Ester Linkage Research Articles

Bridging mRNA and Polycation Using RNA Oligonucleotide Derivatives Improves the Robustness of Polyplex Micelles for Efficient mRNA Delivery.

Polyplex for messenger RNA (mRNA) delivery requires strong yet reversible association between mRNA and polycation for extracellular robustness and selective intracellular disintegration. Herein, RNA oligonucleotide (OligoRNA) derivatives that bridge mRNA and polycation are developed to stabilize polyplex micelles (PMs). A set of the OligoRNAs introduced with a polyol moiety in their 5' end is designed to hybridize to fixed positions along mRNA strand. After PM preparation from the hybridized mRNA and poly(ethylene glycol)-polycation block copolymer derived with phenylboronic acid (PBA) moieties in its cationic segment, PBA moieties form reversible phenylboronate ester linkages with a polyol moiety at 5' end of OligoRNAs and a diol moiety at their 3' end ribose, in the PM core. The OligoRNAs work as a node to bridge ionically complexed mRNA and polycation, thereby improving PM stability against polyion exchange reaction and ribonuclease attack in extracellular environment. After cellular uptake, intracellular high concentration of adenosine triphosphate triggers the cleavage of phenylboronate ester linkages, resulting in mRNA release from PM. Ultimately, the PM provides efficient mRNA introduction in cultured cells and mouse lungs after intratracheal administration, demonstrating the potential of the bridging strategy in polyplex-based mRNA delivery.

Magnetic Self-Healing Hydrogel from Difunctional Polymers Prepared via the Kabachnik-Fields Reaction.

The development of high quality magnetic self-healing hydrogels containing well-dispersed magnetic nanoparticle has been a challenging procedure due to unavailable methods of facilely introducing groups that can efficiently stabilize these magnetic nanoparticles in the self-healing hydrogels. In this research, a polymer containing both phenylboronic acid (PBA) and phosphonic acid (PA) groups has been developed by the Kabachnik-Fields (KF) reaction. This polymer well disperses iron oxide nanoparticles (IONPs) through the strong interactions between the PA groups and the surface of the IONPs; thus, this polymer effectively mixed IONPs and poly(vinyl alcohol) (PVA) to form a hydrogel containing well-dispersed IONPs. The resulting hydrogel is self-healing, owing to the dynamic borate ester linkages. Moreover, the presence of the IONPs endowed the hydrogel with magnetic properties, also making it heat-responsive in an alternating magnetic field and expanding its application as a contrast agent for magnetic resonance imaging. The magnetic self-healing hydrogel showed excellent biosafety properties in animal experiments, suggesting its potential as an injectable implant material for biological and medical applications. This research exploits a biocompatible magnetic self-healing hydrogel with well-dispersed IONPs, demonstrating the value of the KF reaction in the development of functional polymers and smart materials, which might prompt a broad study of multicomponent reactions in interdisciplinary fields.

The properties of particleboard composites made from three sorghum (Sorghum bicolor) accessions using maleic acid adhesive

It is very important to develop green composite materials owing to increasing global environmental issues. One of the alternative raw materials for the production of green composites is biomass. Bagasse sorghum is a promising alternative raw material for the manufacturing of particleboard composites. The influence of sorghum accessions on the performance of particleboard composites was analyzed in this study. In addition, the particleboard quality was made using maleic acid (MA) adhesive and compared with citric acid (CA) and phenol-formaldehyde (PF) adhesives. Three accessions of sorghum, 4183A, super 1, and Pahat, were used as raw materials in particleboard manufacturing. The 20 wt% MA adhesive was applied in particleboard manufacturing. The board dimensions and density targets were 30 × 30 × 0.9 cm3 and 0.8 g/cm3, respectively. The particle mat was pressed 200 °C for 10 min with a maximum of 6.5 MPa. For reference, the JIS A 5908–2003 was used to evaluate physical and mechanical properties, SNI 7207–2014 was used for the resistance against termites, and JIS K 1571–2004 for evaluated the particleboard against decay. The results showed that the sorghum accession in this research did not affect the quality of the particleboard. The thickness swelling (TS), internal bond (IB), modulus of elasticity (MOE), and modulus of rupture (MOR) of particleboard satisfied JIS A 5908–2003 type 8. The particleboard using MA was comparable with those bonded with CA and had better durability against termites and decay than PF adhesives. The ester linkages were formed due to the reaction between MA (carboxyl groups) and the sorghum bagasse (hydroxyl groups) after being analyzed using Fourier transform infrared (FTIR). Therefore, particleboard in this study has good quality.

Macromolecular helicity induction and static helicity memory of poly(biphenylylacetylene)s bearing aromatic pendant groups and their use as chiral stationary phases for high-performance liquid chromatography.

Two novel poly(biphenylylacetylene)s (PBPAs) bearing achiral alkylphenyl groups at the 4'-position of the biphenyl pendant through ester linkers with different sequences were synthesized by the rhodium-catalyzed polymerization of the corresponding monomers. The influence of the alkylphenyl pendants and the ester sequences on the macromolecular helicity induction and subsequent static helicity memory was investigated. In addition, the chiral recognition ability as chiral stationary phases for high-performance liquid chromatography of the helicity-memorized PBPAs was also examined. Both polymers formed almost perfect right- and left-handed helical conformations through noncovalent chiral interactions with enantiomeric alcohols, and their induced macromolecular helicities were completely retained ("memorized") after removal of the helix inducer. A PBPA bearing a 4-n-butylphenoxycarbonyl pendant group with a static helicity memory showed a remarkably high chiral recognition ability toward a wide variety of chiral aromatics, including simple point chiral compounds, axially chiral biaryls, a chiral spiro compound, helicenes, and planar chiral cyclophanes, particularly under the reversed-phase conditions.

A Validated HPLC-PDA-HRMS Method to Investigate the Biological Stability and Metabolism of Antiparasitic Triterpenic Esters.

Pentacyclic triterpenes (PTs) are commonly found in medicinal plants with well-known antiparasitic effects. Previous research on C-3 and C-27 triterpenic esters showed effective and selective in vitro antiparasitic activities and in vivo effectiveness by parenteral routes. The aim of this study was to determine triterpenic esters’ stability in different biological-like media and the main microsomal degradation products. An HPLC-PDA method was developed and validated to simultaneously analyze and quantify bioactive triterpenic esters in methanol (LOQ: 2.5 and 1.25–100 µg/mL) and plasma (LOQ: 5–125 µg/mL). Overall, both triterpenic esters showed a stable profile in aqueous and buffered solutions as well as in entire plasma, suggesting gaining access to the ester function is difficult for plasma enzymes. Conversely, after 1 h, 30% esters degradation in acidic media was observed with potential different hydrolysis mechanisms. C-3 (15 and 150 µM) and C-27 esters (150 µM) showed a relatively low hepatic microsomal metabolism (<23%) after 1 h, which was significantly higher in the lowest concentration of C-27 esters (15 µM) (>40% degradation). Metabolic HPLC-PDA-HRMS studies suggested hydrolysis, hydroxylation, dehydration, O-methylation, hydroxylation and/or the reduction of hydrolyzed derivatives, depending on the concentration and the position of the ester link. Further permeability and absorption studies are required to better define triterpenic esters pharmacokinetic and specific formulations designed to increase their oral bioavailability.

Influence of covalently-bound graphene oxide on the mechanical properties of carbon fiber composite materials

Graphene was used as an additive in fiber-reinforced plastics. The apparent interfacial shear strength (IFSS) was improved by grafting graphene onto the fibers. In this study, the effect of graphene grafted onto carbon fiber via chemical covalent bonding on the mechanical properties of the fibers was evaluated. This method was used to link graphene and carbon fibers via ester linkages, which are stronger than physical adsorption interactions and cause little damage to the fiber strength. Before grafting through an ester linkage, an electrophoretic deposition was conducted to uniformly coat graphene onto the carbon fibers. The purpose of this study was to establish a fabrication method that could control the density and thickness of the graphene layer covalently bound to the fibers. In addition, the optimal production process and composite form of the reinforced fibers were determined by evaluating the fiber strength and IFSS of various graphene-reinforced fibers. Ultimately, it was determined that graphene could be grafted onto carbon fibers relatively uniformly, and that the graphene layer thickness affected their interfacial shear strength. In terms of optimizing the IFSS, a thin and uniform graphene layer was best, and the IFSS was improved by 42.1% compared with untreated fibers containing sizing agents.

Malonate complexes at γ-alumina surface determined by a multi-technique characterization approach and a surface complex model

γ-Al2O3 is a transition alumina oxide used in many different applications. Its surface chemistry seems to be a key factor in the preparation of heterogeneous catalyst where γ-Al2O3 is used as a support. The modification and description of its surface are necessary to understand the role of the support on the catalyst preparation and on its performance. In this work, the modification of the surface is performed with a carboxylic diacid, malonic acid, which specifically adsorbs at the γ-Al2O3 surface and modifies the surface chemistry (surface sites density and global surface charge). The impact of the impregnation pH, malonic acid content, and drying are studied. By using a multi-technique approach, both the solid/liquid interface and the dried surface were characterized. The infrared spectroscopic information coupled with zetametry measurements indicate the formation of an inner sphere complex adsorbed via both side-on ester linkage and bridging bidentate mode involving the two carboxylic groups. A surface complexation model was built to support the experimental results and obtain complementary information. It underlines the different reactivity of the γ-Al2O3 facets and of the surface sites responsible for the adsorption. The whole (100) facet is involved in the adsorption while only the µ1-AlVI-OH and µ1-AlIV-OH sites of the (110) facet participate in the malonic acid adsorption. The model also confirms the consumption of 3–4 surface hydroxyls per adsorbed molecule, in accordance with ester linkage and bridging bidentate structure. This molecular level description of the surface chemistry is of interest in different environmental fields such as wastewater treatment and pollutant removal. In the catalysis field, the detailed surface chemistry will be very useful to understand the impact of this modified support on the catalytic performance.

Near-Infrared Fluorescent Micelles from Poly(norbornene) Brush Triblock Copolymers for Nanotheranostics.

This contribution describes the design and synthesis of multifunctional micelles based on amphiphilic brush block copolymers (BBCPs) for imaging and selective drug delivery of natural anticancer compounds. Well-defined BBCPs were synthesized via one-pot multi-step sequential grafting-through ring-opening metathesis polymerization (ROMP) of norbornene-based macroinitiators. The norbornenes employed contain a poly(ethylene glycol) methyl ether chain, an alkyl bromide chain, and/or a near-infrared (NIR) fluorescent cyanine dye. After block copolymerization, post-polymerization transformations using bromide-azide substitution, followed by the strain-promoted azide-alkyne cycloaddition (SPAAC) allowed for the functionalization of the BBCPs with the piplartine (PPT) moiety, a natural product with well-documented cytotoxicity against cancer cell lines, via an ester linker between the drug and the polymer side chain. The amphiphilic BBCPs self-assembled in aqueous media into nano-sized spherical micelles with neutral surface charges, as confirmed by dynamic light scattering analysis and transmission electron microscopy. During self-assembly, paclitaxel (PTX) could be effectively encapsulated into the hydrophobic core to form stable PTX-loaded micelles with high loading capacities and encapsulation efficiencies. The NIR fluorescent dye-containing micelles exhibited remarkable photophysical properties, excellent colloidal stability under physiological conditions, and a pH-induced disassembly under slightly acidic conditions, allowing for the release of the drug in a controlled manner. The in vitro studies demonstrated that the micelles without the drug (blank micelles) are biocompatible at concentrations of up to 1 mg mL-1 and present a high cellular internalization capacity toward MCF-7 cancer cells. The drug-functionalized micelles showed in vitro cytotoxicity comparable to free PPT and PTX against MCF-7 and PC3 cancer cells, confirming efficient drug release into the tumor environment upon cellular internalization. Furthermore, the drug-functionalized micelles exhibited higher selectivity than the pristine drugs and preferential cellular uptake in human cancer cell lines (MCF-7 and PC3) when compared to the normal breast cell line (MCF10A). This study provides an efficient strategy for the development of versatile polymeric nanosystems for drug delivery and image-guided diagnostics. Notably, the easy functionalization of BBCP side chains via SPAAC opens up the possibility for the preparation of a library of multifunctional systems containing other drugs or functionalities, such as target groups for recognition.

Synthesis and mesomorphic properties of new organosiloxane chiral calamitic liquid crystals

A new chiral calamitic compound consisting of a phenyl core that is connected through ester linkers to a benzoate carrying a chiral (S)-2-methylbutoxy group at one side and a biphenyl carboxylate with an undecenyloxy chain at other side has been synthesized. Additionally, the siloxane substituted derivatives and a dimer with these two identical chiral calamitics linked by a disiloxane spacer have been obtained via hydrosilylation reaction to study the effect of combining the chiral moiety and siloxane segments within the same structure on liquid crystalline properties. The chiral calamitic compound and derivatives with a siloxane end-group or a siloxane spacer have been characterized using classical spectroscopic methods (1H NMR, 13C NMR, 29Si NMR and MS) and elemental analysis (EA). The liquid crystalline properties of all new compounds were investigated by differential scanning calorimetry, optical polarizing microscopy, X-ray scattering and electro-optic methods. With the introduction of a siloxane end-group to the vinyl-terminated calamitic compound exhibiting enantiotropic chiral nematic phase (N*) and chiral tilted smectic phase (SmC*), the occurrence of stable smectic phase was strongly promoted. In a similar way, the dimer with two identical calamitic mesogens connected by a disiloxane spacer exhibited a wider smectic mesophase interval in addition to the presence of N* mesophase. The new mesogens exhibit a ferroelectric switching with PS of around 200 nC cm−2 in their chiral tilted smectic (SmC*) mesophase range. The transition temperatures of organosiloxanes are considerably lower than that of olefinic precursor.

Pentaalkoxytriphenylene monoesters and their dyads; structural factors influencing columnar and nematic mesophase behaviour

ABSTRACT Ester linkages are frequently employed in the design of discotic liquid crystals, and indeed the first examples of discotic liquid crystals reported by Chandrasekhar, Sadashiva and Suresh were hexaesters of benzene. Within the wide range of liquid crystalline triphenylene systems so far reported, the symmetrical hexa(aryl) esters are particularly noteworthy because they form the relatively rare and technologically important discotic nematic mesophase. An alternative strategy for inducing nematogenic behaviour is to build linked and twinned structures, and here we report examples of materials that combine the two design features. Pentahexyloxy triphenylenes bearing a single aryl ester retain the columnar mesophase. Linked dyad structures promote nematic phase formation and stability is influenced by the link type and bonding arrangement within isomeric series (phthalates) and related constructs.

Hydroxyethyl Starch Curcumin Enhances Antiproliferative Effect of Curcumin Against HepG2 Cells via Apoptosis and Autophagy Induction.

It is well documented that curcumin (CUR), as a polyphenol molecule originated from turmeric, has many advantages such as antioxidative, anti-inflammatory, neuroprotective, and antitumor effects. However, because of its poor water solubility and low bioavailability, the biomedical applications of CUR are limited. So, in this study, we modified CUR with conjugation to a food-derived hydrophilic hydroxyethyl starch (HES) via an ester linkage to fabricate the amphiphilic conjugate HES-CUR prior to self-assembling into uniform nanoparticles (HES-CUR NPs). And, the results of the 1H NMR spectra and FT-IR spectrum showed successful synthesis of HES-CUR NPs; moreover, the solubility and the drug loading efficiency of CUR were significantly increased. Next, we further explored the differences on the antitumor effects between HES-CUR NPs and CUR in HepG2 cells, and the results of the CCK8-assay and cell counting experiment showed that HES-CUR NPs exhibited a more significant antiproliferative effect than that of CUR in HepG2 cells. And HepG2 cells were more sensitive to apoptosis induced by HES-CUR NPs as evidenced by flow cytometry, increased cytochrome c level, and decreased full length caspase-3 and Bcl-2 protein expressions. Additionally, we found that the efficacy of HES-CUR NPs against HepG2 cells might be related to the enhanced degree of mitochondrial damage (decrease of the mitochondrial membrane potential and ATP) and autophagy (increased levels of Beclin-1 and LC3-II proteins). So, the findings in this study suggest that HES-CUR NPs have a great application potential in antitumor efficacy and play an important role in multiple signal pathways.

Enzymatic hydrolysis of kaempferol 3-O-(2‴-O-sinapoyl-β-sophoroside), the key bitter compound of rapeseed (Brassica napus L.) protein isolate.

The use of rapeseed protein for human nutrition is primarily limited by its strong bitterness, which is why the key bitter compound, kaempferol 3-O-(2‴-O-sinapoyl-β-sophoroside), is enzymatically degraded. Mass spectrometry analyses of an extract from an untreated rapeseed protein isolate gave three signals for m/z 815 [M-H]. The predominant compound among the three compounds was confirmed as kaempferol-3-O-(2‴-O-sinapoyl-β-sophoroside). Enzymatic hydrolysis of this key bitter compound was achieved using a sinapyl ester cleaving side activity of a ferulic acid esterase (FAE) from the basidiomycete Schizophyllum commune (ScoFAE). Recombinant ferulic acid esterases from Streptomyces werraensis (SwFAE) and from Pleurotus eryngii (PeFAE) possessed better cleavage activity towards methyl sinapate but did not hydrolyze the sinapyl ester linkage of the bitter kaempferol sophoroside. Kaempferol-3-O-(2‴-O-sinapoyl-β-sophoroside) was successfully degraded by enzymatic treatment with ScoFAE, which may provide a means to move the status of rapeseed protein from feed additive to food ingredient. © 2021 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

PH-Responsive Water-Soluble Polymer Carriers for Cell-Selective Metabolic Sialylation Labeling.

Cell-surface sialic acids can be metabolically labeled and subsequently modified using bioorthogonal chemistry. The method has great potential for targeted therapy and imaging; however, distinguishing the sialylation of specific cells remains a major challenge. Here, we described a cell-selective metabolic sialylation labeling strategy based on water-soluble polymer carriers presented with pH-responsive N-azidoacetylmannosamine (ManNAz) release. 2-Methacryloyloxyethyl phosphorylcholine contributed to increased water solubility and reduced nonspecific attachment to cells. Lactobionic acid residues, used for cell selectivity, recognized overexpressed receptors on target hepatoma cells and mediated cellular internalization. ManNAz caged by acidic pH-responsive carbonated ester linkage on the polymer was released inside target cells and expressed as azido sialic acid. Additionally, longer copolymer carriers enhanced the metabolic labeling efficiency of sialylation. This approach provides a platform for cell-selective labeling of sialylation and can be applied to high-resolution bioimaging and targeted therapy.

Thermoresponsive Polymer-Antibiotic Conjugates Based on Gradient Copolymers of 2-Oxazoline and 2-Oxazine.

A polymer-antibiotic conjugate with thermoresponsive properties near body temperature is presented. The backbone polymer is a copolymer of 2-n-propyl-2-oxazine (PropOzi) and methoxycarbonylethyl-2-oxazoline (C2MestOx) which is conjugated with the broad-spectrum antibiotic, cefazolin, via modification of the methyl ester group of C2MestOx. The resulting polymer-antibiotic conjugate has a cloud point temperature near body temperature, meaning that it can form a homogenous solution if cooled, but when injected into a skin-mimic at 37 °C, it forms a drug depot precipitate. Cleavage of the ester linker leads to quantitative release of the pristine cefazolin (with some antibiotic degradation observed) and redissolution of the polymer. When Escherichia coli were treated with polymer-antibiotic conjugate total clearance is observed within 12 h. The power of this approach is the potential for localized antibiotic delivery, for example, at a specific tissue site or into infected phagocytic cells.

Preparation and characterization of Gum Arabic Schiff's bases based on 9-aminoacridine with in vitro evaluation of their antimicrobial and antitumor potentiality

The conjugation between drug and biopolymers through an easily hydrolysable bond such as ester linkage, disulfide linkage, or imine-bond have been extensively employed to control the drug release pattern and improve its bioavailability. This work described the conjugation of 9-aminoacridine (9-AA) to Gum Arabic (GA) via Schiff's base, as a pH-responsive bond. First, GA was oxidized to Arabic Gum dialdehyde (AGDA), then a different amount of 9-AA (10, 25, and 50 mg 9-AA) was coupled to defined amount of AGDA, the coupling was confirmed by elemental analysis and different spectroscopic tools. In addition, the physical features of Schiff's base conjugates including surface morphology, thermal stability, and crystalline structure were examined. The thermogravimetric analysis revealed that the incorporation of 9-AA slightly improved the thermal stability. The coupling of 9-AA to AGDA dramatically enhanced its in vitro antimicrobial and antitumor activities. All conjugates exhibited broad-spectrum activity against Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, Bacillus subtilis, and Candida albicans. Moreover, AGA 25 and AGA 50 demonstrated promising capability to suppress the proliferation of human colon cancer cell line (Caco-2), with IC50 190.10 and 180.80 μg/mL respectively.

Adenylated proteins in mouse B16-F10 melanoma cells cluster in functional categories: a new paradigm for cellular regulation?

In mammals, AMPylation of cellular proteins is carried out by Huntingtin yeast-interacting protein E, and pseudokinase SelO. Lysates from mouse B16-F10 melanoma cells have been fractionated by immuno-precipitation using magnetic Dynabeads coated with antibodies against both adenosine 5′-monophosphate in phosphate ester linkage to tyrosine, and adenosine-phosphate. Proteins pulled down with both these antibodies were subject to post-translational modification, most likely AMPylation. Using tandem mass spectrometry, analysis of these protein fractions identified 333 proteins that could be pulled down by both antibodies. Many of these proteins clustered in 13 functional Ingenuity Pathway Analysis categories of 4 or more adenylated proteins including some from the cytoskeleton, and some involved with initiating the unfolded protein response. Supplemental data for this article is available online at https://doi.org/10.1080/15257770.2021.1995608 .

Insights into alkaline choline chloride-based deep eutectic solvents pretreatment for Populus deltoides: Lignin structural features and modification mechanism

Deep eutectic solvent (DES) is a kind of green solvent for biorefinery, which favors the progress of being more environmentally friendly and effective. A better understanding of structural changes of lignin is necessary to optimize pretreatment conditions and efficient utilization of the resultant lignin. The current study reported the structural features of lignin recovered from alkaline ChCl/imidazole and ChCl/urea DES pretreatment, and the mechanism of lignin modification was revealed. The profiling demonstrated that lignin samples possessed a high purity (>94.4%), low molecular weight ranging from 1544 to 2562 g/mol and an excellent uniformity (PDI < 1.6). Noteworthy, the content of β-O-4′ linkages in lignin was over 75% (i.e. 72.2%–77.4% retention); S/G ratio was increased whereas the content of -OCH3 groups were decreased. It was revealed that slight cleavage of β-O-4′ linkages, preferential breakdown of G units, and demethylation reaction were occurred during alkaline ChCl-based DES pretreatment. Specifically, cleavage of ester linkages between PB and lignin macromolecule was taking place during ChCl/imidazole pretreatment at a high temperature; whereas oxidation only appeared in ChCl/urea system. Despite the modification, well β-O-4′ preserved and less condensed lignin samples were recovered after low-temperature pretreatment. Consequently, high contents of phenol derivatives (26.3–30.6%) were achieved in lignin oil. The present study provides critical information on alkaline ChCl-based DES pretreatment, which will contribute to the valorization of lignin by-products and will be beneficial to the development of biorefineries.

Perfectly Alternating Copolymerization of CO and Epoxides to Aliphatic Polyester Oligomers via Cooperative Organoboron–Cobalt Complexes

The carbonylative polymerization of epoxides provides a promising but challenging strategy to synthesize polyhydroxyalkanoates (PHAs) which are of high commercial value in the field of biomedical materials and engineering plastics. Herein, a suite of well-defined bifunctional organoboron–cobalt catalysts, featuring simple preparation, high yields, and low metal content, are exploited for the carbonylative polymerization of epoxides to PHA oligomers. The organoboron–cobalt-mediated carbonylative polymerization exhibits high polyester selectivity (over 95%, four epoxide examples), and the obtained PHAs have more than 99% ester linkages on the polymer main chain. Detailed investigations based on in situ reactIR and 1H NMR analyses first found the concurrence of the direct alternating copolymerization of epoxides/CO, the ring expansion carbonylation of the epoxides to afford β-lactones, and the in situ homopolymerization of β-lactones under a single catalyst. This rare discovery provides a fundamentally different mechanism in the preparation of PHAs from CO/epoxides, extending the arsenal of catalytic systems that can copolymerize CO with epoxides.

Stimuli‐responsive polymeric additives for anticorrosion

AbstractCorrosion is a significant issue for metals and alloys items because it critically affects their lifetimes. To protect the metal from corrosion, corrosion inhibitors can be added into coatings, but the inhibitor can leach into the environment. Polymer‐corrosion inhibitor conjugates are developed to solve this problem. However, corrosion can occur in various fields of applications, which then need a different level and type of metal's protection. β‐thiopropionate and ester linkages between polymer and inhibitor are selected as model for very labile and moderately labile linkages, respectively. The rate of inhibitor's release is controlled by the linkage of conjugated payloads. Corrosion measurements indicated that polymers with the β‐thiopropionate linkage are suitable for severe corrosion and short‐term applications, whereas the polymers with ester linkage can be used for mild corrosion and long‐term applications.

Catalyst-free curing and closed-loop recycling of carboxylated functionalized rubber by a green crosslinking strategy

Current adopted rubber curing methods undergo large amounts of environmental issues, such as the release of toxic volatile organic compounds (VOCs) during curing process and difficulties in recycling of end-of-life rubbers. Many new curing reactions and cross-linking structures have been developed to solve these problems. A green curing strategy based on epoxy-acid reactions and ester linkages could be a potential alternative to the current curing ones. However, the curing reactions between epoxy and carboxyl groups generally require a catalysis to improve curing rate, and the recycling process requires toxic organic solution or high temperature. It is of great desired to develop a real environmentally friendly crosslinking strategy for rubber materials. In this paper, we report a facile and high-efficiency green crosslinking strategy for the carboxyl-functionalized rubber. N,N,N′,N'-tetraglycidyl-4,4′-diaminodiphenylmethane (TGDDM) was selected as a multifunctional amine-type high-efficiency crosslinker for carboxylated nitrile rubber (XNBR). TGDDM-cured XNBR exhibit extremely fast crosslinking rate and high crosslinking efficiency due to the four epoxy terminated units and tertiary amine structure acting as an internal catalyst. Besides, the mechanical properties and crosslinking density of TGDDM-cured XNBR can be regulated by TGDDM content. Furthermore, the ester linkage formed by curing reaction could be selectively and efficiently cleaved in a mixed solution of ethanol and water under mild condition. The closed-loop recovered XNBR maintains chemical structure and molecular weight and exhibit good mechanical performance. This strategy offers a promising way for high-efficient crosslinking of diene rubber as well as a real cost-effective and environmentally friendly recovery of end-of-life rubber materials.