ACYLATIVE CLEAVAGE OF CYCLIC ETHERS CATALYZED BY SAMARIUM TRICHLORIDE

Oxiranes as well as four and five membered rings of cyclic ethers were cleaved with acyl chloride in the presence of samarium trichloride or Eu(hfe)_3 as Lewis-acid catalyst under mild conditions,the oorresponding chloroesters were obtained readily and smoothly in excellent yields.

Low expression of fatty acid oxidation related gene ACADM indicates poor prognosis of renal clear cell carcinoma and is related to tumor immune infltration

This research aims to identify the key fatty acid beta-oxidation(FAO)genes that are altered in kidney renal clear cell carcinoma(KIRC)and to analyze the role of these genes in KIRC The Gene Expression Omnibus(GEO)and FAO datasets were used to identify these key genes.Wilcoxon rank sum test was used to assess the levels of acyl-CoA dehydrogenase medium chain(ACADM)between KIRC and non cancer samples.The logistic regression and Wilcoxon rank sum test were used to explore the association between ACADM and clinical features.The diagnostic performance of ACADM for KIRC was asessed using a diagnostic receiver operating ch aracteristic(ROC)curve.The co-expressed genes of ACADM were identifed in LinkedOmics database,and their function and pathway enrichment were analyzed.The correlation between ACADM expression level and immune infitration was analyzed by Gene Set Variation Analysis(GSVA)method Additionally,the proliferation,migration,and invasion abilities of KIRC cells were assessed after overexpressing ACADM.Following differential analysis and intersection,we identifed six hub genes,induding ACADM.We found that the expression level of ACADM was decreased in KIRC tissues and had a better diagnostic efect(AUC=0.916).Survival analysis suggested that patients with decreased ACADM expression had a worse prognosis.According to correlation analysis,a variety of dinical features were associated with the expression level of ACADML By analyzing the infiltration level of immune cells,we found that ACADM may be related to the enrichment of immune cells.Finally,ACADM overexpression inhibited proliferation,migration,and invasion of KIRC cells.In conclusion,our findings suggest that reduced ACADM expression in KIRC patients is indicative of poor prognosis.These results imply that ACADM may be a diagnostic and prognostic marker for individuals with KIRC,offering a reference for dinicians in diagnosis and treatment.

Synthesis of Phenylpropanoid Glycoside Analogs

The regioselective acylation of unprotected phenylethyl glucoside withcinnamoyl chloride leads to 6-OH cin-namoylated glucoside. In this manner, thirteen phenylpropanoidglycoside analogs were designed and prepared. Their structure was confirmed by ~1H NMR and ^(13)CNMR spectra.

Hrd1转基因小鼠的构建与验证

背景 内质网应激在糖尿病视网膜病变（DR）中发挥着重要作用.羟甲基戊二酰辅酶A还原酶降解蛋白1（Hrd1,又名Syvn1）作为一种内质网相关蛋白降解（ERAD）途径中的核心蛋白,能够减少内质网应激. 目的 构建Hrd1高表达小鼠,为今后研究Hrd1在DR中的作用提供动物模型. 方法 构建Hrd1系统表达重组质粒,酶切、测序后显微注射3 p1到685枚C57BL/6小鼠受精卵中,移植到代孕母鼠,得到Hrd1转基因小鼠.利用鼠尾PCR检测法鉴定F0代小鼠的基因型.得到Hrd1基因检测阳性鼠后,使其分别与野生型鼠杂交,得到F1代Hrd1转基因小鼠,取鼠尾组织,用PCR检测法再次鉴定F1代小鼠基因型. 结果 成功构建了Hrd1重组载体,重组质粒pRP.ExBi-EF1 a-Syvn1-IRES-eGFP的全序列测定结果显示,cDNA序列均正确.接受了Hrd1-pcDNA显微注射的685枚受精卵中成活598枚.将存活的受精卵移植到代孕母鼠后共产子鼠41只,获F0代子鼠8只,生理活动均良好.PCR电泳显示339 bp处阳性条带,该基因型可以传递到子代F1.结论 成功构建了Hrd1转基因小鼠.

ACYL RADICAL CYCLISATIONS

Several phenylselenyl esters were selected as precursors of acyl radicals and synthesised by our established method. Treatment of these phenylselenyl esters with tributyltinhydride and AIBN generated the corresponding acyl radicals, which were found to proceed in 5 exo trig or 6 endo trig cyclisations to afford high yields of cyclopentanones and cyclohexanones, The substitution groups on the substrates have played an important role on the regioselectivity of cyclisations.

A magnetic biocatalyst based on mussel-inspired polydopamine and its acylation of dihydromyricetin

A support made of mussel-inspired polydopamine-coated magnetic iron oxide nanoparticles （PD-MNPs） was prepared and characterized. The widely used Aspetyillus niger lipase （ANL） was immobilized on the PD-MNPs （ANL@PD-MNPs） with a protein loading of 138 mg/g and an activity recovery of 83.6% under optimized conditions. For the immobilization, the pH and immobilization time were investigated. The pH and thermal and storage stability of the ANL@PD-MNPs significant- ly surpassed those of free ANL. The ANL@PD-MNPs had better solvent tolerance than free ANL. The secondary structure of free ANL and ANL@PD-MNPs was analyzed by infrared spectroscopy, A kinetic study demonstrated that the ANL@PD-MNPs had enhanced enzyme-substrate affinity and high catalytic efficiency. The ANL@PD-MNPs was applied as a biocatalyst for the regioselective acylation of dihydromyricetin （DMY） in DMSO and gave a conversion of 79.3%, which was higher than that of previous reports. The ANL@PD-MNPs retained over 55% of its initial activity after 10 cycles of reuse. The ANL@PD-MNPs were readily separated from the reaction system by a magnet. The PD-MNPs is an excellent support for ANL and the resulting ANL@PD-MNPs displayed good potential for the efficient synthesis of dihydromyricetin-3-acetate by enzymatic regioselective acylation.

法国公司推出防治母猪尿道和生殖道疾病的营养方案

母猪尿道和生殖系统的疾病是生猪饲养当中经常发生的问题，不管从经济上还是技术上，都会导致一些饲养者无法忽视的后果。在法国，根据饲养的类型不同，这类疾病所导致的损失每百头母猪高达一千五百到两千欧元。因病症出现很晚，这类疾病又很难检测，因此提高尿液的酸性程度，能够起到限制细菌生长的作用，是一种有效的预防措施。

Anti-oxidant and anti-inflammatory effects of hydrogenrich water alleviate ethanol-induced fatty liver in mice

AIM To investigate the effects of hydrogen-rich water(HRW) treatment on prevention of ethanol(Et OH)-induced early fatty liver in mice.METHODS In vitro reduction of hydrogen peroxide by HRW was determined with a chemiluminescence system. Female mice were randomly divided into five groups: control,Et OH,Et OH + silymarin,Et OH + HRW and Et OH + silymarin + HRW. Each group was fed a Lieber-De Carli liquid diet containing Et OH or isocaloric maltose dextrin(control diet). Silymarin was used as a positive control to compare HRW efficacy against chronic Et OH-induced hepatotoxicity. HRW was freshly prepared and given at a dosage of 1.2 m L/mouse trice daily. Blood and liver tissue were collected after chronic-binge liquid-diet feeding for 12 wk.RESULTS The in vitro study showed that HRW directly scavenged hydrogen peroxide. The in vivo study showed that HRW increased expression of acyl ghrelin,which was correlated with food intake. HRW treatment significantly reduced Et OH-induced increases in serum alanine aminotransferase,aspartate aminotransferase,triglycerol and total cholesterol levels,hepatic lipid accumulation and inflammatory cytokines,including tumor necrosis factor-alpha(TNF-α) and interleukin(IL)-6. HRW attenuated malondialdehyde level,restored glutathione depletion and increased superoxide dismutase,glutathione peroxidase and catalase activities in the liver. Moreover,HRW reduced TNF-α and IL-6 levels but increased IL-10 and IL-22 levels.CONCLUSION HRW protects against chronic Et OH-induced liver injury,possibly by inducing acyl ghrelin to suppress the pro-inflammatory cytokines TNF-α and IL-6 and induce IL-10 and IL-22,thus activating antioxidant enzymes against oxidative stress.

interrelationships between ghrelin, insulin and glucose homeostasis: physiological relevance

Ghrelin is a 28 amino acid peptide mainly derived from the oxyntic gland of the stomach. Both acylated(AG) and unacylated(UAG) forms of ghrelin are found in the circulation. Initially, AG was considered as the only bioactive form of ghrelin. However, recent advances indicate that both AG and UAG exert distinct and common effects in organisms. Soon after its discovery, ghrelin was shown to promote appetite and adiposity in animal and human models. In response to these anabolic effects, an impressive number of elements have suggested the influence of ghrelin on the regulation of metabolic functions and the development of obesityrelated disorders. However, due to the complexity ofits biochemical nature and the physiological processes it governs, some of the effects of ghrelin are still debated in the literature. Evidence suggests that ghrelin influences glucose homeostasis through the modulation of insulin secretion and insulin receptor signaling. On the other hand, insulin was also shown to influence circulating levels of ghrelin. Here, we review the relationship between ghrelin and insulin and we describe the impact of this interaction on the modulation of glucose homeostasis.

Tribological Performances of Fatty Acyl Amino Acids Used as Green Additives in Lubricating Oil

The friction and wear characteristics of lauroyl glutamine, lauroyl glycine and lauroyl alanine, used as green additives in HVI 350 mineral lubricating oil, were evaluated on a four-ball tribotester. The morphologies and chemical species of the worn surfaces were analyzed by scanning electron microscope （SEM） and X-ray photoelectron spectroscope （XPS）, respectively. The test results indicated that the three fatty acyl amino acids could effectively improve the anti-wear and friction-reducing abilities of the HVI 350 mineral oil. The improvement in anti-wear and friction-reducing abilities of the mineral oil by the related amino acids was mainly ascribed to the formation of a composite boundary lubrication film due to the adsorption of amino acids on the friction surfaces.

Silica gel supported AlCl_3 catalyzed Friedel-Crafts acylation of aromatic compounds

Silica gel supported aluminium trichloride（SiO2-AlCl3） has been shown to be a mild,efficient,and chemoseiective heterogeneous Lewis acid catalyst for the acylation of aromatic compounds with acid chlorides.The catalyst can be reused up to five times after simple washing with ether and is stable（as a bench top catalyst）.

一种高效简易的聚(4-乙烯基三溴化吡啶)催化乙醇合成乙酸盐的方法(英文)

Poly(4-vinylpyridinium tribromide) is an efficient catalyst for the conversion of various alcohols to their corresponding acetate derivatives with acetic anhydride.This method has some advantages such as mild reaction conditions,good to excellent yields,and ease of work-up.

Synthesis, Crystal Structure, Docking and Antifungal Activity of a New Pyrazole Acylurea Compound

The title compound N-（（3,5-dimethylphenyl）carbamoyl）-1-methyl-3-（trifluoromethyl）-1 H-pyrazole-4-carboxamide（C（15）H（15）F3N4O2） was synthesized, and its structure was confirmed by 1 H NMR, H RMS and X-ray diffraction. It crystallizes in the triclinic system, space group P1 with a = 11.7147（5）, b = 11.7935（5）, c = 13.6620（5） A, α = 69.755（7）°, β = 66.182（6）°, γ = 72.100（7）°, Dc = 1.423 g/cm^3, Z = 4, V = 1588.88（11） A^3, the final R = 0.0347 and wR = 0.1005 for 7171 observed reflections with I 〉 2σ（I）. The preliminary biological test showed that the title compound has antifungal activities against Fusarium oxysporum, Pseudomonas syringae, Corynespora mazei and Botrytis cinerea at 100 μg/mL as 5.19%, 53.50%, 88.55% and 70.62%, respectively. The docking results indicated the hydrogen bonds formed between the compound and SHD.

Regioselective enzymatic acylation of troxerutin in nonaqueous medium

A series of monosubstituted troxerutin esters have been synthesized by enzyme-catalyzed regioselective acylation of troxerutin in nonaqueous medium.Using divinyl dicarboxylates(CH_2=CH-OOC-(CH_2)_n-COO-CH=CH_2,n = 2,3,4,7,8,11) featuring different chain length as acyl donors and alkaline protease from Bacillus subtilis as catalyst,troxerutin was regioselective acylated at B ethoxyl group.The results indicated that the regioselectivity of the enzyme-catalyzed acylation was not affected by the chain length o...

Analysis of Sucrose Esters with Long Acyl Chain by Coupling of HPLC-ELSD with ESI-MS System

The analysis of sucrose esters with long acyl chain by improved high performance liquid chromatographic method with evaporative light scattering detection （HPLC-ELSD） and electrospray ionization mass spectrum （ESI-MS） is investigated. The improved HPLC-ELSD method for the separation and quantitation of commercial and synthesized sucrose esters is described. Samples are analyzed by means of a reversed-phase （RP） HPLC using a Hypersil C8 column （250 mm× 4.6 mm, 5 μm particle size） with methanol-tetrahydrofuran （vo）ume ratio of 90 ： 10） and water under gradientcondition as the mobile phase, in which the flow rate is 1.0 ml·min^-1 and the column temperature is set at 40℃. This procedure provides a complete separation and determination ot monoester, diester, triester and higher esters with different acyl chain lengths in each fraction by a single run, in combination with the ESI-MS technology. With this method, it is possible to determine the approximate compositions of monoto polyesters in one analysis and quantitate pure positional isomers precisely using an external standard method. It is found that the method of ESI-MS coupling with HPLC system for the analysis of sucrose esters is straight forward, rapid and inexpensive, and can be readily applied in synthesis, purification and structure studies.

Two new C-glycosylflavones from the leaves of Iris lactea var. chinensis

Two new acylated C-glycosylflavones were isolated from the leaves of Iris lactea var. chinensis, and their structures were elucidated on the basis of extensive NMR experiments and mass spectrometry methods and were assigned as 5-hydroxy-4＇- methoxyflavone-7-O-（β-D-2＇＇＇＇4＇＇＇＇-diacetylrhamnopyranosyl）-6-C-[ O-（α-L-6＇＇＇-acetyl-glucpyranosyl）-1→2-β-D-glucopyrano- side] （irislactin A） and 5-hydroxy-4＇,7-dimethoxyflavone-6-C-[O-（α-L-2＇＇＇,3＇＇＇-diacetylrhanmo-pyranosyl）-1→ 2-β-D-glucopyranoside] （irislactin B）.

A mild and facile method for one pot synthesis of 2,5-di-substituted 1,3,4-oxadiazoles at room temperature

2,5-Di-substituted 1,3,4-oxadiazoles 3a-n have been synthesized as a one pot procedure from the reaction of acid hydrazide 1, acyl halides 2 and phosphorus pentoxide in acetonitrile at room temperature. High yield, short reaction time （10-15 min）, mild condition, and easy work-up are advantages of this methodology.

Synthesis and Thermal Crosslinking Behavior of Poly(aryl ether ketone)s Containing 1,4-Naphthalene Moieties

A new monomer, 1,4-bis(4-fluorobenzoyl) naphthalene(compound 2) was synthesized via a two-step reaction. 1,4-Naphthalenedicarboxylic acid chloride(compound 1) was prepared by using the acyl chlorization reaction of 1,4-naphthalenedicarboxylic acid with thionyl chloride. The Friedel-Crafts acylation of compound 1 with fluorobenzene afforded compound 2 in a 80% yield. The polycondensation of compound 2 with various bisphenols in tetramethylene sulfone(TMS) in the presence of excess potassium carbonate as a condensation reagent was carried out at 210 ℃ to quantitatively afford the corresponding poly(aryl ether ketone)s(compounds 3_8) containing 1,4-naphthalene moieties. Thermal analyses showed that the polymers have T g values ranging from 496 to 500 K and are thermally stable in air with initial mass loss above 500 ℃. These novel polymers exhibited an excellent solubility in organic solvents including NMP, DMAc, and chloroform, etc. In addition, the glass transition temperatures of these polymers increased and the polymers became insoluble in chloroform after treated at 260 ℃, indicating the occurrence of a thermal crosslinking reaction.

The effect of operating conditions on acylation of 2-methylnaphthalene in a microchannel reactor

Acylation of 2-methylnaphthalene(2-MN) is a very important reaction in organic synthesis,and the effiency of the continuous reactor is more than one of the batch reactor.Considering that the Friedel–Crafts acylation is a rapid exothermic reaction,in this study,we perform the acylation of 2-MN in a stainless steel microchannel flow reactor,which is characterized by high mass and heat transfer rates.The effect of reactant ratio,mixing temperature,reaction temperature,and reaction time on product yield and selectivity were investigated.Under the optimal conditions,2-methyl-6-propionylnaphthalene(2,6-MPN) was obtained in 85.8% yield with 87.5% selectivity.Compared with the conventional batch system,the continuous flow microchannel reactor provides a more efficient method for the synthesis of 2,6-MPN.

Comparison of total/active ghrelin levels in primary open angle glaucoma,pseudoexfoliation glaucoma and pseudoexfoliation syndrome

AIM：To investigate the levels of ghrelin（Gh）,acylated ghrelin（AGh） and AGh/Gh ratio in the humor aqueous（HA） of cases with pseudoexfoliation syndrome（PXS）,pseudoexfoliation glaucoma（PXG）,primary open angle glaucoma（POAG） and to compare these with control subjects.METHODS：A prospective examination was made of the total Gh,and AGh levels in HA of 67 patients undergoing cataract surgery.Patients were divided into 4 groups.HA samples were aspirated at the beginning of the surgery,stored at -70℃.Gh and AGh quantification was performed with ELISA kits and the AGh/total-Gh ratios were calculated.ANOVA,Kruskal-Wallis,Chi-square and post-hoc tests were used for statistical analysis.RESULTS：Total Gh levels in HA were 189.2±45.6 pg/mL in the control group,199.2±32.9 pg/mL in PXS,180.6±20.9 pg/mL in PXG and 176.8±21.4 pg/mL in POAG groups（P〉0.05）.AGh levels in HA were 23.09±5.01 pg/mL in the control group,24.13±5.22 pg/mL in PXS,22.29±1.55 pg/m L in PXG and 19.69±2.93 pg/mL in POAG groups（P〉0.05）.The ratio of AGh/Gh was 10.3%±2.34% in the control group,13.03%±2.58% in PXS,12.3%±1.54% in PXG and 11.79%±1.41% in POAG groups（P=0.044）.The difference between the PXS and control groups was significant（P=0.03）.CONCLUSION：In spite of statistically insignificant results,the HA total Gh levels were lower than those of the control subjects but not parallel with the AGh levels in glaucoma patients.The relative increase in the AGh/Gh ratio in glaucoma cases supports the view that proportional increases of AGh might play a role in the pathogenesis of glaucoma.