the synthesized polymer membrane was confirmed by SEM, ATR-FTIR, XRD, AFM, zeta potential and contact angle. Findings revealed that the addition of PMVEAMA to the PEES polymer enhances the porosity (17.7%-28.9%), water content (29.8%-39.8%), and pure water flux (186 Lm-2h-1 to 349 Lm-2h-1). The effect of PMVEAMA concentration on the PEES membrane exhibited more finger like pores, better porosity and hydrophilicity, reduced surface roughness, fouling and increased permeability. The fouling studies exhibit an improved 57% PCP rejection and permeation flux of 22.3 Lm-2h-1 due to the addition of the hydrophilic additive. Surprisingly, the incorporation of PMVEAMA into the bare PEES membrane resulted in a high flux recovery ratio of 73.7%. The antifouling properties and enhanced permeability of the PEES/PMVEAMA membrane indicates its potential application in water purification sectors for the efficient separation of contaminants.

Toward the Improvement of Maleic Anhydride Functionalization in Polyhydroxybutyrate (PHB): Effect of Styrene Monomer and Sn(Oct)2 Catalyst.

In this work, polyhydroxybutyrate (PHB) was maleic anhydride (MA)-grafted in the molten state, using dicumyl peroxide (DCP) as a reaction initiator. Tin(II) 2-ethylhexanoate (Sn(Oct)2) and styrene monomer (St.) were used to maximize the maleic anhydride grafting degree. When PHB was modified with MA/DCP and MA/DCP/Sn(Oct)2, viscosity was reduced, suggesting chain scission in relation to pure PHB. However, when the styrene monomer was added, the viscosity increased due to multiple grafts of MA and styrene into the PHB chain. In addition, the FTIR showed the formation of a new band at 1780 cm-1 and 704 cm-1, suggesting a multiphase copolymer PHB-g-(St-co-MA). The PHB (MA/DCP) system showed a grafting degree of 0.23%; however, the value increased to 0.39% with incorporating Sn(Oct)2. The highest grafting efficiency was for the PHB (MA/DCP/St.) system with a value of 0.91%, while the PHB (MA/DCP/St./Sn(Oct)2) hybrid mixture was reduced to 0.73%. The chemical modification process of PHB with maleic anhydride increased the thermal stability by about 20 °C compared with pure PHB. The incorporation of 0.5 phr of the Sn(Oct)2 catalyst increased the efficiency of the grafting degree in the PHB. However, the St./Sn(Oct)2 hybrid mixture caused a deleterious effect on the maleic anhydride grafting degree.

Mechanism of the Photochemical Isomerization and Oxidation of 2-Butenedial: A Theoretical Study.

Under tropospheric conditions, 2-butenedial is photochemically removed to produce secondary organic aerosol. Upon solar irradiation in the lower troposphere, the main photochemical products are ketene-enol (a key intermediate product), furanones, and maleic anhydride. The oxidative reaction mechanism was studied using the multireference method CASSCF to explore the hypersurface of the two most accessible singlet excited states, and by DFT for the ground state. Photoisomerization of 2-butenedial in the first excited state directly produces ground state ketene-enol upon nonradiative relaxation. From this intermediate, furan-2-ol and successively 3H-furan-2-one and 5H-furan-2-one are formed. The cooperative effect of two water molecules is essential to catalyze the cyclization of ketene-enol to furan-2-ol, followed by hydrogen transfers to furanones. Two water molecules are also necessary to form maleic anhydride from furan-2-ol. For this last reaction, in which one extra oxygen must be acquired, we hypothesize a mechanism with singlet oxygen as the oxidant.

Elucidation of Late-Stage Biosynthesis of Phomoidride: Proposal of Cyclization Mechanism Affording Characteristic Nine-Membered Ring of Fungal Dimeric Anhydride.

Antihypercholesterolemic agent phomoidride (PMD) B has a highly elaborated bicyclo[4.3.1]deca-1,6-diene core scaffold derived from dimeric anhydride with a nine-membered ring. This report elucidated the late stage transformation from an anhydride monomer to PMD B through the heterologous expression of three enzyme genes, TstC, TstK, and TstE. Additional in vitro studies of TstK and TstE provided evidence on the formation of PMD via dimerization, three-step oxidation, and unusual methylation-triggered bicyclic ketal formation. Elucidation of the function of cyclase TstC prompts us to examine the cyclization mechanism of TstC by using a computational approach. Computational analytical data on PMD and structurally related glaucanic acid indicated that the initial decarboxylation of monomer results in enolate and subsequent double Michael reactions of another monomer, followed by an optional aldol reaction proceeding in an endo-selective manner to give cycloadducts, supporting the fact that the starting orientation of two monomers is directly transferred to the product configurations.

Aliphatic Polyesters with White-Light Clusteroluminescence.

Single-molecule white-light emission (SMWLE) has many advantages in practical applications; however, the fabrication of SMWLE from nonconjugated luminescent polymers, namely, clusteroluminogens (CLgens), is still a big challenge. Herein, the first example of linear nonconjugated polyesters with SMWLE is reported. Twenty-four kinds of nonconjugated aliphatic polyesters with tunable clusteroluminescence (CL) colors and efficiency were synthesized by the copolymerization of six epoxides and four anhydrides. Experimental and calculation results prove that, at the primary structure level, the balance of structural flexibility and rigidity via adjusting the side-chain length significantly enhances the efficiency of CL without wavelength change. However, altering the chemical structures of the monomer from succinic anhydride to trans-maleic anhydride (MA), cis-MA, and citraconic anhydride (CA), secondary structures of these polyesters change from helix to straight and folding sheet accompanied by gradually red-shifted CL from 460 to 570 nm due to the increase in through-space n-π* interactions, as demonstrated by the computational and experimental results. Then, pure SMWLE with CIE coordination (0.30, 0.32) based on overlapped short-wavelength and long-wavelength CL is achieved in CA-based polyesters. This work not only provides further insights into the emission mechanism of CL but also provides a new strategy to manipulate the properties of CL by regulating the hierarchical structures of CLgens.

Chemical Degradation-Inspired Total Synthesis of the Antibiotic Macrodiolide, Luminamicin.

This article describes the first total synthesis of luminamicin using a strategy combining chemical degradation with synthesis. Chemical degradation studies provided a sense of the inherent reactivity of the natural product, and deconstruction of the molecule gave rise to a key intermediate, which became the target for chemical synthesis. The core structure of the southern part of luminamicin was constructed by a 1,6-oxa-Michael reaction to form an oxa-bridged ring, followed by coupling with a functionalized organolithium species. Modified Shiina macrolactonization conditions forged the strained 10-membered lactone containing a tri-substituted olefin. Diastereoselective α-oxidation of the 10-membered lactone completed the center part to provide the key intermediate. Inspired by the degradation study, an unprecedented enol ether/maleic anhydride moiety was constructed with a one-pot chlorosulfide coupling and thiol ß-elimination sequence. Finally, macrolactonization to the 14-membered ring in the presence of the highly electrophilic maleic anhydride moiety was accomplished using modified Mukaiyama reagents to complete the synthesis of luminamicin.

CdSe/ZnS quantum dot-encoded maleic anhydride-grafted PLA microspheres prepared through membrane emulsification for multiplexed immunoassays of tumor markers.

Early diagnosis of tumor markers is of great importance for the successful treatment of cancer. As a high-throughput and high-sensitivity detection technology, liquid suspension biochips based on quantum dot (QD) encoded microspheres have been widely used in the immunodetection of tumor markers. In this work, maleic anhydride grafted PLA (PLA-MA) microspheres based on quantum dot encoding were used as carriers for liquid phase suspension biochips for the immunoassay of tumor markers. PLA-MA fluorescent beads are prepared by embedding CdSe/ZnS quantum dots in PLA-MA using Shirasu porous glass (SPG) membrane emulsification technology, which has high fluorescence intensity, good stability, and good dispersion. Fluorescent immunoassays on dipsticks found that PLA-MA microspheres have high biological activity and good stability, which is conducive to immunoassays. Based on this, using the characteristics of CdSe/ZnS quantum dots and flow cytometry, monochromatic and two-color coding methods were developed, and 9 distinguishable coding beads were prepared. The results showed that PLA-MA fluorescent microspheres exhibited good biocompatibility, stable coding signals, low background noise, and low detection limits when performing quaternary immunoassays on tumor markers CA125, CA199, CA724, and CEA by CdSe/ZnS QD-encoded PLA-MA microsphere binding flow cytometry.

Hydrated Hydroxide Complex Dominates the AIE Properties of Nonconjugated Polymeric Luminophores.

Nontraditional intrinsic luminescence (NTIL) which always accompanied with aggregation-induced emission (AIE) features has received considerable attention due to their importance in the understanding of basic luminescence principle and potential practical applications. However, the rational modulation of the NTIL of nonconventional luminophores remains difficult, on account of the limited understanding of emission mechanisms. Herein, the emission color of nonconjugated poly(methyl vinyl ether-alt-maleic anhydride) (PMVEMA) can be readily regulated from blue to red by controlling the alkalinity during the hydrolysis process. The nontraditional photoluminescence with AIE property is from the new formed p-band state, resulting from the strong overlapping of p orbitals of the clustered O atoms through space interactions. Hydrated hydroxide complexes embedded in the entangled polymer chain make big difference on the clustering of O atoms which dominates the AIE property of nonconjugated PMVEMA. These new insights into the photoluminescence mechanism of NTIL should stimulate additional experimental and theoretical studies and can benefit the molecular-level design of nontraditional chromophores for optoelectronics and other applications.

Novel biogenic gold nanoparticles stabilized on poly(styrene-co-maleic anhydride) as an effective material for reduction of nitrophenols and colorimetric detection of Pb(II).

Biogenic gold nanoparticles (AuNPs) have been extensively studied for the catalytic conversion of nitrophenols (NP) into aminophenols and the colorimetric quantification of heavy metal ions in aqueous solutions. However, the high self-agglomeration ability of colloidal nanoparticles is one of the major obstacles hindering their application. In the present study, we offered novel biogenic AuNPs synthesized by a green approach using Cistanche deserticola (CD) extract as a bioreducing agent and stabilized on poly(styrene-co-maleic anhydride) (PSMA). The prepared Au@PSMA nanoparticles were characterized by various techniques (HR-TEM, SEAD, FE-SEM, DLS, TGA, XRD, and FTIR) and studied for two applications: the catalytic reduction of 3-NP by NaBH4 and the sensing detection of Pb2+ ions. The optimal conditions for the synthesis of AuNPs were investigated and established at 60 °C, 20 min, pH of 9, and 0.5 mM Au3+. Morphological studies showed that AuNPs synthesized by CD extract were mostly spherical with a mean diameter of 25 nm, while the size of polymer-integrated AuNPs was more than two-fold larger. Since PSMA acted as a matrix keeping the nanoparticles from coagulation and maintaining the optimal surface area, AuNPs integrated with PSMA showed higher catalytic efficiency with a faster reaction rate and lower activation energy than conventional nanoparticles. Au@PSMA could completely reduce 3-NP within 10 min with a rate constant of 0.127 min-1 and activation energy of 9.96 kJ/mol. The presence of PSMA also improved the stability and recyclability of AuNPs. Used as a sensor, Au@PSMA exhibited excellent sensitivity and selectivity for Pb2+ ions with a limit of detection of 0.03 µM in the linear range of 0-100 µM. The study results suggested that Au@PSMA could be used as a promising catalyst for the reduction of NP and the colorimetric sensor for detection of Pb2+ ions in aqueous environmental samples.

Scavenging of hexavalent chromium from aqueous solution by Macadamia nutshell biomass modified with diethylenetriamine and maleic anhydride.

Based on the premise that aqueous anions of hexavalent chromium (Cr(VI)) are capable of electrostatic interaction with cationic and polar active sites, acid-washed Madacamia nutshell biomass was sequentially treated with diethylenetriamine (DETA) and maleic anhydride (MA) to graft poly(diethylenetriamine-co-maleic anhydride). By displaying a new peak at 1685 cm-1 ascribed to amide CO stretching vibrations, Fourier transform infrared spectroscopy highlighted the formation of amide groups through reaction of DETA with carboxyl groups on the biomass surface. Scanning electron microscopic images of the MA-modified biomass displayed polymeric growths attributed to copolymerization of DETA with MA. The polar and ionizable amide and amine groups of the grafted copolymer endowed the adsorbent with Cr(VI) removal capabilities over a wide pH range demonstrated by removal efficiencies between 70.9% and 81.7% in the pH 1.6 to pH 10.0 range for the treatment of 20 mL solutions containing 100 mg L-1 Cr(VI) with 200 mg of adsorbent. Conformity of the adsorption isotherm data to the Freundlich model revealed the heterogeneous nature of the adsorbent surface, which comprised a variety of functional groups capable of interaction with Cr(VI) species in solution. The Sips isotherm model provided the best fit to the equilibrium experimental data, and the adsorption capacity was 779.1 mg g-1 at pH 1.6, room temperature and an adsorbent dosage of 5.0 g L-1. The findings indicate that Cr(VI) adsorption onto diethylenetriamine and maleic anhydride modified Madacamia nutshell biomass is a promising option for Cr(VI) removal from aqueous solutions.

Poly(maleic anhydride-alt-1-octadecene)-based bioadhesive nanovehicles improve oral bioavailability of poor water-soluble gefitinib.

The poor water solubility and inadequate oral bioavailability of gefitinib (Gef) remain a critical issue to achieve the therapeutic outcomes. Herein, we designed a poly(maleic anhydride-alt-1-octadecene) (PMA/C18) based lipid nanovehicle (PLN) to improve the intestinal absorption and oral bioavailability of poorly water-soluble Gef. PLN was nanometer-sized particles, and Gef was dispersed in the PLN formulation as amorphous or molecular state. At 4 h of oral administration, the tissue concentration of Gef in duodenum, jejunum, and ileum was profoundly enhanced 3.37-, 8.94-, and 8.09-fold by PLN when comparing to the counterpart lipid nanovehicle. Moreover, the oral bioavailability of Gef was significantly enhanced 2.48-fold by the PLN formulation when comparing to the free drug suspension. Therefore, this study provides an encouraging bioadhesive delivery platform to improve the oral delivery of poorly water-soluble drugs.

Maleic Anhydride-Grafted PLA Preparation and Characteristics of Compatibilized PLA/PBSeT Blend Films.

Poly(butylene sebacate-co-terephthalate) (PBSeT) is a biodegradable flexible polymer suitable for melt blending with other biodegradable polymers. Melt blending with a compatibilizer is a common strategy for increasing miscibility between polymers. In this study, PBSeT polyester was synthesized, and poly(lactic acid) (PLA) was blended with 25 wt% PBSeT by melt processing with 3-6 phr PLA-grafted maleic anhydride (PLA-g-MAH) compatibilizers. PLA-g-MAH enhanced the interfacial adhesion of the PLA/PBSeT blend, and their mechanical and morphological properties confirmed that the miscibility also increased. Adding more than 6 phr of PLA-g-MAH significantly improved the mechanical properties and accelerated the cold crystallization of the PLA/PBSeT blends. Furthermore, the thermal stabilities of the blends with PLA-g-MAH were slightly enhanced. PLA/PBSeT blends with and without PLA-g-MAH were not significantly different after 120 h, whereas all blends showed a more facilitated hydrolytic degradation rate than neat PLA. These findings indicate that PLA-g-MAH effectively improves PLA/PBSeT compatibility and can be applied in the packaging industry.

Water-Tree Characteristics and Its Mechanical Mechanism of Crosslinked Polyethylene Grafted with Polar-Group Molecules.

In order to restrain electric-stress impacts of water micro-droplets in insulation defects under alternating current (AC) electric fields in crosslinked polyethylene (XLPE) material, the present study represents chemical graft modifications of introducing chloroacetic acid allyl ester (CAAE) and maleic anhydride (MAH) individually as two specific polar-group molecules into XLPE material with peroxide melting approach. The accelerated water-tree aging experiments are implemented by means of a water-blade electrode to measure the improved water resistance and the affording mechanism of the graft-modified XLPE material in reference to benchmark XLPE. Melting−crystallization process, dynamic viscoelasticity and stress-strain characteristics are tested utilizing differential scanning calorimeter (DSC), dynamic thermomechanical analyzer (DMA) and electronic tension machine, respectively. Water-tree morphology is observed for various aging times to evaluate dimension characteristics in water-tree developing processes. Monte Carlo molecular simulations are performed to calculate free-energy, thermodynamic phase diagram, interaction parameter and mixing energy of binary mixing systems consisting of CAAE or MAH and water molecules to evaluate their thermodynamic miscibility. Water-tree experiments indicate that water-tree resistance to XLPE can be significantly improved by grafting CAAE or MAH, as indicated by reducing the characteristic length of water-trees from 120 to 80 µm. Heterogeneous nucleation centers of polyethylene crystallization are rendered by the grafted polar-group molecules to ameliorate crystalline microstructures, as manifested by crystallinity increment from 33.5 to 36.2, which favors improving water-tree resistance and mechanical performances. The highly hydrophilic nature of CAAE can evidently inhibit water molecules from aggregating into water micro-droplets in amorphous regions between crystal lamellae, thus acquiring a significant promotion in water-tree resistance of CAAE-modified XLPE. In contrast, the grafted MAH molecules can enhance van der Waals forces between polyethylene molecular chains in amorphous regions much greater than the grafted CAAE and simultaneously act as more efficient crystallization nucleation centers to ameliorate crystalline microstructures of XLPE, resulting in a greater improvement (relaxation peak magnitude increases by >10%) of mechanical toughness in amorphous phase, which primarily accounts for water-tree resistance promotion.

Activation of Vegetable Oils by Reaction with Maleic Anhydride as a Renewable Source in Chemical Processes: New Experimental and Computational NMR Evidence.

Vegetable oils are bio-based and sustainable starting materials that can be used to develop chemicals for industrial processes. In this study, the functionalization of three vegetable oils (grape, hemp, and linseed) with maleic anhydride was carried out either by conventional heating or microwave activation to obtain products that, after further reactions, can enhance the water dispersion of oils for industrial applications. To identify the most abundant derivatives formed, trans-3-octene, methyl oleate, and ethyl linoleate were reacted as reference systems. A detailed NMR study, supported by computational evidence, allowed for the identification of the species formed in the reaction of trans-3-octene with maleic anhydride. The signals in the 1H NMR spectra of the alkenyl succinic anhydride (ASA) moieties bound to the organic chains were clearly identified. The reactions achieved by conventional heating were carried out for 5 h at 200 °C, resulting in similar or lower amounts of ASA units/g of oil with respect to the reactions performed by microwave activation, which, however, induced a higher viscosity of the samples.

Confined Crystallization of Thin Plasma-Polymerized Nanocomposite Films with Maleic Anhydride and Cellulose Nanocrystals under Hydrolysis.

The creation of novel surface morphologies through thin-film patterning is important from a scientific and technological viewpoint in order to control specific surface properties. The pulsed-plasma polymerization of thin nanocomposite films, including maleic anhydride (MA) and cellulose nanocrystals (CNC), may result in different metastable film morphologies that are difficult to control. Alternatively, the transformation of deposited plasma films into crystalline structures introduces unique and more stable morphologies. In this study, the structural rearrangements of plasma-polymerized (MA+CNC) nanocomposite films after controlled hydrolysis in a humid atmosphere were studied, including effects of plasma conditions (low duty cycle, variable power) and monomer composition (ratio MA/CNC) on hydrolysis stability. The progressive growth of crystalline structures with fractal dendrites was observed in confined thin films of 30 to 50 nm. The structures particularly formed on hydrophilic substrates and were not observed before on the more hydrophobic substrates, as they exist as a result of water penetration and interactions at the film/substrate interface. Furthermore, the nucleating effect and local pinning of the crystallites to the substrate near CNC positions enhanced the film stability. The chemical structures after hydrolysis were further examined through XPS, indicating esterification between the MA carboxylic acid groups and CNC surface. The hydrolysis kinetics were quantified from the conversion of anhydride groups into carboxylic moieties by FTIR analysis, indicating enhanced hydrolytic stability of p(MA+CNC) nanocomposite films relative to the pure p(MA) films.