487-35-4Relevant articles and documents
Syringaresinol: A Renewable and Safer Alternative to Bisphenol A for Epoxy-Amine Resins
Janvier, Marine,Hollande, Louis,Jaufurally, Abdus Samad,Pernes, Miguel,Ménard, Rapha?l,Grimaldi, Marina,Beaugrand, Johnny,Balaguer, Patrick,Ducrot, Paul-Henri,Allais, Florent
, p. 738 - 746 (2017)
A renewable bisepoxide, SYR-EPO, was prepared from syringaresinol, a naturally occurring bisphenol deriving from sinapic acid, by using a chemo-enzymatic synthetic pathway. Estrogenic activity tests revealed no endocrine disruption for syringaresinol. Its glycidylation afforded SYR-EPO with excellent yield and purity. This biobased, safe epoxy precursor was then cured with conventional and renewable diamines for the preparation of epoxy-amine resins. The resulting thermosets were thermally and mechanically characterized. Thermal analyses of these new resins showed excellent thermal stabilities (Td5 %=279–309 °C) and Tgranging from 73 to 126 °C, almost reaching the properties of those obtained with the diglycidylether of bisphenol A (DGEBA), extensively used in the polymer industry (Td5 %=319 °C and Tg=150 °C for DGEBA/isophorone diamine resins). Degradation studies in NaOH and HCl aqueous solutions also highlighted the robustness of the syringaresinol-based resins, similar to bisphenol A (BPA). All these results undoubtedly confirmed the potential of syringaresinol as a greener and safer substitute for BPA.
Preparation and relevance of a cross-coupling product between sinapyl alcohol and sinapyl p-hydroxybenzoate
Lu, Fachuang,Ralph, John,Morreel, Kris,Messens, Eric,Boerjan, Wout
, p. 2888 - 2890 (2004)
Cross-coupling of sinapyl p-hydroxybenzoate and sinapyl alcohol was investigated. The cross-coupling reaction between 1a and 1b produces an intermediary bis-quinone methide, but one such moiety is internally trapped by the single 9-OH. The cross-coupling product 2ab in plants is compelling evidence that sinapyl p-hydroxybenzoate must therefore be an authentic monomer in the lignin pathway. The results show that sinapyl p-hydroxybenzoate 1b is an authentic precursor of lignification.
Dirigent Proteins Guide Asymmetric Heterocoupling for the Synthesis of Complex Natural Product Analogues
Kim, Stacie S.,Sattely, Elizabeth S.
supporting information, p. 5011 - 5021 (2021/05/04)
Phenylpropanoids are a class of abundant building blocks found in plants and derived from phenylalanine and tyrosine. Phenylpropanoid polymerization leads to the second most abundant biopolymer lignin while stereo- and site-selective coupling generates an array of lignan natural products with potent biological activity, including the topoisomerase inhibitor and chemotherapeutic etoposide. A key step in etoposide biosynthesis involves a plant dirigent protein that promotes selective dimerization of coniferyl alcohol, a common phenylpropanoid, to form (+)-pinoresinol, a critical C2 symmetric pathway intermediate. Despite the power of this coupling reaction for the elegant and rapid assembly of the etoposide scaffold, dirigent proteins have not been utilized to generate other complex lignan natural products. Here, we demonstrate that dirigent proteins from Podophyllum hexandrum in combination with a laccase guide the heterocoupling of natural and synthetic coniferyl alcohol analogues for the enantioselective synthesis of pinoresinol analogues. This route for complexity generation is remarkably direct and efficient: three new bonds and four stereocenters are produced from two different achiral monomers in a single step. We anticipate our results will enable biocatalytic routes to difficult-to-access non-natural lignan analogues and etoposide derivatives. Furthermore, these dirigent protein and laccase-promoted reactions of coniferyl alcohol analogues represent new regio- and enantioselective oxidative heterocouplings for which no other chemical methods have been reported.
Pinoresinol-lariciresinol reductase: Substrate versatility, enantiospecificity, and kinetic properties
Davin, Laurence B.,Hwang, Julianne K.,Lewis, Norman G.,Moinuddin, Syed G. A.
, (2020/03/26)
Two western red cedar pinoresinol-lariciresinol reductase (PLR) homologues were studied to determine their enantioselective, substrate versatility, and kinetic properties. PLRs are downstream of dirigent protein engendered, coniferyl alcohol derived, stereoselective coupling to afford entry into the 8- and 8′-linked furofuran lignan, pinoresinol. Our investigations showed that each PLR homolog can enantiospecifically metabolize different furofuran lignans with modified aromatic ring substituents, but where phenolic groups at both C4/C4′ are essential for catalysis. These results are consistent with quinone methide intermediate formation in the PLR active site. Site-directed mutagenesis and kinetic measurements provided additional insight into factors affecting enantioselectivity and kinetic properties. From these data, PLRs can be envisaged to allow for the biotechnological potential of generation of various lignan skeleta, that could be differentially “decorated” on their aromatic ring substituents, via the action of upstream dirigent proteins.
Syringaresinol inhibits UVA-induced MMP-1 expression by suppression of mapk/ap-1 signaling in hacat keratinocytes and human dermal fibroblasts
Joo, Yung Hyup,Karadeniz, Fatih,Ko, Jaeyoung,Kong, Chang-Suk,Oh, Jung Hwan
, (2020/06/08)
Ultraviolet (UV) irradiation induces detrimental changes in human skin which result in photoaging. UV-induced intracellular changes cause degradation of extracellular matrix (ECM). UV-stimulated cleavage of collagen in ECM occurs via matrix metalloproteinases (MMPs). (±)syringaresinol (SYR), a phytochemical which belongs to the lignan group of polyphenols, was investigated for its ability to reverse the UVA-induced changes in human HaCaT keratinocytes and dermal fibroblasts (HDFs) in vitro. Effect of SYR on UVA-induced changes was investigated by production and activation of MMPs and its transcriptional upstream effectors; mitogen-activated protein kinases (MAPKs) and pro-inflammatory mediators. Levels of expression were determined using ELISA, RT-PCR and immunoblotting. UVA irradiation stimulated the production of MMP-1 and inhibited collagen production. SYR treatment suppressed MMP-1 and enhanced collagen production in UVA-irradiated HaCaT keratinocytes and HDFs. SYR repressed the UV-induced phosphorylation of p38, ERK and JNK MAPKs in HaCaT keratinocytes while only suppressing JNK phosphorylation in HDFs. In addition, SYR was able to inhibit UVA-induced production of inflammatory cytokines; TNF-α, COX-2, IL-1β and IL-6. Moreover, SYR suppressed the activator protein-1 (AP-1), a heterodimer of phosphorylated transcription factors c-Jun and c-Fos. SYRtreatment decreased nuclear levels of activated c-Fos and c-Jun as a mechanism to inhibit UVAinduced transcriptional activities leading to MMP-1 production. In conclusion, current results demonstrated that SYR could inhibit UVA-induced upregulation of MMP-1 by suppressing MAPK/AP-1 signaling in HaCaT keratinocytes and HDFs. Therefore, SYR was suggested as a potential compound with antiphotoaging properties against UVA-induced skin aging.
