Fragmentation Mechanism of Trans-α-Aryl-β-enamino Esters

Electron impact induced fragmentation mechanisms of trans α aryl β enamino esters were investigated using mass analyzed ion kinetic energy (MIKE) spectrometry and high resolution accurate mass data. It was found that the main characteristic fragmentations of compounds studied were: an odd electron ion M +· -EtOH was formed by losing a neutral molecule of ethanol; and the skeletal rearrangements took place; and the ring opening reaction happened after losing a carbon monoxide; and the typical McLafferty rearrangement underwent in ester group. The cyclization reaction caused by losing neutral molecule of TsNH 2 due to the ortho effects of substituted group of aromatic ring was also observed.

Pathogenic contribution of cholesteryl ester accumulation in the brain to neurodegenerative disorders

Cholesteryl esters(CEs) have been increasingly implicated in neurodegenerative disorders such as Alzheimer's disease(AD).Alois Alzheimer noted three prominent neuropathologic features in his original analysis of the AD brain:senile plaques,neurofibrillary tangles,and lipid granule accumulation.Senile plaques,which are aggregates of amyloid-beta(Aβ),and neurofibrillary tangles,which are aggregates of phosphorylated tau,have been regarded as more consistent characteristics of the AD brain compared with lipid granule accumulation and thus have been studied more intensively(Foley,2010).

Exploring Ester Prodrugs: A Comprehensive Review of Approaches, Applications, and Methods

The review provides an overview of the approaches, applications, and methods for ester prodrugs. Ester prodrugs are pharmacologically inactive compounds in their original form but become active drugs on biotransformation within the body, which offers advantages concerning the solubility, stability, and targeted delivery of the active drug. Several approaches of ester prodrugs have been reviewed in this review, including simple ester prodrugs, amino acid ester prodrugs, sugar ester prodrugs, lipid ester prodrugs, and polymeric ester prodrugs. This review incorporates in vitro and in vivo methods as well as the characterization of physical and chemical properties for ester prodrugs, cell culture systems, enzymatic assays, and animal models—all of these having a very important bearing on the evaluation of stability, bioavailability, and efficacy for ester prodrugs. While the benefits of using ester prodrugs are significant, there are also disadvantages like instability, poor or variable enzymatic hydrolysis, and toxicity from released promoieties or by-products. This review discusses solutions to the various limitations that include enhancing stability with ionizable promoieties and using physiologically-based pharmacokinetic modeling. The review also highlights the application of ester prodrugs in neurological disorders, such as Parkinson’s disease, and the ongoing efforts to address the critical limitations in treatment efficacy. Future prodrug strategies are poised to advance significantly by harnessing diverse transport mechanisms across the blood-brain barrier and integrating nanotechnology.

Design,synthesis,and insecticidal activity of novel terpenoid ester compounds containing bicyclo[2.2.1]heptane against Aphis gossypii Glover

To discover novel and efficient compounds against Aphis gossypii Glover,a series of novel terpene ester derivatives containing the structure of bicyclo[2.2.1]heptane were designed and synthesized using tschimganin as the lead compound.Bioactivity assays showed that most tschimganin analogs exhibited moderate to outstanding insecticidal activity against A.gossypii.In particular,compound 56(LC_(50)=0.28μg mL^(-1)),identified as(1S,2S,4R)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl nicotinate,exhibited the best activity,which was significantly superior to that of imidacloprid(LC_(50)=0.54μg mL^(-1))and sulfoxaflor(LC_(50)=0.70μg mL^(-1)).The precise and dependable 3D-QSAR model suggests a promising direction for further design of more active tschimganin-based insecticides.Metabolomics showed that compound 56 disrupted detoxification,amino acid biosynthesis,and energy metabolism and may affect the central nervous system of A.gossypii.The results of this study indicated that tschimganin analogs are a potential new class of green insecticides that can be used for the integrated management of A.gossypii.

Insight into the effect of geographic location and intercropping on contamination characteristics and exposure risk of phthalate esters(PAEs)in tea plantation soils

Phthalate esters(PAEs)are an emerging pollutant due to widespread distribution in environmental mediums that have attracted widespread attention over recent years.However,there is little information about tea plantation soil PAEs.A total of 270 soil samples collected from 45 tea plantations in the major high-quality tea-producing regions of Jiangsu,Zhejiang,and Anhui provinces in China were analyzed for seven PAEs.The detection frequency of PAEs in tea plantation soil was 100%.DBP,DEHP,and DiBP were the main congeners in tea plantation soil.The PAEs concentrations in the upper soil were significantly higher than those in the lower soil.The concentration of tea plantation soil PAEs in Jiangsu Province was significantly lower than those in Zhejiang and Anhui provinces.Intercropping with chestnuts can effectively reduce the contamination level of PAEs in tea plantation soil.Correlation analysis,redundancy analysis,partial correlation analysis,and structural equation modeling methods further confirmed the strong direct influence of factors such as chestnut–tea intercropping,temperature,and agricultural chemicals on the variation of PAEs in tea plantation soil.The health and ecological risk assessments indicated that non-carcinogenic risk was within a safe range and that there was a high carcinogenic risk via the dietary pathway,with DBP posing the highest ecological risk.

Structural characteristics of phenylboronic acid-modified astaxanthin ester and its effect on DSS-induced ulcerative colitis by blocking reactive oxygen species and maintaining intestinal homeostasis

A novel and reactive oxygen species(ROS)responsive astaxanthin phenylboronic acid derivative(AstaDPBA)was constructed by grafting phenylboronic acid(PBA)onto astaxanthin succinate diester(AstaD),and its chemical structure and physicochemical property were identified.AstaD-PBA could effectively improve the ROS quenching ability in the lipopolysaccharide(LPS)-induced RAW264.7 cell inflammation model.Then,the bioactivity of AstaD-PBA was studied by 4 zebrafish ROS-responsive infl ammatory models induced by LPS,copper(Cu^(2+)),high-fat diet,and dextran sodium sulfate(DSS).The results suggest that AstaD-PBA might have high biosafety and the best effect on ulcerative colitis(UC)induced by DSS.Furtherly,AstaDPBA significantly alleviated and treated weight loss and colonic shrinkage,inhibited infl ammatory cytokines,and maintained microbiota homeostasis to improve UC in C57BL/6J mice.Alistipes and Oscillibacter were expected to be considered UC marker fl ora according to the Metastats analysis and Pearson correlation Mantel test(P<0.01)of 16S rRNA gene sequencing data.In conclusion,AstaD-PBA has been promised to be a functional compound to improve UC and maintain intestinal microbiota homeostasis.

Carboxyl Ester Lipase Protects Against Metabolic Dysfunction-Associated Steatohepatitis by Binding to Fatty Acid Synthase

Carboxyl ester lipase(CEL),a pivotal enzyme involved in lipid metabolism,is recurrently mutated in obese mice.Here,we aimed to elucidate the functional significance,molecular mechanism,and therapeutic potential of CEL in metabolic dysfunction-associated steatohepatitis(MASH).Hepatocyte-specific carboxyl ester lipase gene(Cel)knockout(Cel^(DHEP))and wildtype(WT)littermates were fed with cholinedeficient high-fat diet(CD-HFD)for 16 weeks,or methionine-and choline-deficient diet(MCD)for three weeks to induce MASH.Liquid chromatography–mass spectrometry and co-immunoprecipitation were employed to identify the downstream targets of CEL.CD-HFD/MCD-fed WT mice received intravenous injections of CEL-adeno-associated viral,serotype 8(AAV8)to induce specific overexpression of CEL in the liver.We observed a decrease in CEL protein levels in MASH induced by CD-HFD or MCD in mice.Cel^(DHEP) mice fed with CD-HFD or MCD exhibited pronounced hepatic steatosis,inflammation,lipid peroxidation,and liver injury compared to WT littermates,accompanied by increased hepatic nuclear factor kappa-light-chain-enhancer of activated B cell(NF-jB)activation.Consistently,Cel knockdown in mouse primary hepatocytes and AML12 cells aggravated lipid accumulation and inflammation,whereas CEL overexpression exerted the opposite effect.Mechanistically,CEL directly bound to fatty acid synthase(FASN),resulting in reduced FASN SUMOylation,which in turn promoted FASN degradation through the proteasome pathway.Furthermore,inhibition of FASN ameliorated hepatocyte lipid accumulation and inflammation induced by Cel knockdown in vivo and in vitro.Hepatocyte-specific CEL overexpression using AAV8-Cel significantly mitigated steatohepatitis in mice fed with CD-HFD or MCD.CEL protects against steatohepatitis development by directly interacting with FASN and suppressing its expression for de novo lipogenesis.CEL overexpression confers a therapeutic benefit in steatohepatitis.

Research progress on classification,source,application of phytosterol esters,and their thermal oxidation stability

Phytosterol esters can effectively decrease serum cholesterol concentration in the human body and prevent cardio-cerebrovascular diseases.It was found that phytosterol esters exhibited better solubility and bioavailability than free phytosterols.In recent years,phytosterol esters have attracted increasing attention.However,during food processing,phytosterol esters are susceptible to degradation at high temperatures,resulting in certain losses and formation of potentially harmful substances for humans.This paper reviews the relevant literatures and updates on the thermal oxidation stability of phytosterol esters in recent years from the following aspects:(i)Sources,physiological activities,and applications of phytosterol esters;(ii)Oxidation mechanism of phytosterol esters;(iii)Effects of phytosterols species,the volume of addition,food matrix,heating temperature and time,and antioxidants on the thermal loss and oxidation stability of phytosterol esters.The research progress on the safety of phytosterol esters is also discussed in detail.Additionally,the prospects for future research are highlighted.

Non-flammable long chain phosphate ester based electrolyte via competitive solventized structures for high-performance lithium metal batteries

Safety remains a persistent challenge for high-energy-density lithium metal batteries(LMBs).The development of safe and non-flammable electrolytes is especially important in harsh conditions such as high temperatures.Herein,a flame-retardant,low-cost and thermally stable long chain phosphate ester based(tributyl phosphate,TBP)electrolyte is reported,which can effectively enhance the cycling stability of highly loaded high-nickel LMBs with high safety through co-solvation strategy.The interfacial compatibility between TBP and electrode is effectively improved using a short-chain ether(glycol dimethyl ether,DME),and a specially competitive solvation structure is further constructed using lithium borate difluorooxalate(LiDFOB)to form the stable and inorganic-rich electrode interphases.Benefiting from the presence of the cathode electrolyte interphase(CEI)and solid electrolyte interphase(SEI)enriched with LiF and Li_(x)PO_(y)F_(z),the electrolyte demonstrates excellent cycling stability assembled using a 50μm lithium foil anode in combination with a high loading NMC811(15.4 mg cm^(-2))cathode,with 88%capacity retention after 120 cycles.Furthermore,the electrolyte exhibits excellent high-temperature characteristics when used in a 1-Ah pouch cell(N/P=0.26),and higher thermal runaway temperature(238℃)in the ARC(accelerating rate calorimeter)demonstrating high safety.This novel electrolyte adopts long-chain phosphate as the main solvent for the first time,and would provide a new idea for the development of extremely high safety and high-temperature electrolytes.

Screening of Degrading Bacteria for Phthalic Acid Esters Under Cadmium Stress and Its Application

In order to enrich the degrading microbial resources for phthalic acid esters(PAEs)under cadmium stress,a degrading bacterium B-7 for di(2-ethylhexyl)phthalate(DEHP)was screened from the strains stored in the laboratory by means of inorganic salt liquid medium containing DEHP and cadmium,and the characteristics of the strain were studied.Strain B-7 was Bacillus amyloliquefaciens,which had high biosafety and excellent degradability to DEHP.The optimum temperature for degradation was 25–40℃,and the optimum pH value was 6–8.Strain B-7 was cultured in inorganic salt medium(MSM)with an initial DEHP concentration of 400 mg/L and cadmium content of 10 mmol/L for 4 d,and its degradation rate of DEHP was up to 93.1%.In addition,the strain had a strong degradation ability to dimethyl phthalate(DMP),diethyl phthalate(DEP),and dibutyl phthalate(DBP).In soil contaminated by cadmium and DEHP,the synergic degradation of B-7 and indigenous microorganisms in soil significantly increased the degradation rate of DEHP,indicating that this strain had potential application value in the field of microbial remediation of soil contaminated by cadmium and PAEs.

Removal of Dye Using Lignin-Based Biochar/Poly(ester amide urethane)Nanocomposites from Contaminated Wastewater

The pursuit of incorporating eco-friendly reinforcing agents in polymer composites has accentuated the exploration of various natural biomass-derived materials.The burgeoning environmental crisis spurred by the discharge of synthetic dyes into wastewater has catalyzed the search for effective and sustainable treatment technologies.Among the various sorbent materials explored,biochar,being renewable,has gained prominence due to its excellent adsorption properties and environmental sustainability.It has also emerged as a focal point for its potential to replace other conventional reinforcing agents,viz.,fumed silica,aluminum oxide,treated clays,etc.This study introduces a novel class of polymer nanocomposites comprising of lignin-based biochar particles and poly(ester amide urethane)matrix via a feasible method.The structural evaluation of these nanocomposites was accomplished using Fourier-transform infrared spectroscopy,X-ray photoelectron spectroscopy,and powder X-ray diffraction.The polymer nanocomposites exhibited superior mechanical properties with an increment in tensile strength factor by 45%in comparison to its pristine matrix,along with an excellent toughness value of 90.22 MJm^(−3)at a low loading amount of only 1 wt%.The composites showed excellent improvement in thermal properties with a sharp rise in the glass transition temperature(Tg)value from−28.15℃to 84℃,while also championing sustainability through inherent biodegradability attributes.Beyond their structural prowess,these polymer nanocomposites demonstrated excellent potential as adsorbents,displaying efficient removal of malachite green and tartrazine dyes from aqueous systems with a removal efficiency of 87.25%and 73.98%,respectively.The kinetics study revealed the pseudo second order model to be the precision tool to assess the dye removal study.Complementing this,the Langmuir adsorption isotherm provided a framework to assess the sorption features of the polymer nanocomposites.Overall,these renewable biochar integrated polymer matrices boast remarkable recovery capabilities up to seven cycles of usage with an excellent dye recovery percentage of 95.21%for the last cycle,thereby defining sustainability as well as economic feasibility.

Study on the regulatory effect of liver X receptor in HEK293 cells by six main diterpene esters in Semen Euphorbiae

Background:To study the effects of the main diterpene esters in Euphorbia factor L_(1),L_(2),L_(3),L_(7a),L_(7b)and L_(8)on the transcriptional activity and protein expression of liver X receptor(LXR).Methods:The effect of the main diterpene ester components in Semen Euphorbiae on the viability of HEK293 cells were studied by MTT assay.The LXR-Luc plasmid vector was transfected into HEK293 cells and treated with Euphorbia factor L_(1),L_(2),L_(3),L_(7a),L_(7b)and L_(8)for 24 h.The effect of the main diterpene ester components of Semen Euphorbiae on LXR-Luc luciferase activity was investigated by dual luciferase reporter gene system,and the expression of LXRαprotein was detected by Western Blot.Results:Euphorbia factor L_(1),L_(2),L_(3),L_(7a),L_(7b)and L_(8)could significantly reduce the relative luciferase activity(RLU)of LXRα,and the expression level of LXRαprotein was significantly down-regulated.Conclusion:Euphorbia factor L_(1),L_(2),L_(3),L_(7a),L_(7b)and L_(8)can inhibit the expression of LXR protein level,which may be achieved by inhibiting the transcriptional activity of LXR.

The diterpenoid esters from Euphorbia lathyris L. induce intestinal inflammation via LXRα/ABCA1-regulated lipid rafts and TLR4-mediated pathway

Background:Diterpenoid esters are considered to be the main toxic components and bioactive constituents of Euphorbia lathyris L.(EL).Euphorbia factors L1(EF1),L2(EF2),and L3(EF3),the main diterpenoid esters of EL,have been found to cause intestinal diarrhea and induce intestinal inflammation in mice.This research aimed to explore the effects of major diterpenoid esters from EL on intestinal inflammation,as well as to clarify their possible targets and molecular mechanisms in vivo and vitro.Methods:Caco-2 cells and BALB/c mice were intervened with EFL1,EFL2,and EFL3,respectively.The expressions of TLR4,NLRP3,NF-κB p65,LXRα,ABCA1,TNF-αand IL-1βwere measured by Real-time PCR and ELISA.Cholesterol efflux levels were examined using cholesterol efflux kit.Flow cytometry was applied to detect lipid rafts abundance.Confocal microscopy was applied to investigate co-localization of lipid rafts and TLR4.Results:Our results revealed that EFL1,EFL2,and EFL3 inhibited LXRα,ABCA1 expression,and cholesterol efflux,promoted colocalization of TLR4 and lipid rafts,and up-regulated TLR4,NLRP3,NF-κB p65,TNF-αand IL-1βexpressions.Conclusion:These findings reveal that the mechanisms by which EFL1,EFL2,and EFL3 induce intestinal inflammation may be associated with LXRα/ABCA1-regulated lipid rafts and TLR4-mediated pathways.

Recent Advances of Sensitive Electrochemical Sensing Platforms for Rapid Detection of Phthalate Acid Esters

As a kind of plasticizer,phthalic acid esters(PAEs)are often added to plastics to enhance elasticity,transparency,durability and prolong service life.However,it does not chemically bind to plastics and is easy to migrate to the environment.It is difficult to degrade in the environment,and it is also enriched in the human body through the food chain and respiration,which will lead to obvious adverse reactions such as decreased learning and memory function and neurobehavioral disorders.Due to the toxicity,universality and low concentration limitations of PAEs in the environment and food,it is essential to achieve rapid and sensitive detection of PAEs in soil,atmosphere,water and food.Electrochemical(EC)sensors have the advantages of simplicity,fast,low cost,portability,easy operation,high specificity and high sensitivity,so they are applied for the detection of PAEs.Although there are a large number of studies on the detection of PAEs by EC sensors,there is no review on this aspect.In this review,we introduce the detection of PAEs from classical EC sensors,electrochemiluminescence(ECL)sensors and photo-electrochemical(PEC)sensors in the past five years.This review is beneficial to understanding the construction of EC sensors and the detection mechanism of PAEs.We also propose that the development of rapid,accurate and real-time detection methods of PAEs is key to assessing risk and preventing related diseases.

基于红外光谱技术对不同间隔年限栽培丹参土壤的红外光谱特征分析

植物通过根际分泌物介导根际有益菌和病原菌差异性变化导致的连作障碍是制约丹参栽培发展的主要因素。提出一种基于红外光谱技术结合二维相关光谱的方法,快速检测丹参根际分泌物组成及含量变化。采集同一地区本底土(未种植丹参CK)、正在种植丹参(19-ING)、丹参刚采收(19-ED、23-ED)、轮休1年(23-One)、轮休2年(23-Two)、轮休5年(19-Five)等7种丹参土壤样品的光谱,进行平滑降噪、一阶导数等,提取特征图谱,分析土壤化合物指纹图谱。不同间隔年限栽培丹参土壤的红外光谱峰位和峰形相同,主要差异波段在特征吸收峰3622、3380、1638、995、777、693、524和463 cm^(-1)附近,分别表征酚酸中酚羟基—OH、酯类和有机酸类中羰基C=O、亚甲基、苯环的吸收取代、环状酮类等物质的官能团,轮休1年的土壤在各个特征峰处吸光度增强,表明种植过程中酚酸类、酯类等自毒物质不断积累。不同茬次丹参种植土壤2维相关光谱在波段3750~3600、2170~2145、2060~2030和530~585 cm^(-1)处吸收峰的位置、个数、以及颜色都不相同,清晰地表征出官能团的差异。表明采用红外光谱和2D相关光谱相结合的方法能够实现土壤中有机化合物的快速检测和监测土壤化合物动态变化,为探索丹参连作障碍的形成机理及消减机制提供理论依据。

不同拓扑结构聚(丁二酸丁二醇-对苯二甲酸丁二醇)酯的性能

通过溶液流延的方式制备了不同拓扑结构带支链的聚(丁二酸丁二醇-对苯二甲酸丁二醇)酯(PBST-Kx)薄膜,利用^(1)H NMR、GPC、TG、DSC、XRD、流变测试等方法对PBST-Kx的结构及性能进行了研究。实验结果表明,支化剂的引入不会影响PBST-Kx分子链的化学组成、热稳定性和结晶性能,但随支化剂官能度的增加,PBST-Kx的支链数增加,Mn呈减小的趋势,分子量分布变宽。支化结构的引入增加了PBST-Kx的熔体黏度,使其具有更高的弹性和更长的松弛时间,且随着支化度的增加而增大。随支化度的增加,PBST-Kx薄膜的拉伸强度和断裂伸长率降低。

基于微生物固定化的浓香型白酒无窖泥发酵影响因素研究

本实验以丝瓜络为载体,通过固定化窖泥中的功能微生物,从而代替窖泥发酵浓香型白酒。考察了载体添加量、加曲量、发酵时间、载体添加方式等因素对浓香型白酒无窖泥发酵酒醅及酒体中风味物质的影响,并利用冗余分析(redundancy analysis,RDA)方法确定了影响白酒中四大酯含量的主要因素。结果表明,不同因素条件对酒醅的含水率无明显影响,而酸度随着载体添加量、加曲量、发酵时间的增加呈现增加的趋势。在酒体中共检测到79种化合物,其中未添加固定化载体的酒体中检测到26种物质。结合冗余分析发现酒体中己酸乙酯含量与载体添加方式相关性最强,其次是发酵时间。丁酸乙酯与发酵时间呈正相关,而乙酸乙酯与载体添加量和加曲量呈正相关。因此,在后续的生产操作中可以适当调控发酵条件来改善酒体中四大酯的含量。本研究证明了丝瓜络固定复合己酸菌代替窖泥生产浓香型白酒具有实际可行性,为无窖泥发酵浓香型白酒的工艺生产提供了参考。

Anticancer Activities of Substituted Cinnamic Acid Phenethyl Esters on Human Cancer Cell Lines

Caffeic acid phenethyl ester (CAPE) and sixteen substituted cinnamic acid phenethyl esters were prepared via conventional procedures in order to test their in vitro anticancer activities by either MTT assay or SRB assay on six different human cancer cell lines. The results indicated that in the concentration of 10 μmol·L -1 the lead compound CAPE possessed anticancer activities against human HL 60, Bel 7402, and Hela cell lines, and two other compounds possessed potent anticancer activities against Bel 7402 and Hela cell lines.

Highly Efficient and Recyclable Catalyst HBF_4·SiO_2 Catalyzed Synthesis of β-Enamino Compounds Under Solvent-free Conditions

Fluoroboric acid adsorbed on silica-gel（HBF4·SiO2） has been found to be an extremely efficient and recyclable catalyst for the preparation of β-enaminones and β-enamino esters under solvent-free conditions.

Effect of linear carboxylic ester on low temperature performance of LiMn_2O_4-graphite cells

To improve the low-temperature performances of Li-ion cells, three types of linear carboxylic ester-based electrolyte, such as EC/EMC/EA（1：1：2, mass ratio）, EC/EMC/EP（1：1：2, mass ratio） and EC/EMC/EB（1：1：2, mass ratio）, were prepared to substitute for industrial electrolyte（EC/EMC/DMC）. Then, 18650-type Li Mn2O4-graphite cells（nominal capacity of 1150 mA ·h） were assembled and studied. Results show that the cells containing three types of electrolyte are able to undertake 5C discharging current with above 93% capacity retention at-20 °C. Electrochemical impedance spectra show that the discharge capacity fading of Li-ion cells at low temperature is mainly ascribed to the charge transfer resistance increasing with temperature decreasing. In comparison, the cells containing electrolyte of 1.0 mol/L LiPF6 in EC/EMC/EA（1：1：2, mass ratio） have the highest capacity retention of 90% at-40 °C and 44.41% at-60 °C, due to its lowest charge-transfer resistance.