Cinnamoyl Groups Research Articles

(S)-(+)-Decursin and its Analogues as Inhibitors of Cytokines Secretion Induced by DpE in THP-1/EoL-1 Cell Line

(S)-(+)-Decursin and its analogues were synthesized and evaluated for their inhibitory effects on monocyte chemoattractant protein-1 (MCP-1), interleukin-8 (IL-8), and IL-6 secretion induced by Dermatophagoides pteronyssinus extract (DpE) in human acute monocytic leukemia (THP-1) cells and eosinophilic leukemia (EoL-1) cell lines. (S)-(+)- Decursin analogues with alkyl acryloyl groups, apart from (S)-(+)-decursin (1) and (S)-(+)-decursinol angelate (4a), did not influence the regulation of cytokine secretion. (S)-(+)-Decursin analogues (8d, 8f, 8g) with cinnamoyl groups carrying hydroxyl- and acetoxy-substitutes potently inhibited the secretion of MCP-1 and IL-6. The structure-activity relationship study revealed that increasing π-rich environment at the extensions from the eastern alcohol of (S)-(+)-decursin is a key element in building the pharmacophore for achieving the desired biological activity.

Gold nanoparticles–loaded cinnamoyl pluronic F-127/cinnamoyl alginate microparticles prepared by a spray-drying method

ABSTRACTA gold nanoparticle (GNP)–loaded microparticle was prepared by spray drying the mixture solution of GNP, cinnamoyl pluronic F127, and cinnamoyl alginate, and by dimerizing the cinnamoyl groups under the irradiation of UV light. The cinnamic acid content in the cinnamoyl polymers was determined by 1H NMR spectroscopy and colorimetric method. The GNP content in the surface of microparticle was 6.45% (w/w), determined by energy-dispersive X-ray spectroscopy. The cumulative release amount for 12 h at 45°C was markedly higher than that observed at lower temperatures. Near-infrared irradiation significantly promoted the release from the GNP-loaded microparticle because of heat generation from GNP.

Photocrosslinkable Trehalose Derivatives Carrying Mesogenic Groups: Synthesis, Characterization, and in Vitro Evaluation for Fibroblast Attachment.

A photocrosslinkable trehalose derivative carrying mesogenic groups was synthesized by esterification reactions. The derivative (TC-HBPHA) was synthesized by the reaction of partially cinnamoyl-modified trehalose (TC4) with 4-(4-hexyloxybenzoyloxy)phenoxy-6-oxohexanoic acid (HBPHA) as a mesogenic unit. TC-HBPHA showed a nematic liquid crystalline mesophase at a temperature range from 150 °C to 175 °C in the heating process under observation with a polarized optical microscope. The dimerization of the cinnamoyl groups of TC-HBPHA by ultraviolet (UV) light irradiation was monitored by ultraviolet-visible (UV-Vis) spectroscopy and Fourier transform infrared (FT-IR) spectroscopy. The photocrosslinked film was obtained after the UV irradiation of TC-HBPHA, and it kept the liquid crystalline mesophase at almost the same temperature range. Fibroblast cells cultured on the photocrosslinked TC-HBPHA proliferated as well as on the polystyrene culture plate, indicating that the film has no toxicity. Interestingly, some cells on photocrosslinked TC-HBPHA had a spindle shape and aligned characteristically.

Spray‐dried microparticles composed of cinnamoyl poly(N‐isopropylacrylamide‐co‐hydroxyethylacrylate) and gold nanoparticle

ABSTRACTTemperature‐ and NIR irradiation‐responsive microparticles composed of cinnamoyl poly(N‐isopropylacrylamide‐co‐hydroxyethylacrylate) [CinP(NIPAM‐HEA)] and gold nanoparticle (GNP) were prepared by a spray‐drying method. According to the cloud points determined by an optical method, the HEA content in P(NIPAM‐HEA) had no marked effect on the lower critical solution temperature (LCST). However, the cinnamoyl group content in CinP(NIPAM‐HEA) had a significant effect on the LCST. The LCSTs determined by a calorimetric method was in agreement with those determined by an optical method. The hydrodynamic mean diameter of gold nanoparticle (GNP) prepared by reducing gold ions was about 30 nm and it seemed to be a nanosphere on TEM photo. Spray‐dried CinP(NIPAM‐HEA) microparticles containing GNP was 1.5 μm to 12 μm in diameter on SEM photo. Gold was detected on the energy‐dispersive X‐ray spectrum of the microparticles. The amount of FITC‐dextran released for 12 h from the microparticles was much higher at temperatures above the LCST (at 37 °C and 45 °C) than below the LCST (at 20 °C and 25 °C). The cumulative release amount in 12 h was only about 3% without NIR irradiation, whereas the value was about 26.5% when NIR was irradiated to the microparticle suspension. The photothermal energy generated by GNP was believed to render the thermosensitive copolymers de‐swollen and hydrophobic, allowing for the active release of dye from the microparticles. The NIR irradiation‐responsive GNP‐loaded microparticles could be applied to the development of NIR‐responsive drug carriers which release their contents in response to an external stimulus (i.e., NIR irradiation). © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44141.

Synthesis and evaluation of (+)-decursin derivatives as inhibitors of the Wnt/β-catenin pathway

We synthesized (+)-decursin derivatives substituted with cinnamoyl- and phenyl propionyl groups originating from (+)-CGK062 and screened them using a cell-based assay to detect relative luciferase reporter activity. Of this series, compound 8b, in which a 3-acetoxy cinnamoyl group was introduced, most potently inhibited (97.0%) the Wnt/β-catenin pathway. Specifically, compound 8b dose-dependently inhibited Wnt3a-induced expression of the β-catenin response transcription (CRT) and increased β-catenin degradation in HEK293 reporter cells. Furthermore, compound 8b suppressed expression of the downstream β-catenin target genes cyclin D1 and c-myc and suppressed PC3 cell growth in a concentration-dependent manner.

Structure Determination of Monomeric Phloroglucinol Derivatives with a Cinnamoyl Group Isolated from Propolis of the Stingless Bee, Tetragonula carbonaria

AbstractTetragocarbones A and B were isolated from the propolis of an Australian stingless bee, Tetragonula carbonaria. These largely planar structures were proposed as a result of NMR analysis as well as comparison of their NMR data with those of related monomeric phloroglucinol derivatives. To elucidate relative and absolute stereochemistry of tetragocarbone A, the synthesis of the proposed structure of tetragocarbone A was performed. As a result, the synthetic compound bearing stereogenic centers 1R*,3R*,6S* was identical with naturally occurring tetragocarbone A. The absolute stereochemistry of tetragocarbone A was established to be 1R,3R,6S by chiral HPLC separation and X‐ray analysis. Comparison of the NMR data of tetragocarbone A with that of tetragocarbone B indicated that tetragocarbone B would be a natural congener of tetragocarbone A.

Development of fluorescent probes for hydrogen polysulfides by using cinnamate ester as the recognition unit

Hydrogen polysulfides (H2Sn, n>1) are newly discovered intracellular reactive species considered to be involved in cytoprotective processes and redox signaling. The emerging evidences imply that the actual signaling molecule is H2Sn rather than H2S. In this work, we screened a series of coumarinyl cinnamate esters with different electron- withdrawing groups on the phenyl ring of cinnamoyl moiety and found that 3-(trifluoromethyl) cinnamate ester showed a desirable turn-on fluorescence response to H2Sn with high specificity. Based on this result, a turn-on fluorescent probe for H2Sn was constructed by incorporating a 3- (trifluoromethyl) cinnamoyl group to N,N-diethylrhodol. The probe showed good selectivity and sensitivity for H2Sn and proved to be able to assessing H2Sn levels in serum as well as in live cells.

Studies on Photoreactive and Fluorescence Properties of Polymers Composed of 3-Hydroxycinnamic Acid and Lactic Acid

In this paper, a series of novel copolymers with photoreactive and fluorescence properties known as poly (3-hydroxycinnamic acid-co-lactide acid) (P(3HCA-co-LA)) were obtained by the thermal melt-polycondensation of 3-hydroxycinnamic acid and lactide acid. The chemical structures and average molecular weight of the P(3HCA-co-LA) copolymers were analyzed by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (1H NMR) and gel permeation chromatography (GPC). The P(3HCA-co-LA) copolymers showed good photoreactivities and fluorescent properties. Isomerization and [2+2] cycloaddition of the cinnamoyl groups occurred under UV irradiation. Furthermore, fluorescence intensity could be controlled by controlling the composition of P(3HCA-co-LA) copolymers.

Synthesis, self-assembly, and formation of photo-crosslinking-stabilized fluorescent micelles covalently containing zinc(II)-bis(8-hydroxyquinoline) for ABC triblock copolymer bearing cinnamoyl and 8-hydroxyquinoline side groups

Triblock copolymers (MPEG-b-PCEMA-b-PHQHEMA) bearing cinnamoyl and 8-hydroxyquinoline side groups with different block length are synthesized by a two-step reversible addition fragmentation chain transfer polymerization of cinnamoyl ethyl methacrylate (CEMA) and 2-((8-hydroxyquinolin-5-yl)methoxy)ethyl methacrylate (HQHEMA), respectively. The self-assembly of MPEG-b-PCEMA-b-PHQHEMA in mixture of THF and ethanol is investigated by varying the ratio of THF and ethanol. Spheric micelles with diameter of 63.7 nm and polydispersity of 0.128 are obtained for MPEG113-b-PCEMA15-b-PHQHEMA17 in THF/ethanol with a volume ratio (v/v) of 5/5. The PCEMA inner shell of the resulted micelles is photo-crosslinked under UV radiation to give stabilized micelles. The complex reaction of the stabilized micelles with Zn(II) is investigated under different conditions to give zinc(II)-bis(8-hydroxyquinoline)(Znq2)-containing micelles. When the complex reaction is carried out in THF/ethanol (v/v = 5/5) or THF/toluene (v/v = 6/4) with zinc acetate, fluorescent Znq2-containing micelles are obtained without obvious change in diameters and morphologies. The fluorescent micelles exhibit green emission with λmax at 520 nm. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 1056–1064

Reversible Cross-Linking of Aliphatic Polyamides Bearing Thermo- and Photoresponsive Cinnamoyl Moieties

Photosensitive polymers have gained strong attention in development of different polymeric systems for diverse applications. Particular attention is paid to polymers with cinnamoyl groups either in polymer backbone or in pendent position owing to their excellent photoreactivity and thermoreactivity upon UV light irradiation or heating. This work aims at synthesizing a novel photo- and thermosensitive aliphatic polyamide by anionic ring-opening copolymerization of ε-caprolactam and α-cinnamoylamido-ε-caprolactam. The photochemical reversible cross-linking of solutions and thermal cross-linking of spin-coated films made up of these new cinnamoyl-functionalized polyamides were monitored by UV–vis spectroscopy. These aliphatic polyamide copolymers were characterized by magic angle spinning solid-state NMR, and their thermal behaviors were studied by thermogravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis.

Liquid-crystalline polymer systems: From the past to the present

In the first part of this review, in a brief historical perspective, we consider the evolution of the scientific activity of Nikolai Al’fredovich Plate, Academician of the Russian Academy of Sciences: from grafted polymer systems to comb-shaped and liquid-crystalline polymers. The main biographical data on Plate are related to his scientific work at Moscow State University, and his research-development strategy to create and study of LC polymers with comb-shaped structure is considered. The second part of the article is devoted to discussion of scientific directions in this area that were developed in the last five years at the Laboratory of Chemical Transformations of Polymers, where Plate started his scientific activity. Special attention is paid to the research data on photochromic liquid-crystal polymers and composites. A concept of the preparation of multifunctional comb-shaped LC polymers containing mesogenic, photochromic, and chiral groups, as well as functional (crown ether) fragments, is presented. The photo-orientational processes occurring in photochromic LC polymers, which were used to prepare “command” surfaces and photo-orientators, are considered in detail. The preparation of a new class of photochromic polyamides with azobenzene, cinnamoyl and coumarin groups, which have been proposed for the obtaining of polymer films with latent data recording, is described. The phase behaviors and photo-optical properties of synthesized photochromic triple LC block copolymers are reported. Examples of holograms based on cholesteric LC blends, which allow double recording on the same polymer film, are presented. The results of investigations of light-controlled cholesteric polymer-stabilized LC networks with crown ether fragments in the compositions of macromolecules that are able to form complexes with metal ions are presented. The methods of preparation of photocontrolled and electrically controlled polymer LC nanocomposites with nanoparticles, as well as research data on their photo-optical properties, are considered.

Synthesis and biological evaluation of piperlongumine derivatives as potent anti-inflammatory agents

Piperlongumine (PL) and its derivatives were synthesized by the direct reaction between acid chloride of 3,4,5-trimethoxycinnamic acid and various amides/lactams. Later their anti-inflammatory effects were evaluated in lipopolysaccharide (LPS)-induced RAW-264.7 macrophages. Of the piperlogs prepared in this study, the maximum (91%) inhibitory activity was observed with PL (IC50=3μM) but showed cytotoxicity whereas compound 3 (IC50=6μM) which possess α,β-unsaturated γ-butyrolactam moiety offered good level (65%) of activity with no cytotoxicity. This study revealed that amide/lactam moiety connected to cinnamoyl group with minimum 3 carbon chain length and α,β-unsaturation is fruitful to show potent anti-inflammatory activity.

Cinnamoyl Alginate Microspheres: Effect of UV-Treatment on Release of FITC-Dextran

Cinnamoyl alginate microspheres were prepared using the water droplets of W/O emulsions as a template. Cinnamoyl alginates having variable content of the cinnamoyl group were prepared by a condensation reaction. The photo-dimerization degree of the cinnamoyl group increased as the molar ratio of pyranose unit/cinnamoyl group increased from 1:0.043 to 1:0.18. The air/water interfacial activity of cinnamoyl alginate also increased with increasing the molar ratio. Aqueous solution of cinnamoyl alginate was dispersed in mineral oil to obtain W/O emulsion. UV light (254 nm, 6 W) was irradiated to the emulsion to dimerize the cinnamoyl groups, and CaCl2 was added to the emulsion to cross-link the cinnamoyl alginate. The surface of UV-treated microspheres was rougher than that of UV-untreated microspheres, possibly due to the photo-dimerization-induced tension on the alginate chains. The release degrees for 24 hours of fluorescein isothiocyanate-dextran (FITC-dextran; MW 4000) from UV-treated microspheres were markedly higher than those from UV-untreated ones. This is possibly due to the intramolecular dimerization of cinnamoyl group. The UV irradiation-induced percentage increase in the maximum release degree was greater as the content of cinnamoyl group was higher.

Nanogels Composed of Cinnamoyl Alginate and Cinnamoyl Pluronic F127

Temperature-responsive nanogels were developed by photo crosslinking cinnamoyl alginate (CinAlg) and cinnamoyl Pluronic F127 (CinPlu). On the 1H NMR spectrum of CinAlg, one molecule of cinnamoyl group was calculated to be attached to every 7.7 units of the pyranose of alginate. On the 1H NMR spectrum of CinPlu, the molar ratio of Pluronic F127 to cinnamoyl group was calculated to be about 1:1.1. The air/water interfacial tension of CinAlg/CinPlu mixture solution was much lower than that of CinPlu solution and that of CinAlg solution, possibly due to their hydrophobic complexation. The nanogels were sphere-like particles on TEM photos. The mean diameter of the nanogel, determined by a dynamic light scattering technique, increased from 106 nm to 177 nm at room temperature when a UV light (365 nm, 400 W) was irradiated to the suspension for 60 minutes, possibly due to interparticle crosslinkage. It decreased with increasing temperature possibly because of the heat-induced condensation of Pluronic F127 chains. The absolute value of the negative zeta potential decreased with increasing the irradiation time, possibly due to the photo-induced condensation of alginate chains. And, it increased with increasing the temperature possibly due to the heat-induced condensation of Pluronic F127 chains.

Cinnamoyl Pluronic F127 as a Stimuli-Sensitive Amphiphile

Cinnamoyl Pluronic F127 (CP F127) was prepared by reacting cinnamoyl chloride and Pluronic F127. On the 1H NMR spectrum of CP F127, 1.2 moiety of cinnamoyl group was found to be attached to one molecule of CP F127. Using pyrene as a fluorescence probe, it was found that not only Pluronic F127 but also CP F127 could be readily assembled into micelles, and the critical micelle concentration was around 0.015 mg/ml and 0.03 mg/ml, respectively. Pluronic F127 in aqueous solution (2% w/v) could form no particles in 10–20°C, but particles (ca. 30 nm in diameter) were detected on a dynamic light scattering machine in 25–40°C possibly due to the thermal micellization. However, CP F127 was assembled into particles (ca. 230 nm) even in the lower temperature range, possibly because of the intermolecular hydrophobic interaction of the cinnamoyl group. The particle size of CP F127 strongly depended on the medium temperature and UV irradiation time. CP F127 was a good emulsifier for the preparation of O/W emulsions. The oil droplet size markedly increased upon UV irradiation (254 nm, 6 W), possibly because of the photo-dimerization of cinnamoyl group, but it was little affected by the temperature change (10–40°C).

Effects of hyperbranched and linear architecture on properties of polymers composed of poly(ɛ-caprolactone) and hydroxycinnamic acid

Photoreactive and degradable polymers with linear and hyperbranched architectures which composed of poly(ɛ-caprolactone) and hydroxycinnamic acid or its substituted derivatives were synthesized by thermal melt-polycondensation. The chemical structures of the polymers were confirmed by FTIR and 1H NMR measurements. The polymers showed good photoreactivities and fluorescent properties, and the hyperbranched polymers showed higher photoreactive speed and weaker fluorescence properties. These polymers had excellent thermal stabilities due to the rigid conjugated structures and the π-π strcking interaction of the cinnamoyl group, especially for the hyperbranched polymer. Moreover, the hydrolysis experiments and the XRD results revealed that the hyperbranched and linear polymers are amorphous and crystalline, respectively, and the degradation rate of amorphous polymers are faster than crystalline samples.

Light- and temperature-responsive liposomes incorporating cinnamoyl Pluronic F127

Light- and temperature-responsive liposomes were prepared by immobilizing cinnamoyl Pluronic F127 (CP F127) on the surface of egg phosphatidylcholine liposomes. CP F127 was prepared by a condensation reaction, and the molar ratio of cinnamoyl group to Pluronic F127 was calculated to be 1:1.4 on (1)H NMR spectrum. The cinnamoyl group of CP F127 was readily dimerized under the irradiation of a UV light (254 nm, 6 W). CP F127 decreased the absolute value of the zeta potential of liposome possibly because it can shift the hydrodynamic plane away from the liposome surface. The size of liposome decorated with CP F127, measured on a dynamic light scattering machine and observed on a TEM, was larger than that of bare liposome. The liposome bearing CP F127 seemed to fuse and aggregate each other. The liposome released calcein, a fluorescence dye, in response to a UV irradiation, possibly because the photo-dimerization of cinnamoyl group perturbs the liposomal membrane. Moreover, the liposome released the dye in response to a temperature change, possible due to the phase transition of Pluronic F127 layer on the liposomal surface or the hydrophobic interaction of the polymer with liposomal membrane.

Crystal and Molecular Structure of 1,1-Bis(methylthio)-5-(4-chlorophenyl)-1,4-pentadien-3-one

The 1,1-bis(methylthio)-5-(4-chlorophenyl)-1,4-pentadien-3-one compound crystallizes in the space group C2/c with unit cell parameters a=25.5763 Å, b=8.08863 Å, c=14.1452 Å, and β=108.6∘. The structure was solved by direct methods and refined to an R-factor of 0.0593. Due to the steric interaction between the two methyl groups, one of the methylthio groups is in cis conformation with C11–C10 double bond and the other is in trans conformation. The cinnamoyl group on the carbonyl carbon atom effects more delocalization of the electrons within the molecule so that the structure is highly conjugated and planar.

Healable properties of polymethacrylate derivatives having photo crosslinkable cinnamoyl side groups with surface hardness control

Based on reversible photo crosslinkable properties, a series of polymethacrylate derivatives having cinnamoyl group in the side chain has been designed and synthesized. By simple UV irradiation and thermal treatment on these polymer films, a complete healing behavior accompanied by changes of the surface hardness was observed.

Photo and thermal properties of cinnamoyl Pluronic F-127

Cinnamoyl chloride was covalently attached to the ends of Pluronic F-127 chains. The molar ratio of cinnamoyl groups to Pluronic F-127 of the cinnamoyl Pluronic F-127 (Cin-Plu) was calculated to be about 1:1 on a 1H NMR spectrum. The melting point (around 52 °C) of Cin-Plu was somewhat less than that (around 55 °C) of Pluronic F-127. Furthermore, the melting point of Cin-Plu decreased to around 50 °C on UV irradiation. The micellization temperature of Pluronic F-127 was around 15 °C and it was affected neither by the covalent attachment of cinnamoyl chloride nor the UV irradiation. On the other hand, Pluronic F-127 solution (22% w/v) in distilled water became a gel at around 28 °C and Cin-Plu solution (22% w/v) at around 39 °C. The elevation in the gelation temperature is possibly because the cinnamoyl group interferes with the intermolecular hydrophobic interaction of propylene oxide blocks, a main cause for the gelation. Cin-Plu solution (22% w/v) which had been subjected to UV irradiation (365 nm, 400 W) for 3 h exhibited no gelation temperature but a gradual increase in viscosity when the solution temperature increased from 17 °C to 37 °C, possibly due to the coexistence of dimeric Cin-Plu and monomeric Cin-Plu. © 2013 Society of Chemical Industry