Rosin Derivatives Research Articles

Development of biobased, sustainable and environmentally friendly glycerol ester rosins for the production of thermoplastic road marking paint

AbstractIn recent years, natural rosin derivatives have gained significant importance in the production of sustainable bio‐based materials, including thermoplastic road marking paint (TRMP). This study evaluates the use of sustainable natural glycerol ester rosins as bio‐based binders in TRMP formulations, specifically focusing on pine, wood, and tall oil rosins. Various analytical techniques, such as FT‐IR, TGA, MALDI‐TOF‐MS and GPC‐HPLC, were utilized to analyze both unmodified and glycerol ester rosins. Standard tests, including acid number (mg KOH/g) ASTM D 465‐05 and softening point (°C) ASTM E 28‐99, were also conducted on the samples. The optimum synthesis conditions for glycerol ester rosins (GER) were determined as follows: a rosin/glycerol molar ratio of 2.54, catalyst/rosin weight ratio of 0.5%, and antioxidant/rosin weight ratio of 1.0%. GPC‐HPLC analysis revealed average esterification reaction yields of over 90.85%. Furthermore, TRMPs underwent various tests, including gloss factor (β), chromaticity coordinates (x, y), UVB aging, and softening point (°C). The results demonstrated that GERs exhibited superior performance, especially in the UVB aging test, with all TRMPs classified as UV1 type. These findings highlight the promising potential of GERs derived from different types of rosins in producing sustainable, environmentally friendly, and bio‐based next‐generation TRMPs.

Fabrication of polyethyleneimine grafted maleopimaric acid glycidyl methacrylate ester stationary phase for mixed-mode liquid chromatography

Due to their advantages of low green toxicity, diverse sources, renewable nature, and excellent biocompatibility, natural products have been extensively utilized in the exploration and development of novel stationary phase materials for liquid chromatography. In this study, we fabricated a rosin-based stationary phase material for mixed-mode chromatography by utilizing maleopimaric acid glycidyl methacrylate ester (MPAG) and polyethyleneimine (PEI) as ligands. Initially, silica was functionalized with MPAG through thiol-ene click reaction, followed by the grafting of PEI via an imidization reaction to produce Sil-MPAG-PEI material. This material exhibited both anion exchange and hydrophilic interaction properties due to the presence of PEI, allowing for the switching of its retention mode from reversed-phase mode to a mixed-mode incorporating reversed-phase, hydrophilic interaction and ion-exchange chromatography (RPLC/HILIC/IEC) under different mobile phase conditions. Consequently, Sil-MPAG-PEI demonstrated the ability to provide various interactions, including hydrophobic, π-π, hydrogen bond, hydrophilic, ion exchange, and electrostatic interactions. These interactions enabled selective separation among compounds with different polarities, such as nucleosides/bases, benzoic acids, flavonoids, alkylbenzenes, phenols, anilines, and polycyclic aromatic hydrocarbons (PAHs). Furthermore, Sil-MPAG-PEI demonstrated excellent chromatographic stability, as evidenced by the low relative standard deviations (RSDs) of the retention time for interday precision and interday precision were 0.042 %-0.275 % (n = 10) and 0.159 %-0.932 % (n = 7). The column was also successfully employed for the quantitative determination of evodiamine and rutaecarpine in an extract solution of Evodiae fructus, achieving concentrations of 9.102 and 3.256 mg/g, respectively. These results demonstrate the potential of Sil-MPAG-PEI in the analysis of complexsamples. Briefly, this study investigated and confirmed the potential application of rosin derivatives in mixed-mode liquid chromatography separations has been investigated and verified. The exceptional separation ability of Sil-MPAG-PEI indicates that it is a promising separation material for chromatographic separation.

Pentaerythritol and Glycerol Esters Derived from Gum Rosin as Bio-Based Additives for the Improvement of Processability and Thermal Stability of Polylactic Acid

Gum rosin esters are some of the most common gum rosin derivatives used in different applications, such as coatings, paper, varnishes, chewing gum, and food industries. In this study, gum rosin esters are used as additives for polylactic acid (PLA) to improve its processability and thermal stability. Blends of an amorphous PLA with two different gum rosin esters, pentaerythritol ester and glycerol ester, were prepared by melt extrusion process in concentrations from 1, 3, and 5 phr. Besides the comparison of thermal degradation, microstructure assessment, and melt flow index (MFI) analysis, the processability performance during testing samples production by injection molding process was evaluated. Experimental results showed that MFI values of PLA-gum rosin ester blends increased by 100%, 147%, and 164%, along with increasing content of gum rosin esters addition, in both cases. Also, both derivatives slightly improved PLA thermal stability (around 3ºC higher). Injection molding temperature decreased by at least 20 °C for PLA-gum rosin ester blends compared with neat PLA. Furthermore, the maximum tensile strength of PLA-gum rosin esters was negligibly affected in formulations with low content of gum rosin esters, and the FESEM images revealed a good dispersion and compatibility of gum rosin ester particles into PLA matrix in both concentrations.

Bio-Based Ca2+-Selective Supramolecular Metallohydrogels with Ultra-mechanical Responsiveness, Selective Dye Adsorption, and Recycling.

Water pollution is one of the major problems that need to be solved in modern society, and there is a need to develop an effective adsorbent to purify the polluted water. In this article, three supramolecular metallohydrogels containing a three-dimensional network structure have been prepared from rosin derivatives. The supramolecular metallohydrogels have good thermal stability and maintain mechanical strength at high temperatures. Interestingly, the sodium N-(dehydroabiety1)maleamate/Ca2+ supramolecular metallohydrogels exhibit rare multi-stimulus responsiveness (mechanical vibration, temperature, pH, EDTA, etc.), especially to mechanical vibration with over 10 cycles, indicating ultra-mechanical response properties. More importantly, the unique three-dimensional network structure of the metallohydrogels can effectively adsorb cationic dyes in the wastewater. The adsorption amount and adsorption rate of this supramolecular metallohydrogels for rhodamine 6G after 48 h were at least 160.6 mg/g and 97%, respectively. The adsorption kinetic process of this metallohydrogel follows a quasi-secondary kinetic model, where the adsorption process is mainly electrostatic and weak π-π interactions. And the metallohydrogels can also be recovered by 0.5 mol/L hydrochloric acid solution desorption after adsorption of the dye. This is the first supramolecular metallohydrogel system prepared from the natural product rosin and applied to dye adsorption. This broadens the application of rosin in the field of supramolecular gel and dye adsorption and recycling.

Development of Rosin Derivative Crosslinked Vegetable Oil Based Keratin Fiber Reinforced Biodegradable Composites

Development of Rosin Derivative Crosslinked Vegetable Oil Based Keratin Fiber Reinforced Biodegradable Composites

Ecofriendly Viscoelastic Solutions Formed from a Recyclable Rosin-Based Amine Oxide Surfactant.

Innovations in molecular structures formed using bioresources are efficient means to prepare surfactant aggregates with unique properties. Here, a rosin-based amine oxide surfactant (R-11-3-AO) containing large hydrophobic groups was synthesized from rosin derivatives, namely, dehydroabietic acid and long-chain amino acids. Cryo-transmission electron microscopy showed that R-11-3-AO molecules formed extremely long wormlike micelles with a cross-sectional diameter of 4-5 nm at a concentration of approximately 7 mmol·L-1. A gel-like system was obtained at approximately 30 mmol·L-1 due to the dense entanglement of the wormlike micelles. The solutions also exhibited unique shear thickening behavior at a shear rate of approximately 10 s-1 even at high concentrations. The large hydrophobic group contained in R-11-3-AO is the origin of the strong van der Waals interactions between the surfactant molecules, resulting in the rapid growth of wormlike micelles. This rosin-based surfactant is the first recoverable amine oxide surfactant from solutions through the salting-out effect with high recovery rates. This work demonstrates the unique capabilities of rosin-based surfactants for forming wormlike micelles and provides opportunities for the development of surfactant recovery technologies.

Metal ions recognition and DNA binding properties of four rosin derivatives

Four rosin derivatives containing amide, pyridine and dehydroabietyl sub-units were synthesized. Their selective and sensitive recognition of Cu2+ and Fe3+ ions were confirmed by UV–vis and fluorescence spectra. Their detection limits for Cu2+ and Fe3+ were lower than the maximum allowable levels of Cu2+ and Fe3+ in drinking water. They could displace ethidium bromide (EB) molecules inserted into CT DNA base pairs and induce fluorescence quenching of CT DNA-EB system in a static mode. The negative ΔG values proved that the binding processes of the compounds to CT DNA were spontaneous. The negative values of both ΔH and ΔS solidified that the hydrogen bonds or Van der Waals was the driving force for the interactions between the four compounds and CT DNA. Metal ion recognition and DNA interaction indicate that the number of pyridine rings and the flexibility of the compounds had influence on the strength of the above activities.

Strain-induced orientation facilitates the fabrication of highly stretchable and tough xylan-based hydrogel for strain sensors

Stretchable and tough polysaccharide-based functional hydrogels have gained popularity for various applications. However, it still remains a great challenge to simultaneously own satisfactory stretchability and toughness, particularly when incorporating renewable xylan to offer sustainability. Herein, we describe a novel stretchable and tough xylan-based conductive hydrogel utilizing the natural feature of rosin derivative. The effect of different compositions on the mechanical properties and the physicochemical properties of corresponding xylan-based hydrogels were systematically investigated. Owing to the multiple non-covalent interactions among different components to dissipate energies and the strain-induced orientation of rosin derivative during the stretching, the highest tensile strength, strain, and toughness of xylan-based hydrogels could reach 0.34 MPa, 2098.4 %, and 3.79 ± 0.95 MJ/m3, respectively. Furthermore, by incorporating MXene as the conductive fillers, the strength and toughness of hydrogels were further enhanced to 0.51 MPa and 5.95 ± 1.19 MJ/m3. Finally, the synthesized xylan-based hydrogels were able to serve as a reliable and sensitive strain sensor to monitor the movements of human beings. This study provides new insights to develop stretchable and tough conductive xylan-based hydrogel, especially utilizing the natural feature of bio-based resources.

Curing and thermal comparative study of rosin epoxy thermosets with bio-based imidoamines and commercial curing agents

This paper includes the curing of previously synthesized multifunctional bio-based epoxy resins (PEMPAE/TMPAE) with rosin-based imidoamine curing agents (IAMDK/IASDK/IAEDK) which are nucleophilic addition reaction products of diamino diphenyl ether (DDE) and dimaleopimaryl ketone (DMPK), a dehydrodecarboxylated derivative of MPA. Curing dynamics of rosin-based epoxy resins (PEMPAE/TMPAE) with rosin-based imidoamine curing agents (IAMDK/IASDK/IAEDK) were evaluated using differential scanning calorimetry. For comparison, the bio-based epoxy resins were also cured with rosin derivative dimaleopimaryl ketone (DMPK) and commercial-based diamino diphenyl ether (DDE). The universal testing machine and thermogravimetric analyzer) were used to measure the mechanical properties and thermal stability of the cured epoxy samples. The samples’ chemical resistance was assessed by calculating the weight loss in percent after they were submerged in solutions of NaOH, HCl, and NaCl. We also used scanning electron microscopy (SEM) to examine the morphological changes. Rosin-based epoxy cured with imidoamine curing agents outperformed the commercial epoxy in terms of performance.

Biotesting in an Environmental Monitoring System: Safety Assessment of Rosin Derivatives

Biotesting in an Environmental Monitoring System: Safety Assessment of Rosin Derivatives

Rosin Derivative IDOAMP Inhibits Prostate Cancer Growth via Activating RIPK1/RIPK3/MLKL Signaling Pathway.

Rosin derivatives such as dehydroabietic acid and dehydroabietic amine belonging to diterpenoids have similar structure with androgen that inhibited the occurrence and development of prostate cancer. In this study, the effects and possible mechanism of the rosin derivative IDOAMP on prostate cancer were investigated. Our results showed that IDOAMP effectively inhibited cell viabilities of LNCaP, PC3, and DU145 prostate cells. After the treatment with IDOAMP, the levels of cleaved-PARP, LC3BII/I, and HMGB1 were increased, whereas the expression of GPX4 was decreased. Interestingly, cell viability was reversed by the supplements of necrostatin-1 and necrosulfonamide. Meanwhile, the IDOAMP downregulated the expression of human Aurora kinase A that was overexpressed in prostate cancer. In addition, co-IP results showed that IDOAMP inhibited the binding of Aurora kinase A to the receptor-interacting serine/threonine kinase 1 (RIPK1) and RIPK3. However, the binding of RIPK1 to FADD, RIPK3, or MLKL was significantly promoted. Further studies showed that the phosphorylation levels of RIPK1, RIPK, and MLKL were increased in a concentration-dependent manner. In in vivo model, IDOAMP reduced the tumor volumes and weights. In conclusion, IDOAMP directly inhibited Aurora kinase A and promoted the RIPK1/RIPK3/MLKL necrosome activation to inhibit the prostate cancer.

Water-in-Oil Emulsion Gels Stabilized by a Low-Molecular Weight Organogelator Derived from Dehydroabietic Acid.

High concentrations of surfactants or gelators are usually necessary to prepare emulsions gels with unusual physicochemical properties. This situation may be improved by innovating the aggregate morphology in systems. Herein, a rosin-based molecule is designed and synthesized using dehydroabietic acid as the starting material (denoted as R-Lys-R). The molecule acts as an effective organogelator and can gelate several hydrocarbon compounds with a minimum gelation concentration of 0.2% (w/v). Analysis using atomic force microscopy (AFM) and circular dichroism (CD) reveals that in n-decane, R-Lys-R forms left-handed helical fibers with a cross-sectional diameter of approximately 15 nm. The directional hydrogen bonding of the amide group is helpful to the formation of aggregates. At concentrations of R-Lys-R above 2%, water-in-oil emulsions are transformed into emulsion gels owing to the aptitude of R-Lys-R in gelating the oil phase. The concentrations of the emulsifier can be adjusted to obtain emulsion gels with different formulations. This work reveals the potential of rosin derivatives for the formation of small molecular weight organogels and provides a novel method for the utilization of natural resources in soft materials and home care products.

Discovery of Natural Rosin Derivatives Containing Oxime Ester Moieties as Potential Antifungal Agents to Control Tomato Gray Mold Caused by Botrytis cinerea.

Inspired by the application of natural products against pathogenic fungi, two series of dehydroabietyl oxime ester derivatives were synthesized using rosin as a raw material. Based on the evaluation and screening of in vitro antifungal activities against Botrytis cinerea (B. cinerea), Sclerotinia sclerotiorum, Valsa mali, Rhizoctonia solani, Fusarium oxysporum, and Alternaria alternata, compound 4f exhibited the best antifungal activity against B. cinerea, and its EC50 was 0.798 mg/L, which was lower than that of the positive control trifloxystrobin (1.112 mg/L). The in vivo antifungal activity results showed that 4f had satisfactory protective and curative effects on tomato. Physiological and biochemical studies showed that the action mechanism of compound 4f against B. cinerea is to change the morphology and the ultrastructure of the mycelium, increase the permeability of the cell membrane, and cause nucleus and mitochondrial dysfunction, thus leading to apoptosis. In addition, qualitative and quantitative structure-activity relationship studies showed that the inductive and conjugative interactions between compound 4f and the target receptor form an electron transfer process, thereby achieving an antifungal effect. These results indicated that compound 4f, which was derived from the natural product rosin, is a novel potential fungicidal candidate against B. cinerea.

Synthesis and evaluation of new coatings based on chemically modified rosin and PMMA for steel substrates

Rosin derivatives used as coatings on a variety of substrates provide electrical insulation and corrosion protection. This paper explores the feasibility of using two chemically modified rosins, which are the glycerol rosin ester (GRE) and GRE-poly(methyl methacrylate) (GRE-PMMA) used as stainless steel coatings to reduce friction and wear rate. The chemical structures of GRE and GRE-PMMA are investigated via FTIR to evaluate frictions and wear characteristics of coated stainless steel-substrates; these are tested on a ball-on-disc tribometer, followed by a careful observation of the obtained surface using an optical microscope. The FTIR results reveal structural differences among rosin, GRE, and PMMA; which relates to the suppression of –COOH groups and the appearance of new –OH and –COOR groups. The GRE and GRE-PMMA coatings on the substrate, reduce the friction coefficient by 49% and 46% (before coating 0.59 and after coating 0.30 and 0.32) and wear rate by 29% and 26% (before coating 6.8 and after coating 4.8 and 5.0) respectively. These findings suggest that GRE and GRE-PMMA are effective coatings as protective agents for stainless-steel substrates due to the attractive forces between the organic molecule and the metal surface.

Robust pH-switchable pickering emulsions stabilized solely by organic Rosin-based particles with adjustable wettability

Pickering emulsions that are stabilized by organic particles that are issued from renewable sources have attracted considerable attention. However, developing green and robust Pickering emulsions of various types via simple methods has always been an important challenge. Herein, a rosin derivative, namely, maleopimaric acid (MPA), which has three carboxylic acid groups, is used to stabilize Pickering emulsions. Various types of gel-like Pickering emulsions can be obtained by adjusting the wettability of rigid MPA by changing the pH, such as water (W) in oil (O), O/W, double, and multiple emulsions. With increasing MPA concentration and volume fraction of the oil phase, phase inversion occurs from W/O to O/W and from O/W to W/O, respectively. The formed gel-like Pickering emulsions have excellent external stimulus and mechanical stabilities and can withstand high temperature (70 °C), freeze-thaw treatment and high centrifugal forces. These outstanding properties are due to the stable interfacial film and the network structure that are formed by the self-assembly of MPA with heterogeneous ionization degrees. This study provides a natural rosin-based solid stabilizer with adjustable wettability and further advances the design of stable Pickering emulsions with various structural features based on practical application needs.

Multifunctional novel rosin derivatives based on dehydroabietylamine with metal ion sensing and DNA/BSA binding activities

Three novel rosin derivatives based on dehydroabietylamine which is an important modified product of rosin, pyridine and substituted phenol were synthesized and fully characterized. The DNA binding study results obtained by using fluorescence spectroscopy, thermal denaturation, viscosity and circular dichroism (CD) spectroscopy, reveal that they could interact with calf thymus DNA (CT DNA) through intercalation. The interactions of the title compounds with bovine serum albumins (BSA) were investigated through various spectroscopic techniques. The obtained experimental data show that they could quench the intrinsic fluorophore of BSA by a static quenching mechanism and induce structural alteration in BSA. The molecular docking technique was used to ascertain their interactions toward DNA and BSA. Furthermore, they could selectively and irreversibly recognize some individual metal ions very well, even to the extent of naked eye recognition. DNA/BSA binding, molecular docking and metal ion recognition findings together prove that the substituent on the phenol group had a great influence on their functions. This work provides a reference for the rational investigation of novel bioactive derivatives of rosin.

Sustainable Polyurethane Networks Based on Rosin with Reprocessing Performance.

Rosin is an abundant natural product. In this paper, for the first time, a rosin derivative is employed as a monomer for the preparation of polyurethane vitrimers with improved properties. A novel rosin-based polyurethane vitrimers network was constructed by the reaction between isocyanates (HDI) as curing agent and monomers with alcohol groups modified from rosin. The dynamic rosin-based polyurethane vitrimers were characterized by FTIR and dynamic mechanical analysis. The obtained rosin-based polyurethane vitrimers possessed superior mechanical properties. Due to the dynamic urethane linkages, the network topologies of rosin-based polyurethane vitrimers could be altered, contributing self-healing and reprocessing abilities. Besides, we investigated the effects of healing time and temperature on the self-healing performance. Moreover, through a hot press, pulverized samples of 70%VPUOH could be reshaped several times, and the mechanical properties of the recycled samples were restored, with tensile strength being even higher than the of that of the original samples.

Characterization and evaluation of novel sustainable polymers derived from renewable rosin

PurposeThis study aims to prepare low-cost biomaterials from renewable natural resources (rosin).Design/methodology/approachPreparation of different biomaterials, ethylene glycol maleic rosin (EGMR), glycerol maleic rosin, pentaerythritol maleic rosin and sorbitol maleic rosin (SMR) esters, then evaluated by stability studies, moisture absorption, swelling index parameters, thermogravimetric analysis and skin irritation studies.FindingsThe prepared rosin derivatives had excellent moisture safety, according to the results. From EGMR to SMR, the swelling indices increase.Research limitations/implicationsThese rosin biomaterials were used in coating, especially in the field of pharmaceutical coating, and good results were obtained in this study.Practical implicationsAs these biomaterials rosin derivatives have excellent moisture resistance, they are recommended for use as coating materials for moisture-sensitive drugs.Originality/valueThere has recently been a lot of interest in researching the effects of rosin derivatives in various drug delivery systems.

Rosin-Based Epoxy Vitrimers with Dynamic Boronic Ester Bonds.

Rosin is an abundantly available natural product. In this paper, for the first time, a rosin derivative is employed as the main monomer for preparation of epoxy vitrimers to improve the mechanical properties of vitrimers. Novel epoxy vitrimer networks with dynamic reversible covalent boronic ester bonds are constructed by a reaction between thiols in 2,2′–(1,4–phenylene)–bis (4–mercaptan–1,3,2–dioxaborolane) (BDB) as a curing agent and epoxy groups in the rosin derivative. The rosin-based epoxy vitrimer networks are fully characterized by Fourier transform infrared spectroscopy (FTIR), an equilibrium swelling experiment, and dynamic mechanical analysis (DMA). The obtained rosin-based epoxy vitrimers possess superior thermostability and good mechanical properties. Due to transesterification of boronic ester bonds, rosin epoxy vitrimer network topologies can be altered, giving welding, recycle, self-healing, and shape memory abilities to the fabricated polymer. Besides, the effects of treating time and temperature on welding capability is investigated, and it is found that the welding efficiency of the 20% C-FPAE sample is >93% after treatment for 12 h at 160 °C. Moreover, through a hot press, the pulverized samples of 20% C-FPAE can be reshaped several times and most mechanical properties are restored after reprocessing at 200 °C for 60 min. Finally, chemical degradation is researched for the rosin-based epoxy vitrimers.

Effect of Natural Crosslinker on the Properties of Chicken Feather and Modified Vegetable Oil Based Green Composites

ABSTRACT For the past few decades environmental concerns had been influencing the researchers to employ natural fibers and polymers from renewable resources as a replacement for petroleum-based resins and synthetic fibers. In this work, materials from renewable resources were used to prepare the composites. Modified epoxidised soybean oil as resin was employed to prepare the composites with chicken feather fibers as the reinforcing agent by compression molding technique. Epoxidised soybean oil (ESO) was modified by reacting with methacrylic acid and methacrylic anhydride to form resin. Rosin acid derivative was synthesized to serve as the crosslinker for replacement of the petroleum based divinylbenzene (DVB). For comparison, divinylbenzene (DVB) was also employed to copolymerize with the same resin. Chemical structure of rosin derivative was verified by 1H-NMR spectroscopy. FT-IR study showed the interaction between resin, chicken feather fiber (CFF) and rosin derivatives. The morphological features of the composites were evaluated by scanning electron microscopy (SEM), where it indicated a uniform interaction among the components of the composites. Different experimental results showed that the composites with higher amount of rosin acid derivative showed better properties. Results demonstrated that rosin acid derivative can serve as a substitute for petroleum-based rigid compounds for preparing biocomposites.