- Activities of Arabidopsis sinapoylglucose:malate sinapoyltransferase shed light on functional diversification of serine carboxypeptidase-like acyltransferases
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Analysis of the catalytic properties of the serine carboxypeptidase-like (SCPL) 1-O-sinapoyl-β-glucose:l-malate sinapoyltransferase (SMT) from Arabidopsis showed that the enzyme exhibits besides its primary sinapoylation of l-malate, minor hydrolytic and disproportionation activities, producing free sinapic acid and 1,2-di-O-sinapoyl-β-glucose, respectively. The ability of the enzyme to liberate sinapic acid from the donor molecule 1-O-sinapoyl-β-glucose indicates the existence of a short-lived acylenzyme intermediate in the proposed random sequential bi-bi mechanism of catalysis. SMT-catalyzed formation of disinapoylglucose has been corroborated by docking studies with an established homology structure model that illustrates the possible binding of two 1-O-sinapoyl-β-glucose molecules in the active site and the intermolecular reaction of the two glucose esters. The SMT gene is embedded in a tandem cluster of five SCPL sinapoyltransferase genes, which encode enzymes with high amino acid sequence identities and partially overlapping substrate specificities. We assume that in recent duplications of genes encoding SCPL proteins, neofunctionalization of the duplicates to accept 1-O-sinapoyl-β-glucose as acyl donor was gained first, followed by subfunctionalization leading to different acyl acceptor specificities.
- Stehle, Felix,Brandt, Wolfgang,Schmidt, Juergen,Milkowski, Carsten,Strack, Dieter
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Read Online
- Dependency of the hydrogen bonding capacity of the solvent anion on the thermal stability of feruloyl esterases in ionic liquid systems
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Three feruloyl esterases, EC 3.1.1.73, (FAEs), namely FAE A from Aspergillus niger (AnFaeA), FAE C from Aspergillus nidulans (AndFaeC), and the FAE activity in a commercial β-glucanase mixture from Humicola insolens (Ultraflo L) were tested for their ability to catalyse esterification of sinapic acid with glycerol in four ionic liquid (IL) systems. The IL systems were systematically composed of two selected pairs of cations and anions, respectively: [BMIm][PF6], [C2OHMIm][PF6], [BMIm][BF4], and [C2OHMIm][BF4]. AnFaeA had activity in [PF6]--based ILs, whereas the AndFaeC and the FAE in Ultraflo L had no appreciable activities and were generally unstable in the IL systems. FAE stability in the IL systems was apparently highly dependent on enzyme structure, and notably AnFaeA's similarity to IL-compatible lipases may explain its stability. The thermal stability of AnFaeA was higher in buffer than in the IL systems, but at 40 °C and below there was no significant difference in AnFaeA stability between the buffer and the [PF6] --based systems: AnFaeA was stable in the [BMIm][PF6] and [C2OHMIm][PF6] systems for 2 h at 40 °C. However, the IL anion had a major effect on stability: [BF4]- caused rapid inactivation of AnFaeA, while [PF6]- did not. The cation did not have a similar effect. These observations could be explained in terms of the hydrogen bonding capacity of IL cations and anions via COSMO-RS simulations.
- Zeuner, Birgitte,Stahlberg, Tim,Van Buu, Olivier Nguyen,Kunov-Kruse, Andreas Jonas,Riisager, Anders,Meyer, Anne S.
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Read Online
- Total Syntheses and Anti-inflammatory Activities of Syringin and Its Natural Analogues
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Syringin (1), a natural bioactive glucoside isolated from the root of Acanthopanax senticosus (Rupr. Maxim.) Harms, possesses significant anti-inflammatory activity. In this study, we have accomplished the total syntheses of syringin (1), along with its natural analogues 2-12, from a common starting material, syringaldehyde (13), in 4-8 steps with an overall yields of 11.8-61.3%. The anti-inflammatory activities of these compounds were determined against NO production in the LPS-stimulated RAW264.7 cells. Among them, compounds 1-5, 7, and 9 exhibited different levels of anti-inflammatory activity.
- Dong, Hongbo,Du, Weihong,He, Yujiao,Shi, Zheng,Wang, Yingying,Wu, Min
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supporting information
p. 2866 - 2874
(2021/11/12)
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- Amino Group Functionalized Hf-Based Metal-Organic Framework for Knoevenagel-Doebner Condensation
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A Hf(IV) metal-organic framework (MOF) with di-amino functionalized linker was obtained as a crystalline solid with UiO-67 topology under solvothermal reaction conditions. The guest free form of Hf(IV) MOF (1′) was efficiently employed as a heterogeneous catalyst to synthesize cinnamic acid derivatives via Knoevenagel-Doebner reaction for the first time. The catalyst (1′) was efficiently active to directly achieve cinnamic acid from benzaldehyde and malonic acid. The solid retained its activity up to 6th cycle with no decay in its activity. The noticeable advantages of the catalyst are its milder reaction conditions, high yield, high stability, recyclable nature towards catalysis and wide substrate scope as well as shape-selective behaviour. The possible mechanism of the reaction was also studied thoroughly with suitable control experiments.
- Das, Aniruddha,Anbu, Nagaraj,Gogoi, Chiranjib,Dhakshinamoorthy, Amarajothi,Biswas, Shyam
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p. 3396 - 3403
(2021/08/20)
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- Tetracyclic Triterpenoids, Steroids and Lignanes from the Aerial Parts of Oxypetalum caeruleum
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The MeOH extract from dried aerial parts of Oxypetalum caeruleum (Apocynaceae) plants yielded seventeen compounds, including four new tetracyclic triterpenoids, one pregnane glycoside, two lignane glycosides, and ten known compounds. The structures of the
- Warashina, Tsutomu,Shirota, Osamu
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p. 226 - 231
(2021/02/09)
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- First total syntheses of two natural glycosides
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Isosyringinoside (1) and 3-(O-β-D-glucopyranosyl)-α-(O-β-D-glucopyranosyl)-4-hydroxy phenylethanol (2), the natural bioactive compounds contained unique structures, were first totally synthesized using easily available materials in short convenient routes with overall yields of 20.2% and 27.0%, respectively. An efficient total synthesis of 1 was developed in six steps, which contained two key steps of highly regioselective glycosylation without any selective protection steps. The seven-step synthesis of 2 involved two steps of regioselective glycosylations using BF3–O(C2H5)2 and TMSOTf as catalysts, respectively.
- Dong, Hongbo,Du, Weihong,Yao, Zhongquan,Wu, Min,Luo, Hongbing,He, Yujiao,Cao, Shenghua
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- Dual Nickel/Ruthenium Strategy for Photoinduced Decarboxylative Cross-Coupling of α,β-Unsaturated Carboxylic Acids with Cycloketone Oxime Esters
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Herein, a dual nickel/ruthenium strategy is developed for photoinduced decarboxylative cross-coupling between α,β-unsaturated carboxylic acids and cycloketone oxime esters. The reaction mechanism is distinct from previous photoinduced decarboxylation of α,β-unsaturated carboxylic acids. This reaction might proceed through a nickelacyclopropane intermediate. The C(sp2)-C(sp3) bond constructed by the aforementioned reaction provides an efficient approach to obtaining various cyanoalkyl alkenes, which are synthetically valuable organic skeletons in organic and medicinal chemistry, under mild reaction conditions. The protocol tolerates many critical functional groups and provides a route for the modification of complex organic molecules.
- Gao, Ang,Jiang, Run-Chuang,Liu, Chuang-Chuang,Liu, Qi-Le,Lu, Xiao-Yu,Xia, Ze-Jie
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supporting information
p. 8829 - 8842
(2021/06/30)
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- Bioassay of ferulic acid derivatives as influenza neuraminidase inhibitors
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Four series of ferulic acid derivatives were designed, synthesized, and evaluated for their neuraminidase (NA) inhibitory activities against influenza virus H1N1 in vitro. The pharmacological results showed that the majority of the target compounds exhibited moderate influenza NA inhibitory activity, which was also better than that of ferulic acid. The two most potent compounds were 1m and 4a with IC50 values of 12.77 ± 0.47 and 12.96 ± 1.34 μg/ml, respectively. On the basis of the biological results, a preliminary structure–activity relationship (SAR) was derived and discussed. Besides, molecular docking was performed to study the possible interactions of compounds 1p, 2d, 3b, and 4a with the active site of NA. It was found that the 4-OH-3-OMe group and the amide group (CON) of ferulic acid amide derivatives were two key pharmacophores for NA inhibitory activity. It is meaningful to further modify the natural product ferulic acid to improve its influenza NA inhibitory activity.
- Cui, Man-Ying,Xiao, Meng-Wu,Xu, Lv-Jie,Chen, Yun,Liu, Ai-Lin,Ye, Jiao,Hu, Ai-Xi
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- Expeditious and sustainable two-step synthesis of sinapoyl-l-malate and analogues: Towards non-endocrine disruptive bio-based and water-soluble bioactive compounds
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Faced with the increasing demand from both the cosmetic industries and consumers for bio-based, safe and natural skin products, sinapoyl-l-malate, widely described for its UV protection in plants, appears to be an excellent alternative to substitute chemical filters in sunscreens. Unfortunately, the only synthetic routes described in the literature were not only tedious but also exhibit a strong negative environmental impact, thus seriously limiting the industrialization and commercialization of sinapoyl-l-malate. Herein, a shorter and greener synthetic pathway involving Meldrum's acid opening with unprotected naturally occurring hydroxy acids and its subsequent Knoevenagel-Doebner condensation with biomass-derived p-hydroxybenzaldehydes was designed and developed. This two-step procedure, whom sustainability has been assessed using green metrics (atom economy (AE), process atom economy (PAE), E-factor and LCA), is a great alternative to the already reported procedures and allows the access to sinapoyl-l-malate and several analogs in average to good yield. The study of the anti-UV properties, stability against UV radiation, radical scavenging and antimicrobial activities of the targets revealed attractive properties as photostable UV filters, antioxidants and preservatives. Moreover, the water solubility brought by the free carboxylic acids facilitates the incorporation of these molecules in cosmetic formulations. Finally, their innocuousness toward endocrine disruption was demonstrated.
- Peyrot, Cédric,Mention, Matthieu M.,Fournier, Robin,Brunissen, Fanny,Couvreur, Julien,Balaguer, Patrick,Allais, Florent
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supporting information
p. 6510 - 6518
(2020/11/09)
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- Acylglycosides and Acylquinic Acids from Roots of Panax ginseng
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Glucose esters of sinapic and ferulic acids including a novel O-acylglycoside (1) and coumaroyl- and feruloylquinic acids were found for the first time in roots of Panax ginseng C. A. Mey. (Araliaceae). Compound 1 was 4-O-sinapoyl-α/β-D-glucopyranose according to UV and NMR spectroscopic and mass spectrometric data. A comparison of the biological activities of the isolated compounds found high antiradical activity (IC50 36.79–37.75 μM) for the sinapic-acid derivatives.
- Olennikov
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p. 1044 - 1047
(2020/11/03)
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- Selective Depolymerisation of γ-Oxidised Lignin via NHC Catalysed Redox Esterification
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The development of new catalytic methods for the processing of lignocellulose-derived renewable feedstocks continues to gain momentum, despite the considerable challenges associated with the use of complex biopolymers such as lignin. Here, we report a new two-step depolymerisation method for lignin involving primary alcohol oxidation followed by a NHC-mediated redox esterification-depolymerisation step. The process takes advantage of the inherent structure of the β-aryl ether units present in the specific type of lignin that was used (butanosolv) and delivers 4 novel aromatic monomers which retain the C3 side chain present in the lignin subunits. The utility of the major product is assessed suggesting that rapid access to a wide range of interesting chemical could be achieved from this renewable building block.
- Xiao, Ganyuan,Lancefield, Christopher S.,Westwood, Nicholas J.
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p. 3182 - 3186
(2019/06/24)
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- Pd-Catalyzed decarboxylative cross-coupling reactions of epoxides with α,β-unsaturated carboxylic acids
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A Pd-catalyzed decarboxylative cross-coupling of α,β-unsaturated carboxylic acids with cyclic and acyclic epoxides has been developed. Both β-monosubstituted and β-disubstituted unsaturated carboxylic acids, as well as conjugated diene unsaturated carboxylic acids are suitable reaction substrates. Substituted homoallylic alcohols were obtained in moderate to good yields. The product was obtained as a mixture of diastereomers favoring the anti diastereomer of the cyclic epoxides. This work provides a method for the modification of complex organic molecules containing α,β-unsaturated carboxylic acids.
- Lu, Xiao-Yu,Li, Jin-Song,Wang, Shi-Qun,Zhu, Yu-Jing,Li, Yue-Ming,Yan, Lu-Yu,Li, Jia-Mei,Wang, Jin-Yu,Zhou, Hai-Pin,Ge, Xiu-Tao
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supporting information
p. 11123 - 11126
(2019/09/20)
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- Investigating isomer specific photoprotection in a model plant sunscreen
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Sinapate esters are used throughout the plant kingdom, for example in photoprotection from ultraviolet radiation. Sinapate esters are naturally produced in their E-isomeric form; however, upon exposure to ultraviolet radiation, photoisomerization drives Z-isomer formation. To elucidate the photoprotection capacity of E vs. Z forms of sinapate esters, we explore the photochemistry of the model system, Z-ethyl sinapate. Following a novel Z-ethyl sinapate synthesis, we demonstrate that photoprotection is isomer independent. This suggests that, regarding photoprotection, there were no evolutionary pressures for biosynthesis of either isomer.
- Horbury,Flourat,Greenough,Allais,Stavros
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supporting information
p. 936 - 939
(2018/02/07)
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- First total synthesis of a new phenylpropanoid glycoside: natural cytotoxic compound from Cirsium japonicum
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Phenylpropanoid glycoside compound 1, the natural anti-tumor compound isolated from the erial parts of Cirsium japonicum, was first totally synthesized using easily available materials in short, convenient route with overall yield of 13.9%.
- Dong, Hong-Bo,Hou, Ming,Ma, Wen-Bo,Zhang, Jing-Xia,Li, Zhe-Yu,Luo, Hong-Bing,Tang, Ke-Hui,Cao, Sheng-Hua
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- COMPOUNDS FOR INHIBITING LIPID OXIDATION AND A METHOD FOR PRODUCING THE SAME
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The present invention relates to a compound for inhibiting lipid oxidation, and a producing method thereof. The compound for inhibiting lipid oxidation is synthesized by a transesterification reaction though a vinyl reaction and a lipase-catalyzed reaction. The produced compound for inhibiting lipid oxidation has an excellent effect of inhibiting oxidation according to a total oxidation value (TOTOX) which is a combination of a P-anisidine value (P-AnV) and a peroxide value (PV) and an analysis of a thiobarbituric acid reaction substance (TBARS).COPYRIGHT KIPO 2016
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Paragraph 0135-0136; 0143
(2017/05/03)
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- Triethylamine: A potential N-base surrogate for pyridine in Knoevenagel condensation of aromatic aldehydes and malonic acid
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Cinnamic acids are intermediates with significant potential for synthesis of several industrially important chemicals. Classically, cinnamic acids are produced through Knoevenagel condensation of aromatic aldehydes and malonic acid in the presence of an organocatalyst and large amounts of carcinogenic pyridine. An alternative pyridine free reaction scheme for Knoevenagel condensation of malonic acid and aromatic aldehydes was investigated by replacing pyridine with an aliphatic tertiary amine surrogate in toluene as the reaction medium. Of the three aliphatic tertiary amines used, namely, triethyl amine (TEA), trioctyl amine (TOA) and tributyl amine (TBA), only TEA afforded cinnamic acids in comparable yields to those obtained with pyridine. Validation through a computational analysis is attempted to provide an explanation for the observed role of TEA as an aliphatic N-base instead of TBA and TOA. The use of TEA as a mild base in place of pyridine can be seen as playing the dual role of a base catalyst as well as a phase transfer agent evidenced by the in-process ATR-FITR spectroscopy. Use of the TEA-toluene system in place of pyridine can be seen as resulting in a process that affords ease of handling, separation and recycling of the solvent and the catalyst.
- Pawar, Hitesh S.,Wagh, Adhirath S.,Lali, Arvind M.
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p. 4962 - 4968
(2016/07/06)
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- Design, synthesis, and docking studies of afatinib analogs bearing cinnamamide moiety as potent EGFR inhibitors
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Two series of afatinib derivatives bearing cinnamamide moiety (10a-n and 11a-h) were designed, synthesized and evaluated for the IC50 values against four cancer cell lines (A549, PC-3, MCF-7 and Hela). Two selected compounds (10e, 10k) were further evaluated for the inhibitory activity against EGFR and VEGFR2/KDR kinases. Seven of the compounds showed excellent cytotoxicity activity and selectivity with the IC50 values in single-digit μM to nanomole range. Three of them are equal to more active than positive control afatinib against one or more cell lines. The most promising compound 10k showed the best activity against A549, PC-3, MCF-7 and Hela cancer cell lines and EGFR kinase, with the IC50 values of 0.07 ± 0.02 μM, 7.67 ± 0.97 μM, 4.65 ± 0.90 μM and 4.83 ± 1.28 μM, which were equal to more active than afatinib (0.05 ± 0.01 μM, 4.1 ± 2.47 μM, 5.83 ± 1.89 μM and 6.81 ± 1.77 μM), respectively. Activity of compounds 10e (IC50 9.1 nM) and 10k (IC50 3.6 nM) against EGFR kinase were equal to the reference compound afatinib (IC50 1.6 nM). Structure-activity relationships (SARs) and docking studies indicated that replacement of the aqueous solubility 4-(dimethylamino)but-2-enamide group by cinnamamide moiety didn't decrease the antitumor activity. The results suggested that methoxy substitution had a significant impact on the activity and methoxy substituted on C-4 or C-2,3,4 position was benefit for the activity.
- Tu, Yuanbiao,Ouyang, Yiqiang,Xu, Shan,Zhu, Yan,Li, Gen,Sun, Chao,Zheng, Pengwu,Zhu, Wufu
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p. 1495 - 1503
(2016/03/15)
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- Design, Synthesis and Pharmacological Evaluation of Novel Piperlongumine derivatives as Potential Antiplatelet Aggregation Candidate
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A series of novel piperlongumine derivatives (4a-i, 6a-i) were designed and synthesized. The inhibitory activities of platelet aggregation induced by ADP and AA in vitro have been evaluated by bron turbidimetry and liver microsomal incubated assay. The assay results show that compounds 4e and 6e exhibited remarkable potency to that of the positive control piplartine and aspirin.
- Wang, Yujun,Wang, Jie,Li, Jiaming,Zhang, Yanchun,Huang, Weijun,Zuo, Jian,Liu, Huicai,Xie, Di,Zhu, Panhu
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p. 833 - 840
(2016/05/19)
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- Regioselective enzymatic β-carboxylation of para-hydroxy-styrene derivatives catalyzed by phenolic acid decarboxylases
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Abstract We report on a 'green' method for the utilization of carbon dioxide as C1 unit for the regioselective synthesis of (E)-cinnamic acids via regioselective enzymatic carboxylation of para-hydroxystyrenes. Phenolic acid decarboxylases from bacterial sources catalyzed the β-carboxylation of para-hydroxystyrene derivatives with excellent regio- and (E/Z)-stereoselectivity by exclusively acting at the β-carbon atom of the C=C side chain to furnish the corresponding (E)-cinnamic acid derivatives in up to 40% conversion at the expense of bicarbonate as carbon dioxide source. Studies on the substrate scope of this strategy are presented and a catalytic mechanism is proposed based on molecular modelling studies supported by mutagenesis of amino acid residues in the active site.
- Wuensch, Christiane,Pavkov-Keller, Tea,Steinkellner, Georg,Gross, Johannes,Fuchs, Michael,Hromic, Altijana,Lyskowski, Andrzej,Fauland, Kerstin,Gruber, Karl,Glueck, Silvia M.,Faber, Kurt
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p. 1909 - 1918
(2015/06/02)
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- The synthesis and analysis of advanced lignin model polymers
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If the lignin-first biorefinery concept becomes a reality, high quality lignins close in structure to native lignins will become available in large quantities. One potential way to utilise this renewable material is through depolymerisation to aromatic chemicals. This will require the development of new chemical methods. Here, we report the synthesis and characterisation of advanced lignin model polymers to be used as tools to develop these methods. The controlled incorporation of the major linkages in lignin is demonstrated to give complex hardwood and softwood lignin model polymers. These polymers have been characterised by 2D HSQC NMR and GPC analysis and have been compared to isolated lignins.
- Lancefield,Westwood
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supporting information
p. 4980 - 4990
(2015/11/16)
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- Design, synthesis and biological evaluation of novel trimethylpyrazine-2- carbonyloxy-cinnamic acids as potent cardiovascular agents
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A series of novel trimethylpyrazine-2-carbonyloxy-cinnamic acids and esters were designed, synthesized and evaluated for their inhibitory effect on adenosine diphosphate (ADP)-induced platelet aggregation in vitro and also assayed for their protective effect against hydrogen peroxide (H 2O2)-induced oxidative damage on Ea.hy926 cells. The results showed that many compounds exhibited high activity in one or both of the assays, of which, compound F′10 displayed the highest protective effect on the proliferation of the damaged Ea.hy926 cells (EC50 = 1.7 μM), presenting almost 40 times higher potency than that of lipoic acid, and compound F3 was the most active anti-platelet aggregation agent with IC 50 = 9.6 μM, comparable to that of clopidogrel. The structure-activity relationships of these compounds were also discussed.
- Chen, Hongfei,Li, Guoning,Zhan, Peng,Li, Hong,Wang, Shouxun,Liu, Xinyong
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supporting information
p. 711 - 718
(2014/06/10)
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- Synthesis and biological evaluation of hydroxycinnamic acid hydrazide derivatives as inducer of caspase-3
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In order to generate compounds with superior antitumor activity and reduced toxicity, twelve new hydroxycinnamic acid hydrazide derivatives were synthesized and evaluated for their antiproliferative activities against two cancer cell lines (H1299 lung carcinoma cells and MCF-7 breast cancer cells), and compared to two normal counterparts (NL-20 lung epithelial cells and H184B5F5/M10 breast cells) by MTT method. The results demonstrated that some of these compounds possessed good antiproliferative activity against the two cancer cell lines. Among them, compound 2c was active against the growth of H1299 lung carcinoma cells with IC50 values of 1.50 μM, which was more active than the positive topotecan (IC50 = 4.18 μM). Simultaneously, it showed lower cytotoxic effects on normal NL-20 lung epithelial cells (IC50 > 10 μM). Mechanism studies indicated that it induced cell cycle arrest at G2/M phase followed by activation of caspase-3, and consequently caused the cell death. Further studies on the structure optimization are ongoing.
- Wu, Zheng-Rong,Liu, Jian,Li, Jian-Ying,Zheng, Li-Fang,Li, Yang,Wang, Xing,Xie, Qing-Jian,Wang, Ai-Xia,Li, Ying-Hui,Liu, Rong-Hui,Li, Hong-Yu
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p. 778 - 783
(2014/11/08)
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- New acylated oligosaccharides from Pistacia integerrima
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Integrisides A (1) and B (2), new acylated oligosaccharides, have been isolated from the n-butanol-soluble sub-fraction of the methanolic extract collected from the aerial parts of Pistacia integerrima. Their structures were elucidated by spectroscopic techniques and hydrolysis.
- Ullah, Zia,Mehmood, Rashad,Imran, Muhammad,Malik, Abdul,Afzal, Rehana A.
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p. 2027 - 2032
(2014/01/06)
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- Synthesis of a new urea derivative: A dual-functional organocatalyst for Knoevenagel condensation in water
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A phenylalanine-urea compound-catalyzed Knoevenagel condensation in water is reported. Various aldehydes and active methylene compounds undergo condensation at room temperature to give the desired products in high yields. The mechanism of the condensation of aldehydes with Meldrum's acid catalyzed by the novel urea derivative is also disclosed.
- Le, Wen-Jun,Lu, Hong-Fei,Zhou, Jun-Tao,Cheng, He-Long,Gao, Yu-Hua
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supporting information
p. 5370 - 5373
(2013/09/12)
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- Triacylated peonidin 3-sophoroside-5-glucosides from the purple flowers of Moricandia ramburii Webb.
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Triacylated peonidin 3-sophoroside-5-glucosides were isolated from the purple flowers of Moricandia ramburii Webb. (Family: Brassicaceae), and determined to be peonidin 3-O-[2-O-(2-O-(trans-feruloyl)-glucosyl)-6-O-(trans-p- coumaroyl)-glucoside]-5-O-[6-O-(malonyl)-glucoside] (1), peonidin 3-O-[2-O-(2-O-(trans-feruloyl)-glucosyl)-6-O-(cis-p-coumaroyl)-glucoside] -5-O-[6-O-(malonyl)-glucoside] (2) and peonidin 3-O-[2-O-(2-O-(trans-sinapoyl)- glucosyl)-6-O-(trans-p-coumaroyl)-glucoside]-5-O-[6-O-(malonyl)-glucoside] (3), respectively, by chemical and spectroscopic methods. In addition, one known acylated cyanidin glycoside, cyanidin 3-O-[2-O-(2-O-(trans-feruloyl)-glucosyl)- 6-O-(trans-p-coumaroyl)-glucoside]-5-O-[6-O-(malonyl)-glucoside] (4), was also identified in the flowers. Peonidin glycosides have not been reported hitherto in floral tissues in to Brassicaceae.
- Tatsuzawa, Fumi,Ito, Kanako,Muraoka, Hiroki,Namauo, Toshiharu,Kato, Kazuhisa,Takahata, Yoshihito,Ogawa, Satoshi
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experimental part
p. 73 - 77
(2012/06/30)
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- Synthesis and structure-activity relationships and effects of phenylpropanoid amides of octopamine and dopamine on tyrosinase inhibition and antioxidation
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Phenylpropanoid amides of octopamine (OA) 1a-1e and dopamine (DA) 2a-2e were synthesised and the structure-activity relationships (SARs) for antioxidant and tyrosinase inhibition activities were analysed. Among synthesised compounds, 2c, which contains two catechol moieties, exhibited the most DPPH radical-scavenging activity (EC50 = 16.2 ± 2.4 μM), and 1d exhibited significant tyrosinase inhibitory activity (IC50 = 5.3 ± 1.8 μM). Interestingly, with the same acid moiety, OA derivatives showed more inhibitory effect on tyrosinase than did compounds derived from DA, whereas DA derivatives were found to have higher antioxidant activity than compounds derived from OA. The relationship between their structures and their potencies, demonstrated in the current study, will be useful for the design of optimal agents.
- Wu, Zhengrong,Zheng, Lifang,Li, Yang,Su, Feng,Yue, Xiaoxuan,Tang, Wei,Ma, Xiaoyan,Nie, Junyu,Li, Hongyu
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scheme or table
p. 1128 - 1131
(2012/07/28)
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- Biologically active bergenin derivatives from bergenia stracheyi
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New bergenin derivatives, bergecins A and B (1 and 2, resp.), have been isolated from the AcOEt-soluble fraction of Bergenia stracheyi, along with bergenin (3), and their structures were elucidated on the basis of 1H- and 13C-NMR spectra, and by COSY, HMQC, and HMBC experiments. Compound 2 showed potent inhibitory potential against the enzyme lipoxygenase, while 1 was moderately active. On the other hand, both compounds exhibited significant antioxidant activities in 1,1-diphenyl-2-picrylhydrazyl (DPPH) scavenging assay. Copyright
- Siddiq, Farah,Fatima, Itrat,Malik, Abdul,Afza, Nighat,Iqbal, Lubna,Lateef, Mehreen,Hameed, Saira,Khan, Sher Wali
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body text
p. 91 - 98
(2012/04/10)
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- Oxidative depolymerization of lignin in ionic liquids
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Beech lignin was oxidatively cleaved in ionic liquids to give phenols, unsaturated propylaromatics, and aromatic aldehydes. A multiparallel batch reactor system was used to screen different ionic liquids and metal catalysts. Mn(NO3)2 in 1-ethyl-3-methylimidazolium trifluoromethanesulfonate [EMIM][CF3SO3] proved to be the most effective reaction system. A larger scale batch reaction with this system in a 300mL autoclave (11g lignin starting material) resulted in a maximum conversion of 66.3% (24h at 100 °C, 84 × 105 Pa air). By adjusting the reaction conditions and catalyst loading, the selectivity of the process could be shifted from syringaldehyde as the predominant product to 2,6-dimethoxy-1,4-benzoquinone (DMBQ). Surprisingly, the latter could be isolated as a pure substance in 11.5 wt% overall yield by a simple extraction/crystallization process.
- St?rk, Kerstin,Taccardi, Nicola,B?smann, Andreas,Wasserscheid, Peter
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experimental part
p. 719 - 723
(2011/12/21)
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- FLAVAN-3-OL CONTAINING FOODSTUFFS
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The use of a compound for the reduction or elimination of bitterness caused by flavan-3-ols is provided. Compositions having greater than 0.01 wt % flavan-3-ols and that comprise an effective amount of the compound are also provided. The compound conforms to the general formula (I): wherein R1 represents C2-C3 saturated or unsaturated divalent hydrocarbon radical, n is an integer from 0 to 3, and each X is independently selected from C1-C3 alkyloxy and OH; and wherein if n is 0 then R1 is C3 saturated divalent hydrocarbon radical or C2-C3 unsaturated divalent hydrocarbon radical; and wherein if n is greater than 0 then the compound has formula (II)
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- INHIBITION OF THE FORMATION OF AGEs
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The present invention relates to the use of an active substance that promotes the inhibition of the formation of AGEs, for preparing a composition to prevent and/or combat the reduction in elastic and plastic properties of tissues, and in particular of the skin, for inhibiting the formation of AGEs, or for preventing and/or combating glycation of proteins in the skin. The invention also relates to a method of screening such active substances.
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- Synthesis and antioxidant activity of hydroxycinnamic acid xylan esters
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Naturally occurring hydroxycinnamic acids, such as ferulic and sinapic acids, are known to possess antioxidant activity. In this study, ferulic acid and sinapic acid were covalently attached to oat spelt arabinoxylan and birch wood glucuronoxylan by esterification in a two-step feasible synthesis to generate modified xylans with various degrees of substitution. The obtained derivatives were fully analyzed by FT-IR, NMR, and HPSEC experiments to confirm the esterification of xylans and the degree of substitution. The antioxidative potential of the conjugates was evaluated using the emulsion lipid oxidation test. The results demonstrate that the derivatized xylans inhibited lipid oxidation notably better than the native oat spelt and birch wood xylans. It was found that ferulic acid esters of glucuronoxylan were more efficient antioxidants than those of arabinoxylan and that sinapic acid xylan esters were more efficient than their ferulic acid counterparts.
- Wrigstedt, Pauli,Kylli, Petri,Pitkaenen, Leena,Nousiainen, Paula,Tenkanen, Maija,Sipilae, Jussi
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body text
p. 6937 - 6943
(2011/08/09)
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- Insights into lignin primary structure and deconstruction from Arabidopsis thaliana COMT (caffeic acid O-methyl transferase) mutant Atomt1
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The Arabidopsis mutant Atomt1 lignin differs from native lignin in wild type plants, in terms of sinapyl (S) alcohol-derived substructures in fiber cell walls being substituted by 5-hydroxyconiferyl alcohol (5OHG)-derived moieties. During programmed lignin assembly, these engender formation of benzodioxane substructures due to intramolecular cyclization of their quinone methides that are transiently formed following 8-O-4′ radical-radical coupling. Thioacidolytic cleavage of the 8-O-4′ inter-unit linkages in the Atomt1 mutant, relative to the wild type, indicated that cleavable sinapyl (S) and coniferyl (G) alcohol-derived monomeric moieties were stoichiometrically reduced by a circa 2:1 ratio. Additionally, lignin degradative analysis resulted in release of a 5OHG-5OHG-G trimer from the Atomt1 mutant, which then underwent further cleavage. Significantly, the trimeric moiety released provides new insight into lignin primary structure: during polymer assembly, the first 5OHG moiety is linked via a C8-O-X inter-unit linkage, whereas subsequent addition of monomers apparently involves sequential addition of 5OHG and G moieties to the growing chain in a 2:1 overall stoichiometry. This quantification data thus provides further insight into how inter-unit linkage frequencies in native lignins are apparently conserved (or near conserved) during assembly in both instances, as well as providing additional impetus to resolve how the overall question of lignin macromolecular assembly is controlled in terms of both type of monomer addition and primary sequence.
- Moinuddin, Syed G. A.,Jourdes, Michael,Laskar, Dhrubojyoti D.,Ki, Chanyoung,Cardenas, Claudia L.,Kim, Kye-Won,Zhang, Dianzhong,Davin, Laurence B.,Lewis, Norman G.
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experimental part
p. 3928 - 3946
(2010/09/17)
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- A new diterpenoid and other constituents from Acanthopanax brachypus harms
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Phytochemical investigation of the stem bark of Acanthopanax brachypus afforded a new labdanetype diterpene glycoside, 3α-trans-sinapoyloxy- jhanol 18-O-β-D-glucopyranoside (1), together with four known compounds, including one diterpene acid, acanthoic a
- Hu, Hao-Bin,Fan, Jun
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experimental part
p. 1186 - 1190
(2010/08/20)
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- New cardenolide and acylated lignan glycosides from the aerial parts of Asclepias curassavica
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Three new cardenolide glycosides and six new acylated lignan glycosides were obtained along with nineteen known compounds from the aerial parts of Asclepias curassavica L. (Asclepiadaceae). The structure of each compound was determined based on interpreta
- Warashina, Tsutomu,Shikata, Kimiko,Miyase, Toshio,Fujii, Satoshi,Noro, Tadataka
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experimental part
p. 1159 - 1163
(2009/10/02)
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- Synthesis and antioxidant activities of 3,5-dialkoxy-4-hydroxycinnamamides
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A series of 3,5-dialkoxy-4-hydroxycinnamamides 6 and 7 was synthesized, and their antioxidant activity was assessed using the thiobarbituric acid reactive substance (TBARS) assay. Interestingly, cinnamamides with longer alkoxy groups on the C-3 and C-5 positions display enhanced inhibition, and most of the compounds in the series tested exhibit excellent lipid peroxidation inhibitory activities. Some cinamamides bearing hexyloxy or 2,6-di-tert-butyl-4-methyl phenol groups have submicromolar inhibitory activities.
- Kang, Tae-Souk,Jo, Hyang-Ok,Park, Woo-Kyu,Kim, Jong-Pyung,Konishi, Yasuo,Kong, Jae-Yang,Park, No-Sang,Jung, Young-Sik
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p. 1663 - 1667
(2008/12/21)
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- Cosmetic use of derivatives of 3-Phenylpropionic acid
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The use of a compound having formula I wherein Y is selected from the group consisting of H, an alkyl group, a phenyl group, Na, K or NH4, and wherein R1, R2, R3, R4 and R5 are independently selected from the group consisting of H and -O-R6, wherein R6 is selected from the group consisting of H and a linear or branched, saturated or unsaturated alkyl group comprising 1 to 6 carbon atoms, and wherein at least one of the substituents R1, R2, R3, R4 and R5 is not H, for the manufacture of a composition for the cosmetic treatment of human skin, scalp or hair and for the cosmetic treatment of human skin, scalp or hair.
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Page/Page column 10
(2008/06/13)
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- Jasmonate-induced changes in flavonoid metabolism in barley (Hordeum vulgare) leaves
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The effects of jasmonic acid (JA) on secondary metabolism in barley (Hordeum vulgare L.) were investigated. A reversed-phase HPLC analysis revealed that the amount of a particular compound increased in excised barley leaf segments that had been treated with JA. This compound was purified and identified as 6?-feruloylsaponarin (1) by spectroscopic analyses and alkaline hydrolysis. A related compound, 6?-sinapoylsaponarin (2), was also found to accumulate in excised leaves independently of the JA treatment. The accumulation of these compounds was accompanied by a decrease in the saponarin (3) content. [8,9-13C]p-Coumaric acid and [2,3,4,5,6- 2H]L-phenylalanine were effectively incorporated into the hydroxycinnamoyl moieties in 1 and 2, while the degree of incorporation of the labeled precursors into the saponarin part was small. These findings indicate that the hydroxycinnamoyl moieties of 1 and 2 are synthesized de novo from phenylalanine via the phenylpropanoid pathway, and that the saponarin part is mainly provided by the constitutive pool of 3.
- Ishihara, Atsushi,Ogura, Yuki,Tebayashi, Shin-Ichi,Iwamura, Hajime
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p. 2176 - 2182
(2007/10/03)
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- Inter- and intramolecular isotopic correlations in some cyanogenic glycosides and glucosinolates and their practical importance
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Sinalbin is a complex organic salt from white mustard. The δ 13C- values of the aromatic parts of the anion glucosinalbin (p- hydroxyphenylacetic acid) and of the cation sinapin (sinapic acid) are identical (-32.2‰) and both aromatic compounds are depleted by 6.4‰ with respect to the glucose moiety (-25.8‰) bound in glucosinalbin. The δ 13C value of the choline part of the molecule can be correlated to its metabolic origin from glucose. However, there is an unexpected dramatic 13C- enrichment in the first C atom of glucosinalbin, originally the C-2 of tyrosine. This enrichment of approximately 11% relative to the mean value of the aglycone is found in the same position of four other glucosinolates and cyanogenic glycosides derived from phenylalanine or tyrosine. An isotope effect on the phenylalanine-ammonia-lyase reaction is discussed as the most probable cause for this finding. In contrast, sinigrin, the glucosinolate from black mustard, shows a relative 13C-depletion of 6.5‰ in the corresponding first C-atom of the aglycone allyl mustard oil. The proposed reason for this depletion is an isotope effect on an aldol reaction during the biosynthetic introduction of this C-atom into the aglycone skeleton. Synthetic allyl mustard oil is depleted by 14% in the same position relative to the δ 13C-value of the whole molecule, probably owing to an isotope effect on the first step of its chemical synthesis, the binding of allyl amine to CS2. This difference can be used to detect adulterations of mustard.
- Butzenlechner, Maria,Thimet, Susanne,Kempe, Klaus,Kexel, Hugo,Schmidt, Hanns-Ludwig
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p. 585 - 592
(2007/10/03)
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- A SINAPIC ACID ESTER FROM BOREAVA ORIENTALIS
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A new sinapic acid ester, 6-O-β-D-(2'-O-sinapoyl)glucopyranosyl β-D-(1,2-di-O-disinapoyl)glucopyranose, was identified from fruits of Boreava orientalis.Structural elucidation was carried out on the basis of UV, mass, 1H and 13C NMR spectral data, including 2D shift correlation and selective INEPT experiments.
- Sakushima, Akiyo,Coskun, Maksut,Tanker, Mekin,Tanker, Nevin
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p. 1481 - 1484
(2007/10/02)
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- TWO ACYLATED ANTHOCYANINS FROM DIOSCOREA ALATA
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Two new anthocyanins, cyanidin and peonidin 3-gentiobioside acylated with sinapic acid, have been isolated from the tuber of Dioscorea alata L. 'King yam' originated from Sri Lanka.These structures are elucidated by spectroscopic methods.
- Shoyama, Yukihiro,Nishioka, Itsuo,Herath, Water,Uemoto, Shunpei,Fujieda, Kunimitsu,Okubo, Hiroshi
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p. 2999 - 3001
(2007/10/02)
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- BIOSYNTHESIS OF PODOPHYLLUM LIGNANS - I. CINNAMIC ACID PRECURSORS OF PODOPHYLLOTOXIN IN PODOPHYLLUM HEXANDRUM
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Feeding experiments in Podophyllum hexandrum plants have established that phenylalanine, cinnamic acid and ferulic acid are good precursors of the two major aryltetralin lignans podophyllotoxin and 4'-demethylpodophyllotoxin.Sinapic and 3,4,5-trimethoxycinnamic acids were poorly utilized, showing that the substitution pattern of the pendent aryl ring is built up after coupling of the two phenylpropane units.Degradation studies on podophyllotoxin derived from ferulic acid show that the two halves of the lignan molecule are equally labelled supporting a biosynthetic sequence involving oxidative coupling of two similar phenylpropane precursors having the substitution pattern of ferulic acid.Although 3,4-methylenedioxycinnamic acid was readily incorporated, degradative studies prove that this compound is not incorporated intact, but via a metabolic sequence in which the methylenedioxy carbon atom enters the C1-pool and then labels the methylenedioxy and methoxyl substituents of podophyllotoxin.The rest of the skeleton is incorporated via ferulic acid, presumably by way of caffeic acid.Key Word Index - Podophyllum hexandrum; Podophyllaceae; aryltetralin; lignans; biosynthesis; podophyllotoxin.
- Jackson, David E.,Dewick, Paul M.
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p. 1029 - 1036
(2007/10/02)
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- THE PREPARATION OF COUMARIC ACIDS VIA STYRYLISOXAZOLES
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The preparation of coumaric acids (2a-f) by hydrolysis of the requisite 3-methyl-4-nitro-5-styrylisoxazoles (1a-f) is reported.
- Chimichi, Stefano,Sio, Francesco De,Donati, Donato,Fina, Giuseppe,Pepino, Roberto,Sarti-Fantoni, Piero
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p. 263 - 267
(2007/10/02)
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- 4-HYDROXYBENZOYLCHOLINE: A NATTURAL PRODUCT PRESENT IN SINAPIS ALBA
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The total fractions of choline esters have been isolated from different parts of Sinapis alba. 4-Hydroxybenzoylcholine has been identified and found to be one of the quantitatively dominating choline esters in seed extracts of S. alba.The identity of the new natural product has been confirmed by comparison with synthetic reference compounds.Several different choline esters are present in this plant but in extracts of seedlings, leaves, and inflorescences they are not so quantitatively dominating as in seeds.The modified ion-exchange technique applied appeared to be an ef ficient tool in the isolation and separation of choline esters and amines from other types of phenolic plant constituents.Key Word Index - Sinapis alba; Cruciferae; choline esters; sinapine; 4-hydroxy-3,5-dimethoxycinnamoylcholine; 4-hydroxybenzoylcholine; 3-hydroxybenzoylcholine; 2-hydroxybenzoylcholine; 4-hydroxy-3-methoxybenzoylcholine; 3-hydroxy-4-methoxybenzoylcholine; phenols; choline ester synthesis.
- Clausen, Svend,Olsen, Ole,Soerensen, Hilmer
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p. 917 - 922
(2007/10/02)
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