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The design and synthesis of organic photocatalysts remain a great challenge due to their strict structural constraints. However, this could be mitigated by achieving structural flexibility by constructing permanent porosity into the materials. Conjugated microporous polymers (CMPs) are an emerging class of porous materials with an amorphous, three-dimensional network structure, which makes it possible to integrate the elaborate functional groups to enhance photocatalytic performance. Here, we report the synthesis of a novel CMP, named TAPFc-TFPPy-CMP, constructed by 1,1'3,3'-tetra(4-aminophenyl)ferrocene (TAPFc) and 1,3,6,8-tetrakis(4-formylphenyl)pyrene (TFPPy) monomers. The integration of the p-type dopant 7,7,8,8-tetracyanoquinodimethane (TCNQ) into the TAPFc-TFPPy-CMP improved the light adsorption performance, leading to a decrease in the optical bandgap from 2.00 to 1.43 eV. The doped CMP (TCNQ@TAPFc-TFPPy-CMP) exhibited promising catalytic activity in photocatalytic CO2 reduction under visible light, yielding 546.8 µmol g-1 h-1 of CO with a selectivity of 96% and 5.2 µmol g-1 h-1 of CH4. This represented an 80% increase in the CO yield compared to the maternal TAPFc-TFPPy-CMP. The steady-state photoluminescence (PL) and fluorescence lifetime (FL) measurements reveal faster carrier separation and transport after the doping. This study provides guidance for the development of organic photocatalysts for the utilization of renewable energy.
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The effective capture and recovery of radioiodine species associated with nuclear fuel reprocessing is of significant importance in nuclear power plants. Porous materials have been proven to be one of the most effective adsorbents for the capture of radioiodine. In this work, we design and synthesize a series of conjugated microporous polymers (CMPs), namely, TPDA-TFPB CMP, TPDA-TATBA CMP, and TPDA-TECHO CMP, which are constructed based on a planar rectangular 4-connected organic monomer and three triangular 3-connected organic monomers, respectively. The resultant CMPs are characterized using various characterization techniques and used as effective adsorbents for iodine capture. Our experiments indicated that the CMPs exhibit excellent iodine adsorption capacities as high as 6.48, 6.25, and 6.37 g g-1 at 348 K and ambient pressure. The adsorption mechanism was further investigated and the strong chemical adsorption between the iodine and the imine/tertiary ammonia of the CMPs, 3D network structure with accessible hierarchical pores, uniform micromorphology, wide π-conjugated structure, and high-density Lewis-base sites synergistically contribute to their excellent iodine adsorption performance. Moreover, the CMPs demonstrated good recyclability. This work provides guidance for the construction of novel iodine adsorbent materials with high efficiency in the nuclear power field.
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Transforming CO2 into value-added chemicals has been an important subject in recent years. The development of a novel heterogeneous catalyst for highly effective CO2 conversion still remains a great challenge. As an emerging class of porous organic polymers, covalent organic frameworks (COFs) have exhibited superior potential as catalysts for various chemical reactions, due to their unique structure and properties. In this study, a layered two-dimensional (2D) COF, IM4F-Py-COF, was prepared through a three-component condensation reaction. Benzimidazole moiety, as an ionic liquid precursor, was integrated onto the skeleton of the COF using a benzimidazole-containing building unit. Ionization of the benzimidazole framework was then achieved through quaternization with 1-bromobutane to produce an ionic liquid-immobilized COF, i.e., BMIM4F-Py-COF. The resulting ionic COF shows excellent catalytic activity in promoting the chemical fixation of CO2 via reaction with epoxides under solvent-free and co-catalyst-free conditions. High porosity, the one-dimensional (1D) open-channel structure of the COF and the high catalytic activity of ionic liquid may contribute to the excellent catalytic performance. Moreover, the COF catalyst could be reused at least five times without significant loss of its catalytic activity.
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As one of the main nuclear wastes generated in the process of nuclear fission, radioactive iodine has attracted worldwide attention due to its harm to public safety and environmental pollution. Therefore, it is of crucial importance to develop materials that can rapidly and efficiently capture radioactive iodine. Herein, we report the construction of three electron-rich porous organic polymers (POPs), denoted as POP-E, POP-T and POP-P via Schiff base polycondensations reactions between Td-symmetric adamantane knot and four-branched "linkage" molecules. We demonstrated that all the three POPs showed high iodine adsorption capability, among which the adsorption capacity of POP-T for iodine vapor reached up to 3.94 g·g-1 and the removal rate of iodine in n-hexane solution was up to 99%. The efficient iodine capture mechanism of the POP-T was investigated through systematic comparison of Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) before and after iodine adsorption. The unique π-π conjugated system between imine bonds linked aromatic rings with iodine result in charge-transfer complexes, which explains the exceptional iodine capture capacity. Additionally, the introduction of heteroatoms into the framework would also enhance the iodine adsorption capability of POPs. Good retention behavior and recycling capacity were also observed for the POPs.
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Iodo , Neoplasias da Glândula Tireoide , Elétrons , Humanos , Iodetos , Iodo/química , Radioisótopos do Iodo , Polímeros/química , Porosidade , Bases de Schiff , Espectroscopia de Infravermelho com Transformada de FourierRESUMO
Sulfuryl fluoride (SO2F2) plays an important role in the operation of gas-insulated switchgear (GIS) equipment where it is widely used as the characteristic gas for discharge diagnostics. However, the formation mechanism of SO2F2 is currently unclear, and as a consequence, we have employed a range of ab initio methods to investigate the hydrolysis reaction of SOF4 that is known to afford SO2F2 in the gas phase. These results suggest that two H2O molecules are incorporated into a low energy transition state to afford an H-bond network that facilitates proton transfer during the hydrolysis of SOF4.
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Ultrathin two-dimensional (2D) crystalline materials show high specific surface area (SA) of high energy (HE) facets, imparting a significant improvement in their performances. Herein we report a novel route to synthesize TiO2 nanofilms (NFs) with atomic thickness (<2.0â nm) through a solvothermal reaction mediated by the hydrogen-bonding networks constructed by hydroquinone (HQ). The resultant TiO2 NFs have nearly 100 % exposed (001) facets and give an extremely high SA up to 487â m(2) g(-1) . The synergistic effect of HQ and choline chloride plays a vital role in the formation of TiO2 NFs and in the exposure of HE (001) facets. Because of its ultrathin feature and exposed (001) facet, the N2 -annealled TiO2 NFs showed fast kinetics of lithium insertion/extraction, demonstrating foreseeable applications in the energy storage.
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A KOH mediated mild, efficient, convenient and gram-scalable protocol for the acetylation of alcohols with EtOAc as acetyl source and solvent. Various types of alcohols were successfully transformed into according acetylated products. Good to excellent yields were offered by primary alcohols and low to moderate yields were offered by secondary alcohols.
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Transition metal-based oxyhydroxides (MOOH) have garnered significant attention as promising catalyst for the Oxygen Evolution Reaction (OER). However, the direct synthesis of MOOH poses challenges due to the instability of trivalent cobalt and nickel salts, attrivuted to their high oxidation states. In this study, theoretical computations predicted that Co(OH)2 nanosheets are exclusively formed on carbon structures, owing to the stronger binding energy between CoOOH and CC compared to Co(OH)2. Furthermore, the presence of FeOOH interface reduces the binding energy between CoOOH and carbon structure. Experiment evidence confirms that CoOOH can be directly synthesized through controlled epitaxial growth on an FeOOH interface using a hydrothermal method. Moreover, the in-situ doping of iron leads to the formation of high-quality Fe0.35Co0.65OOH with exceptional OER performance, displaying a low overpotential of 240 mV at 10 mA cm-2 and a small Tafel slope of 43 mV dec-1. Density functional theory (DFT) calculations uncover the substantial enhancement of oxygen-containing species adsorption abilities by Fe0.35Co0.65OOH, resulting in improved OER activity. This work presents a promising strategy for the efficient preparation of layered cobalt oxyhydroxides, enabling efficient energy conversion and storage.
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Radioactive iodine from nuclear waste poses a huge threat to public safety and raises concerns about environmental pollution. There is thus a growing demand for developing novel adsorbents for highly effective iodine capture. In this work, we design and synthesize three novel conjugated microporous polymers, namely, TPE-PyTTA-CMP, TPE-TAPP-CMP, and TPE-TPDA-CMP, which are constructed by an imidization reaction based on octet and tetratopic linkers. The iodine vapor adsorption experiments show that the three CMPs have an excellent iodine adsorption capacity as high as 3.10, 3.67, and 4.68 g·g-1 under 348 K and ambient pressure conditions, respectively. The adsorbed iodine in the CMPs can be released into methanol in a dramatically rapid manner, and their excellent iodine adsorption performance can still be maintained after multiple cycles. In addition, the CMPs demonstrate good adsorption performance in an n-hexane solution of iodine, and the kinetic experimental data follow the pseudo-second-order model. The hierarchical porosity, extended π-conjugated skeleton, and rich electron-donor nitrogen sites of the CMPs could contribute to their excellent iodine adsorption performance. The knowledge information obtained in this work could open up new possibilities for designing novel CMPs targeting a wide range of environment-related applications.
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A simple and metal-free catalytic system composed of NaOtBu/DMF and an O2 balloon efficiently converted 5-hydroxymethylfurfural (5-HMF) to furan-2,5-dicarboxylic acid with an 80.85% yield. 5-HMF analogues and various types of alcohols were also transformed to their corresponding acids in satisfactory to excellent yield by this catalytic system.
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Covalent organic frameworks (COFs) are an emerging class of crystalline porous polymers that make these materials suitable for use as excellent scaffold in heterogeneous catalysis. Here we synthesize a layered two-dimensional (2D) COF (TADP-COF) through the condensation reaction between four-branched 5,10,15,20-tetrakis(4-aminophenyl)porphyrin (TAPP) and linear 2,5-dihydroxyterephthalaldehyde (Dha) and 1,4-phthalaldehyde (PA) building blocks. Porphyrin units, imine and hydroxyl groups together with imines can provide wide coordination sites for metal docking. Using a programmed synthetic procedure, Cu(ii) ions first coordinated with the imine groups in conjunction with their adjacent hydroxyl groups, and porphyrin units and subsequently added Pd(ii) ions occupied the remaining imine sites in the space between adjacent COF layers. The bimetallic Pd(ii)/Cu(ii)@TADP-COF showed high catalytic activity in a one-pot coupling/oxidation cascade reaction in water. The high surface area, one-dimensional (1D) open channel structure and predesigned catalytic active sites of this material make it ideal candidate for use as heterogeneous catalyst in a wide range of catalytic reactions.
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Developing a new and efficient catalytic route for the production of alkanes by upgrading the aqueous phenolic biofuels still remains a challenge. Here, we designed and synthesized a bifunctional catalyst that uses natural montmorillonite (MMT) as support and combines metal active sites and BrÓ§nsted acid sites in the MMT via ion exchange and reduction roasting process. The catalytic activity of the as-synthesized Pd-MMT (H+) was evaluated by the hydrodeoxygenation (HDO) of a series of lignin-derived phenolic compounds in water. Our model reaction study reveals that the HDO of phenol undergoes an initial hydrogenation of aromatic rings to produce cyclohexanol and cyclohexanone, followed by the dehydration of cyclohexanol to provide intermediate cyclohexene and a final hydrogenation of cyclohexene to create a cyclohexane product. The combination of high metal catalytic activity and BrÓ§nsted acidity in Pd-MMT (H+) synergistically accelerated the HDO of phenol. Furthermore, good catalytic activity and recycling ability were also observed for other lignin-derived phenolic compounds.
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The secondary C(OH)-C bonds are abundant in biomass such as lignin and cellulose. Thus, selective cleavage of the C(OH)-C bonds into value chemicals attracted much attention. Molecular iodine has received considerable attention as an inexpensive and readily available catalyst to yield the corresponding products in excellent yields with high selectivity, but it is highly corrosive and toxic, making its use somewhat unattractive. In this study, I2 was generated in situ from Fe(NO3)3.9H2O/NaI, which was further combined with Fe(NO3)3.9H2O to catalyze the oxidation process. In the reaction, the H2O molecule from the reaction and Fe(NO3)3.9H2O attacked the phenylglyoxal to form benzaldehyde, which was further oxidized to benzoic acid. Aryl primary and secondary benzylic alcohols from lignin were successfully transformed into aryl carboxylic acids by Fe(NO3)3.9H2O/NaI/DMSO. The catalytic system was green and efficient, avoiding the usage of toxic and corrosive molecular I2. From the experiments, it was clear that the yield of the product from the substrates with an electron-donating group was higher than that of electron-withdrawing substituted substrates, which was similar to the aryl secondary alcohols. Aryl alkyl ketones were also successfully conducted by the Fe(NO3)3.9H2O/NaI/DMSO catalytic system.
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Reactive oxygen species (ROS)-based cancer treatments have attracted much attention in recent years. However, most patients respond poorly to the monotypic ROS during these treatments. In this work, a multiple ROS-based cancer immunotherapy synergistic strategy has been developed to enhance the therapeutic effect of cancer. We prepare a three-dimensional covalent organic framework (3D COF-TATB), and embed copper ions (Cu2+) into the skeleton to obtain multifunctional nanomaterial, 3D Cu@COF-TATB. In this system, porphyrins in 3D COF-TATB serve not only as the photosensitizer for photodynamic process to produce singlet oxygen(1O2), but also as the binding sites to complex with Cu2+. Cu2+ can be reduced by the GSH to generate Cu+ to produce hydroxyl radical (â¢OH) through the Fenton-like reaction. Moreover, the generated multiple types of ROS induce the immunogenic cell death (ICD) of cancer cells to improve the immunogenicity and further activate an immune response for attacking the tumor. Combining with the immunoblocking inhibitor (aPD-1), 3D Cu@COF-TATB can effectively inhibit the tumor growth. This work will provide a guidance for multimodal cancer therapy in future clinical treatment settings.
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Estruturas Metalorgânicas , Neoplasias , Linhagem Celular Tumoral , Cobre/química , Humanos , Imunoterapia , Estruturas Metalorgânicas/química , Neoplasias/tratamento farmacológico , Fármacos Fotossensibilizantes/química , Espécies Reativas de Oxigênio/metabolismoRESUMO
OBJECTIVE: To discuss the feasibility of water infusion colonoscopy and its difference with traditional air insufflation colonoscopy in application value. METHODS: A prospective randomized controlled clinical study was designed to include 200 patients who underwent sedation-free diagnostic colonoscopy. Among them, 100 patients were treated with water infusion colonoscopy (observation group) and 100 patients were treated with air insufflation colonoscopy (control group). All operations were performed independently by the same experienced physician. The differences in colonoscopy related values, colon adenoma detection rate, and follow-up findings between the patients of two groups were compared. RESULTS: There was no significant difference in the Boston bowel preparation scale (BBPS) score of the left hemicolon, transverse colon, right hemicolon, total BBPS scores, and bubble amount between the two groups (P>0.05). In the observation group, the scope-forward time, the time to reach the ileocecal junction, and the total operation time were significantly longer than that of the control group (P<0.01). The proportion of patients in whom the ileocecal junction was successfully reached was significantly higher in the observation group. The intraoperative abdominal pain visual analog scale (VAS) score, abdominal distension VAS score, the proportion of postural change, and the proportion of abdominal compression were all significantly lower in the observation group (P<0.05). There were no significant differences in the endoscope hardness adjustment rate, the scope withdrawal time, total detection rate of adenomas, and the size or location of colon adenomatous lesions between the two groups (P>0.05). Compared with control group, the incidence of abdominal pain and VAS scores were significantly lower in the observation group (P<0.05), and the willingness of patients to perform colonoscopy again was significantly higher (P<0.01). CONCLUSION: Patients' tolerance and examination satisfaction are significantly better when using water infusion colonoscopy compared with traditional air insufflation colonoscopy, but the operation times are longer.
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Post-synthetic modification has been the most powerful strategy for covalent organic frameworks (COFs) for their functionalization in many fields. This strategy is typically achieved through the quantitative reaction between existing reactive sites on the linkers (building units) and incoming functional groups. However, usage of linkages (bonds formed to construct COFs) for the post-synthetic modification still remains limited. Herein, we develop a new post-synthetic modification route that is based on the modification of linkages. With this strategy, the imine linkages of a two-dimensional (2D) COF, TFPPy-PyTTA-COF, have been transformed into amine linkages to give the amine-linked isostructure with retention of crystallinity and porosity. The subsequent aminolysis of the amine linkages with 1,3-propane sultone and further metathetical reaction with cobalt acetate [Co(OAc)2] enable the introduction of cobalt alkyl sulfonate to the one-dimensional (1D) channel walls of the COF. The resulting ionic COF with coupled Co2+ in the frameworks shows excellent catalytic activity and good recyclability towards the cycloaddition reactions of epoxides and CO2. This strategy is of interest as it opens a way to use linkage modification for exploring the potential of COFs for different applications.
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Three new labdane-type diterpenoids, callicapene M3-M5 (1-3) were isolated from the Callicarpa macrophylla Vahl. Their structures were identified by spectroscopic method. The isolated compounds were evaluated for inhibitory activity on NO production in LPS-activated RAW 264.7 macrophage cells by using MTT assays. Compounds 1-3 showed potent inhibitory activity, with IC50 value of 48.15, 46.31 and 38.72 µM respectively.
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Callicarpa/química , Diterpenos/isolamento & purificação , Óxido Nítrico/antagonistas & inibidores , Animais , Diterpenos/química , Diterpenos/farmacologia , Concentração Inibidora 50 , Macrófagos/efeitos dos fármacos , Macrófagos/metabolismo , Camundongos , Estrutura Molecular , Óxido Nítrico/biossíntese , Folhas de Planta/química , Células RAW 264.7RESUMO
BACKGROUND: LIM kinase 1 plays an important role in tumor cell invasion and metastasis by regulating architecture of actin cytoskeleton, and inhibiting activity of this kinase may be a promising strategy to prevent cancer cells from distant spread. In our previous studies, we found several extracts from the medical herbs in genus Chloranthus to exhibit anti-metastatic effects. PURPOSE: The aim of this study is to find LIMK1 inhibitors from Chloranthus serratus, a medical herb from genus Chloranthus and to evaluate their effects on cell motility. METHODS: Three sesquiterpenes, chloranthalactone E (compound 1), serralactone A (compound 2, SERA is used in the further testing), and 8ß, 9α-dihydroxylindan-4(5), 7(11)-dien-8α, 12-olide (compound 3) were isolated from Chloranthus serratus, and the anti-LIMK1 activities of these compounds were investigated by kinase-Glo® luminescent kinase assay. Then, the anti-LIMK1 properties of SERA were verified by kinase-Glo® luminescent kinase assay and western blot assay. The effects of SERA on F-actin polymerization and cell migration were investigated by Phalloidin dying, AP 48 chamber system and ORIS™ cell migration assay. Furthermore, the inhibitory effects of SERA on LIMK1 were confirmed by overexpression of LIMK1 and small interfering RNA (siRNA) mediated gene silencing. RESULTS: we reported here that among the three sesquiterpenes, SERA showed significantly inhibition on LIMK1 activity, and the IC50 values on MDA-MB-231 and MDA-MB-468 cells were 3.14 µM and 4.64 µM, respectively. Furthermore, it was also found that SERA significantly suppressed LIMK1 and cofilin1 phosphorylation, F-actin polymerization and also cell migration. Data from LIMK1 overexpression and RNA interfering assay confirmed that the inhibitory effects of SERA on LIMK1 was antagonized and enhanced by the overexpression and knockdown of LIMK1. CONCLUSION: collectively, it was concluded that SERA exhibited significant inhibitory effects on breast cancer cells migration, and these effects of this sesquiterpene are due to its properties reducing the activation of LIM kinase 1.
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Neoplasias da Mama/patologia , Movimento Celular/efeitos dos fármacos , Quinases Lim/metabolismo , Sesquiterpenos/farmacologia , Actinas/metabolismo , Neoplasias da Mama/tratamento farmacológico , Linhagem Celular Tumoral , Regulação para Baixo , Inativação Gênica , Humanos , Estrutura Molecular , Fosforilação , Raízes de Plantas/química , Plantas Medicinais/química , RNA Interferente Pequeno/metabolismo , Viridiplantae/químicaRESUMO
Curcolonol (CCL) is a furan type sesquiterpene isolated from several medical herbs. Based on previous results of anti-migratory activity screening, in this study, we investigated the effects of CCL on cancer cell motility. By in vitro migration assay, we found that CCL significantly inhibited the vertical and horizontal migration of breast cancer cells induced by transforming growth factor (TGF)-ß1. In addition, CCL also exerted inhibitory effects on F-actin polymerization in breast cancer cells when the cells were dyed with phalloidin. Given the close association between F-actin and ADF/cofilin, the effects of CCL on the expression and phosphorylation of cofilin 1 were explored. It was observed that there were minimal changes in the expression of cofilin 1; however, the phosphorylation of cofilin 1 was significantly inhibited by CCL in a dose-dependent manner. Furthermore, CCL significantly inhibited the activity of LIM kinase 1 (LIMK1), although almost no effects were observed on LIMK1 expression and phosphorylation. However, the inhibitory effects of CCL on LIMK1 activity were antagonized and enhanced by the overexpression and knockdown of LIMK1, respectively. Based on the current data, it is thus suggested that the suppressive effects of CCL on breast cancer cell motility are due to its potential to reduce the phosphorylation of cofilin 1, which may be associated with the inhibition of the catalytic activity of LIMK1.
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Neoplasias da Mama/metabolismo , Cofilina 1/metabolismo , Compostos Heterocíclicos com 3 Anéis/farmacologia , Quinases Lim/metabolismo , Actinas/metabolismo , Neoplasias da Mama/tratamento farmacológico , Linhagem Celular Tumoral , Movimento Celular/efeitos dos fármacos , Relação Dose-Resposta a Droga , Regulação para Baixo , Feminino , Regulação Neoplásica da Expressão Gênica/efeitos dos fármacos , Humanos , Fosforilação/efeitos dos fármacos , Fator de Crescimento Transformador beta1/farmacologiaRESUMO
Platelet activation and subsequent accumulation at sites of vascular injury are central to thrombus formation, which is considered to be a trigger of several cardiovascular diseases. Callicarpa nudiflora (C. nudiflora) Hook is a traditional Chinese medicinal herb for promoting blood circulation by removing blood stasis. In our previous study, several compounds extracted from this herb, including luteolin4'OßDglucopyranoside (LGP), were revealed to exert inhibitory effects on adenosine diphosphate (ADP)induced platelet aggregation. The aim of present study was to confirm these antiplatelet effects and elucidate the potential mechanisms. Using a plateletaggregation assay, it was revealed that LGP significantly inhibited platelet aggregation induced by ADP, U46619 and arachidonic acid. It was also found that LGP exhibited marked inhibitory effects on the activation of αIIbß3 integrin, the secretion of serotonin from granules, and the synthesis of thromboxane A2. In addition, the results showed that LGP suppressed Ras homolog family member A and phosphoinositide 3kinase/Akt/glycogen synthase kinase 3ß signal transduction. Data from a radiolabeled ligandbinding assay indicated that LGP exhibited apparent competing effects on thromboxane receptor (TP) and P2Y12 receptors. In conclusion, the data presented here demonstrated that LGP, a natural compound from C. nudiflora Hook, inhibited the development of platelet aggregation and amplification of platelet activation. These inhibitory effects may be associated with its dualreceptor inhibition on P2Y12 and TP receptors.