Highly Oxygenated Limonoids and Lignans from Phyllanthus flexuosus

Two new highly oxygenated limonoids,flexuosoids A(1)and B(2),and three new arylnaphthalene lignan glycosides,phyllanthusmins D–F(3–5),were isolated from the roots of Phyllanthus flexuosus,in addition to three known lignans,phyllanthusmin C,arabelline,and(?)-diasyringaresinol.Their structures were elucidated on the basis of detailed spectroscopic analysis and chemical methods.Compounds 1 and 2,two new decaoxygenated limonoids with a C-19/29 lactol bridge and heptaoxygenated substituents at C-1,C-2,C-3,C-7,C-11,C-17,and C-30,represent the second example of limonoids in the Euphorbiaceae family.Most of the isolates were tested for their antifeedant,anti-herpes simplex virus 1,and cytotoxic activities.The new limonoids 1 and 2 showed promising antifeedant activity against the beet army worm(Spodoptera exigua)with EC50 values of 25.1 and 17.3 lg/cm2,respectively.In addition,both of them displayed moderate cytotoxicity against the ECA109 human esophagus cancer cell line,along with the known lignan glycoside,phyllanthusmin C,with the IC50 values of 11.5(1),8.5(2),and 7.8(phyllanthusmin C)lM,respectively.

Colorectal adenocarcinoma patients with M1a diseases gain more clinical benefits from palliative primary tumor resection than those with M1b diseases: A propensity score matching analysis

BACKGROUND Surgical resection is regarded as the only potentially curative treatment option for patients with metastatic colorectal cancer(CRC).The National Comprehensive Cancer Network clinical practice guidelines do not recommend palliative surgery unless there is a risk of severe symptoms.However,accumulating evidence has shown that palliative surgery is associated with more favorable outcomes for patients with metastatic CRC.AIM To investigate the separate role of palliative primary tumor resection for patients with stage IVA(M1a diseases)and stage IVB(M1b diseases)colorectal adenocarcinoma(CRA).METHODS CRA patients diagnosed from 2010 to 2015 with definite M1a and M1b categories according to the 8th edition of American Joint Committee on Cancer staging system were selected from the Surveillance Epidemiology and End Results(SEER)database.To minimize potential selection bias,the data were adjusted by propensity score matching(PSM).Baseline characteristics,including gender,year of diagnosis,age,marital status,primary site,surgical information,race,grade,chemotherapy,and radiotherapy,were recorded and analyzed.Univariate and multivariate analyses were performed to explore the separate role of palliative surgery for patients with M1a and M1b diseases.RESULTS A total of 19680 patients with metastatic CRA were collected from the SEER database,including 10399 cases of M1a diseases and 9281 cases of M1b diseases.Common independent prognostic factors for both M1a and M1b patients included year of diagnosis,age,race,marital status,primary site,grade,surgery,and chemotherapy.After PSM adjustment,3732 and 3568 matched patients in the M1a and M1b groups were included,respectively.Patients receiving palliative primary tumor resection had longer survival time than those without surgery(P<0.001).For patients with M1a diseases,palliative resection could increase the median survival time by 9 mo;for patients with M1b diseases,palliative resection could prolong the median survival time by 7 mo.For M1a diseases,patients with lung metastasis had more clinical benefit from palliative resection than those with liver metastasis(15 mo for lung metastasis vs 8 mo for liver metastasis,P<0.001).CONCLUSION CRA patients with M1a diseases gain more clinical benefits from palliative primary tumor resection than those with M1b diseases.Those patients with M1a(lung metastasis)have superior long-term outcomes after palliative primary tumor resection.

Five new sucrose esters from the whole plants of Phyllanthus cochinchinensis

Chemical investigation of the whole plants of Phyllanthus cochinchinensis(Euphorbiaceae)led to the isolation of five new sucrose benzoyl esters,3,6'-di-O-benzoylsucrose(1),3,6'-di-O-benzoyl-2'-O-acetylsucrose(2),3,6'-di-O-benzoyl-4'-O-acetylsucrose(3),3,6'-di-O-benzoyl-3'-O-acetylsucrose(4)and 3-O-benzoyl-6'-O-(E)-cinnamoylsucrose(5),together with two known secoiridoid glycosides,jasminoside(6)and jaslanceoside B(7).Their structures were established on the basis of detailed spectroscopic analysis and chemical method.

Relationships of Inflammatory Factors and Risk Factors with Different Target Organ Damage in Essential Hypertension Patients

Background： Atherosclerosis （AS） is an inflammatory disease. Inflammation was considered to play a role in the whole process of AS. This study aimed to analyze the relationships of inflammatory factors and risk factors with different target organ damages （TOD） in essential hypertension （EH） patients and to explore its clinical significance. Methods： A total of 294 EH patients were selected and divided into four groups according to their conditions of TOD. Forty-eight healthy subjects were selected as control. The clinical biochemical parameters, serum amyloid A, serum tryptase, and lipoprotein-associated phospholipase A2 （Lp-PLA2） in each group were detected, and the related risk factors were also statistically analyzed. Results： Fihrinogen （Fbg） was the most significant independent risk factor in acute coronary syndrome （ACS） group （odds ratio [OR]： 22.242, 95% confidence interval [CI]： 6.458-76.609, P 〈 0.001） with the largest absolute value of the standardized partial regression coefficient B＇ （b＇： 1.079）. Lp-PLA2 was the most significant independent risk factor in stroke group （OR： 13.699, 95% CI： 5.236-35.837, P 〈 0.001） with b＂ 0.708. Uric acid （UA） was the most significant independent risk factor in renal damage group （OR： 15.307, 95% CI：4.022 58.250, P〈0.001）with b＇= 1.026. Conclusions： Fbg, Lp-PLA2, and UA are the strongest independent risk factors toward the occurrence of ACS, ischemic stroke, and renal damage in EH patients, thus exhibiting the greatest impacts on the occurrence ofACS, ischemic stroke, and renal damage in EH patients, respectively.

Heptanuclear brucite disk with cyanide bridges in a cocrystal and tracking its pyrolysis to an efficient oxygen evolution electrode

The development of efficient oxygen evolution reaction(OER)catalysts is still lacking in exploration of the mechanism of controlled pyrolysis of precursors among new material platforms.Here,a novel Co-based coordination molecular cluster has been first introduced as precursor to obtain metallic cobalt core shelled by N-doped carbon(Co@NC)structure which operates as an oxygen evolution electrode.Specifically,a new cocrystal compound,[Co7II(l3-CN)6(mmimp)6][CoIICl3N(CN)2]á3CH3OH(Co7+1,mmimp=2-methoxy-6-((methylimino)-methyl)phenol),was isolated consisting of Brucite disks of cobalt where the usual bridging l3-OH is replaced by l3-CN produced by the in-situ decomposition of dicyanamide(NC-N-CNà).The cobalt atoms are bonded through the nitrogen atom of the cyanide.Remarkably,time dependent thermogravimetric-mass spectrometry(TG-MS)analysis was utilized to track its pyrolysis process.It allowed us to propose a possible formation process of the Co@NC structure from Co7+1.Interestingly,an extremely superior OER electrode is optimized for Co@NC-600 having the lowest overpotential of257 m V at 10 m A/cm2in 1 mol/L KOH solution.The present study pins down the importance of clusters of transition metals on realizing distinct nanostructures operating as highly efficient OER electrocatalyst.

Stepwise Crystalline Structural Transformation in 0D Hybrid Antimony Halides with Triplet Turn-on and Color-Adjustable Luminescence Switching

Intelligent stimuli-responsive fluorescence materials are extremely pivotal for fabricating luminescent turn-on switching in solid-state photonic integration technology,but it remains a challenging objective for typical 3-dimensional(3D)perovskite nanocrystals.Herein,by fine-tuning the accumulation modes of metal halide components to dynamically control the carrier characteristics,a novel triple-mode photoluminescence(PL)switching was realized in 0D metal halide through stepwise single-crystal to single-crystal(SC-SC)transformation.Specifically,a family of 0D hybrid antimony halides was designed to exhibit three distinct types of PL performance including nonluminescent[Ph_(3)EtP]_(2)Sb_(2)Cl_(8)(1),yellowemissive[Ph3EtP]2SbCl5·EtOH(2),and red-emissive[Ph_(3)EtP]_(2)SbCl_(5)(3).Upon stimulus of ethanol,1 was successfully converted to 2 through SC-SC transformation with enhanced PL quantum yield from~0%to 91.50%acting as“turn-on”luminescent switching.Meanwhile,reversible SC-SC and luminescence transformation between 2 and 3 can be also achieved in the ethanol impregnation-heating process as luminescence vapochromism switching.As a consequence,a new triple-model turn-on and coloradjustable luminescent switching of off-onI-onII was realized in 0D hybrid halides.Simultaneously,wide advanced applications were also achieved in anti-counterfeiting,information security,and optical logic gates.This novel photon engineering strategy is expected to deepen the understanding of dynamic PL switching mechanism and guide development of new smart luminescence materials in cutting-edge optical switchable device.

Two-thiols-regulated fabrication of plasmonic nanoparticles with co-enhanced Raman scattering and circular dichroism responses

Plasmonicnanoparticles(PNPs)with stable nanogaps are important to achieve strong,uniform and quantitative gap-enhanced Raman scattering(GERS)signals.Chiral PNPs with plasmonic circular dichroism(PCD)responses have been discovered to be suitable for applications in enantiomeric recognition,cancer therapy and activation of immune system.Herein,two-thiolsmodulated growth was demonstrated to result in the acquisition of PNPs with synergistically enhanced GERS and PCD signals.4-Aminothiophenol(4-ATP)and cysteine(Cys)played the role of Raman reporter and chiral stimulus,respectively.At a fixed 4-ATP concentration,the GERS signal of PNPs was significantly enhanced with the increase of the concentration of Cys.Simultaneously,at a fixed concentration of Cys,an increase in PCD response was observed by elevating the concentration of 4-ATP.Both aforementioned molecules acted as morphology controllers,leading to the formation of helical shell.It is suggested that the giant GERS and PCD response were contributed by the‘‘hot spots''within the PNPs and more perfect helical shells.Our research pointed out a novel synthetic guideline to obtain PNPs with multiple functionalities by incorporating multi-ligands into the growth stages.

DBU-catalyzed dearomative annulation of 2-pyridylacetates withα,β-unsaturated pyrazolamides for the synthesis of multisubstituted 2,3-dihydro-4H-quinolizin-4-ones

The reaction of 2-pyridylacetates andα,β-unsaturated pyrazolamides with DBU as the catalyst has been developed.A range of unexplored multisubstituted 2,3-dihydro-4H-quinolizin-4-ones are obtained with satisfactory yields(up to 94%)and excellent diastereoselectivities(all cases>20:1 dr)via a dearomative[3+3]annulation process.This practical method also features transition metal free,mild reaction conditions,wide functional group tolerance,easy scale-up synthesis,and versatile further derivatization.