Synergistic extraction of rare earth by mixtures of 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester and di-(2-ethylhexyl) phosphoric acid from sulfuric acid medium

The extraction of Nd^3＋ and Sm^3＋, including the extraction and stripping capability as well as the separation effect of Nd^3＋ or Sm^3＋, from a sulfuric acid medium, by mixtures of di-（2-ethylhexyl） phosphoric acid （HDEHP, H2A2（0）） and 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester （HEH/EHP, H2L2（0）） were studied. The distribution ratios and synergistic coefficients of Nd^3＋ and Sm^3＋ in different acidities were also determined. A synergistic extractive effect was found when HDEHP and HEH/EHP were used as mixed extractants for Sm^3＋ or Nd^3＋. The chemical compositions of the extracted complex were determined as Nd.（HA2）2-HL2 and Sm.（HA2）2-HL2. The extraction equilibrium constants, enthalpy change, and entropy change of the extraction reaction were also determined.

Solvent extraction equilibrium of dysprosium(Ⅲ) from nitric acid solutions with 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester

In view of the importance of solvent extraction of rare earth metals with the acidic organophosphorous reagent,the development of a chemically based model applicable to high concentration is desired.In the present study,the equilibrium distribution of dysprosium(Ⅲ)between an aqueous nitric acid solution and 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (PC88A)was measured in the range of an initial aqueous dysprosium(Ⅲ)concentration from 1.0×10-3to 1.0×10-1kmol/m 3and PC88A concentration from 0.16 to 0.65 kmol/m3in Shellsol D70 as the diluent.The obtained data were analyzed using the chemically based model in order to correlate the equilibrium distribution ratios.In this model,dysprosium(Ⅲ)was assumed to be extracted with the PC88A dimer as a 1:3 complex,the activities were considered for the aqueous species,and the effective concentration of the PC88A dimer was calculated using Alstad's empirical equation.As a result,the apparent extraction equilibrium constant was determined to be 253(kmol·m- 3)-2with an excellent correlation between the experiment and calculation results in the wide range of the logarithm of the distribution ratio from-2 to 3.5.In conclusion,the methodology in this model would be effective for quantitative description of solvent extraction behavior of general rare earth elements as well as dysprosium.

Synergistic extraction of praseodymium with 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester and 8-Hydroxyquinoline

The synergistic extraction of Pr^3＋ from hydrochloric medium using mixture of 2-ethylhexyl phosphonic acid mono- 2-ethylhexyl ester （P507, HL） and 8-Hydroxyquinoline （HQ） in heptane was investigated. The effect of equilibrium of aqueous acidity on extraction of Pr^3＋ was discussed. The effect of extractant concentraction, different diluents, equilibrium time and acetate ion concentration oil extraction reaction were also studied. With a method of double-logarithmic slope, composition of the extracted species on 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester and 8-Hydroxyquinoline was derived. The result shows that the synergistic extraction system not only overcomes emulsification of 8-Hydroxyquinoline, but also shows perfect capacity of synergistic extraction. The largest synergistic enhancement factor can be calculated to be 5.49 at pH 3.6 for Pr^3＋.

SOLVENT EXTRACTION OF LANTHANIDES BY 2-ETHYLHEXYLPHOSPHONIC ACID MONO-2-ETHYLHEXYL ESTER

The chemistry of extraction of lanthanide and yttrium by 2-ethylhexylphosphonic acidmono-2-ethylhexyl ester in n-dodecane from nitric acid is described. By M W determination, NMR and the slope method, the extraction reaction is studied.Based upon elementery analyses, IR, NMR as well as MW determination, the compositions ofthe complexes formed with La（NO3）3 and Nd（NO3）3 are studied. Both the standard enthalprchanges（-△H°） and the relative free energy and entropy changes （-△Zr°）（△SPr°）of the ex-.traction reaction are also estimated. The regularity of the variations of Kea（concentrationequilibrium constant）, -△AZr° and △Sr°reveals the tetrad effect. The average separationfactor of the adjacent lanthanides is calculated to be as high as 3.04.

Intensified reactive extraction of 4-hydroxypyridine with di(2-ethylhexyl) phosphoric acid in 1-octanol by using tributyl phosphate

The efficient separation of amphoteric organic compounds from dilute solutions is of great importance in the industrial field. In the present work, the reactive extractions of 4-hydroxypyridine(4-HP) with tributyl phosphate(TBP), di(2-ethylhexyl) phosphoric acid(D2EHPA) and TBP + D2EHPA dissolved in 1-octanol were investigated, respectively. The influences of the initial concentrations of TBP, D2EHPA and TBP + D2EHPA on distribution ratio(D) were discussed, as well as the reactive extraction mechanism were proposed. The obvious intensification effect was observed when the mixture of TBP and D2EHPA was used as extractant. The best extraction conditions were found to be of the molar ratio of D2EHPA and TBP at 2:1 and the equilibrium aqueous pH at 3.50-4.50. D values increased with the increase of the total concentration of TBP and D2EHPA in 1-octanol. Especially, the analysis on the extraction mechanisms clearly indicate(i) TBP in 1-octanol shows negligible reactive extraction toward 4-HP,(ii) D2EHPA in 1-octanol exhibits moderate extraction effect by forming 4-HP:D2EHPA(1:1) and 4-HP:2D2EHPA(1:2) type complexes, while(iii) D2EHPA in TBP/1-octanol demonstrates the maximum distribution ratio with the 4-HP:D2EHPA(1:1) type complex domination. The discussion provides new insights on the mechanism and opens a new way for the intensified extraction of amphoteric organic compounds by using the mixture of multiple extractants in the diluent.

Green tea polyphenols alleviate di-(2-ethylhexyl)phthalate-induced liver injury in mice

BACKGROUND Di(2-ethylhexyl)phthalate(DEHP)is a common plasticizer known to cause liver injury.Green tea is reported to exert therapeutic effects on heavy metal exposureinduced organ damage.However,limited studies have examined the therapeutic effects of green tea polyphenols(GTPs)on DEHP-induced liver damage.AIM To evaluate the molecular mechanism underlying the therapeutic effects of GTPs on DEHP-induced liver damage.METHODS C57BL/6J mice were divided into the following five groups:Control,model[DEHP(1500 mg/kg bodyweight)],treatment[DEHP(1500 mg/kg bodyweight)+GTP(70 mg/kg bodyweight),oil,and GTP(70 mg/kg bodyweight)]groups.After 8 wk,the liver function,blood lipid profile,and liver histopathology were examined.Differentially expressed micro RNAs(miRNAs)and mRNAs in the liver tissues were examined using high-throughput sequencing.Additionally,functional enrichment analysis and immune infiltration prediction were performed.The miRNA-mRNA regulatory axis was elucidated using the starBase database.Protein expression was evaluated using immunohistochemistry.RESULTS GTPs alleviated DHEP-induced liver dysfunction,blood lipid dysregulation,fatty liver disease,liver fibrosis,and mitochondrial and endoplasmic reticulum lesions in mice.The infiltration of macrophages,mast cells,and natural killer cells varied between the model and treatment groups.mmu-miR-141-3p(a differentially expressed miRNA),Zcchc24(a differentially expressed mRNA),and Zcchc24(a differentially expressed protein)constituted the miRNA-mRNA-protein regulatory axis involved in mediating the therapeutic effects of GTPs on DEHP-induced liver damage in mice.CONCLUSION This study demonstrated that GTPs mitigate DEHP-induced liver dysfunction,blood lipid dysregulation,fatty liver disease,and partial liver fibrosis,and regulate immune cell infiltration.Additionally,an important miRNAmRNA-protein molecular regulatory axis involved in mediating the therapeutic effects of GTPs on DEHP-induced liver damage was elucidated.

K_(2)CO_(3)/KOH协同醇解废弃涤纶纺织品及其制备再生DMT的研究

废弃涤纶纺织品囤积量逐年上升,而对废弃涤纶纺织品的综合利用回收率却较低。化学法回收中乙二醇醇解-甲醇酯交换法是一种回收废弃涤纶纺织品的方法,然而乙二醇醇解-甲醇酯交换工艺过程中存在对苯二甲酸双羟基乙酯(BHET)单体产率低、低聚物含量高的问题。文章采用K_(2)CO_(3)/KOH协同醇解废弃涤纶纺织品,并结合响应面法优化了醇解工艺参数,通过甲醇酯交换法制得再生对苯二甲酸二甲酯(DMT),研究了K_(2)CO_(3)/KOH协同醇解对乙二醇醇解-甲醇酯交换产物的影响。结果表明,随着KOH添加量的增加,醇解产物中BHET含量呈现先增加后下降的趋势。当KOH的添加量达到2%时,BHET含量达到最高70.2%。同时,优化后的醇解工艺参数为:反应温度210℃、反应时间120 min、K_(2)CO_(3)质量分数2.0%、KOH质量分数2.4%。此时BHET的收率为73.1%;醇解产物与甲醇酯交换得到再生DMT产率为80.1%,通过减压升华纯化后得到再生DMT含量高于99%以上。

雪花状Fe_(2)O_(3)-AgNPs SERS基底在大豆基天然酯绝缘油-糠醛检测中的应用

本文通过一步水热合成了雪花状三氧化二铁(α-Fe_(2)O_(3))纳米材料,并通过化学还原法在其表面原位生长银纳米颗粒(AgNPs),并将其作为表面增强拉曼散射基底用于检测大豆基天然酯油中的糠醛浓度。根据扫面电子显微镜(SEM),透射电子显微镜(TEM),X射线衍射仪(XRD),电化学工作站以及拉曼光谱仪(Raman)分别进行表征。结果表明,以RhB作为探针分子,最低检测限为10-11 mol/L(M),而且相较于单一AgNPs基底,α-Fe_(2)O_(3)-AgNPs的SERS性能更优异。将α-Fe_(2)O_(3)-AgNPs基底进行功能化处理,使其表面修饰4-ATP分子,并用于检测大豆基天然酯绝缘油中的糠醛,最低检测限能达到0.05 mg/L。检测结果完全满足电力行业绝缘油的老化标准(重度老化,4mg/L;中度老化,0.5 mg/L;轻度老化,0.1 mg/L)。

6-氟-4-羟基-3-氧代-3,4-二氢喹喔啉-1(2 H)-羧酸叔丁酯的合成、晶体结构及抗肿瘤活性研究

喹喔啉类化合物由于具有显著的生物活性而被广泛应用于医药、化工领域,特别是抗癌药物研发领域。本文通过四步反应法首次合成了6-氟-4-羟基-3-氧代-3,4-二氢喹喔啉-1(2 H)-羧酸叔丁酯,经溶液结晶法获得其单晶体。晶体学分析表明,该化合物属单斜晶系,空间群C2/c,晶胞常数a=1.28663(10)nm,b=2.25249(17)nm,c=1.01564(7)nm,Z=8,ρ_(c)=1.359 g·cm^(-3),R=0.0538,R_(w)=0.1406。在B3LYP/6-311+G(2d,p)模式下使用密度泛函理论(DFT)计算了该化合物的最佳结构,与X射线单晶衍射确定的晶体结构基本一致。抗肿瘤活性研究表明其有良好的抗肿瘤作用。此外,通过DFT计算了分子的静电势和前沿分子轨道。

山梨坦(2-丙基)庚酯的合成及性能

将煤制烯烃(MTO)的副产物2-丙基庚醇通过氧化反应制得2-丙基庚酸,再以其和山梨醇为原料,通过一步法合成了山梨坦(2-丙基)庚酯,采用FT-IR、GC及HPLC进行了表征。结果表明:粗产物中山梨坦(2-丙基)庚酯单酯质量分数可达59.8%,提纯产物中单酯含量可达95.6%。山梨坦(2-丙基)庚酯产品的防腐抑菌性能达到并优于市售山梨坦辛酸酯的水平,具有较好的乳化、助洗功能。将山梨坦(2-丙基)庚酯替代部分表面活性剂加入洗衣液中,无需添加防腐剂,微生物挑战实验7 d,菌落数即小于10 cfu/g,洗涤性能优异。

超临界CO_(2)萃取石榴籽油及石榴酸甲酯富集

采用超临界CO_(2)萃取技术从石榴籽中提取石榴籽油,对其脂肪酸和甘三酯组成和含量进行分析;通过单因素和正交优化试验研究尿素包合法富集石榴酸甲酯。超临界CO_(2)萃取技术与有机溶剂萃取相比更有利于获得高石榴酸含量的石榴籽油,石榴籽油中检测出14种甘三酯。尿素包合法富集石榴酸甲酯的最佳工艺为尿素包合温度5℃、包合时间20 h、尿素与脂肪酸甲酯的质量比1∶1、尿素和95%乙醇的质量比1∶5,此最佳包合条件下获得的石榴酸甲酯的含量为78.82%。

气相色谱—串联质谱法测定阿哌沙班中2-氯乙酰乙酸乙酯的残留量

目的:建立一种气相色谱—串联质谱(GC-MS/MS)方法,用于测定阿哌沙班中潜在基因毒性杂质2-氯乙酰乙酸乙酯的残留量。方法:用聚乙二醇[VF-WAXms(30 mm×0.25 mm×0.25μm)]为固定液的毛细管色谱柱;进样口温度为230℃;流速1.0 mL/min;载气:氦气;不分流进样。采用电子轰击离子源(EI),选择离子监测模式(SIM)。结果:2-氯乙酰乙酸乙酯在0.05~1.02μg/mL质量浓度范围内呈现良好的线性关系(r=0.9985);定量限浓度是0.02μg/mL;检出限是0.01μg/mL;三份不同浓度水平的平均回收率为97.9%(RSD=4.2%)。结论:所建立的GC-MS/MS测定方法灵敏度高、专属性强和准确度好,可用于阿哌沙班中2-氯乙酰乙酸乙酯的测定。

Azalomycin F_(4a) 2-ethylpentyl ester,a new macrocyclic lactone,from mangrove actinomycete Streptomyces sp.211726

Azalomycin F4a 2-ethylpentyl ester,a new 36-membered macrocyclic lactone antibiotic,was isolated from mangrove actinomycete Streptomyces sp.211726.Its structure was elucidated on the basis of spectroscopic data.The compound showed broad-spectrum antifungal activity and moderate cytotoxicity against human colon tumor cell HCT-116.

Short communication Catalytic synthesis of butyric esters with TiSiW_(12)O_(40)/TiO_2

The catalytic activities of TiSiW_(12)O_(40)/TiO_2 in synthesizing ethylester; propyl ester, n-butyl ester; and amyl ester were reported. It was demonstrated thatTiSiW_(12)O_(40)/TiO_2 is an excellent catalyst. Various factors concerned with esterification wereinvestigated. The optimum conditions were found: the mole ratio of alcohol to acid is 1.3:1, themass ratio of catalyst to reactants is 1.5 percent, and the reaction time is 1.0 h. Under theoptimum conditions, the yields are 88.0 percent for ethyl ester, 94.5 percent for propyl ester, 98.6percent for n-butyl ester, 99.1 percent for n-amyl ester, and 96.7 percent for iso-amyl ester,respectively.

Caffeic acid phenethyl ester up-regulates antioxidant levels in hepatic stellate cell line T6 via an Nrf2-mediated mitogen activated protein kinases pathway

AIM To investigate the antioxidant effect of caffeic acid phenethyl ester (CAPE) in hepatic stellate cell-T6 (HSC-T6) cells cultured in vitro and the potential mechanisms. METHODS HSC-T6 cells were cultured in vitro and treated with various concentrations of CAPE for 24, 48 and 72 h, respectively. Cell proliferation was investigated using the MTT assay, and cell ultrastructural alterations were observed by transmission electron microscopy. Flow cytometry was employed to investigate the effects of CAPE on apoptosis and the levels of reactive oxygen species in HSC-T6 cells cultured in vitro. An enzyme immunoassay instrument was used to evaluate antioxidant enzyme expression. The effect on alpha-smooth muscle actin was shown using immunofluorescence. Gene and protein levels of Nrf2, related factors, and mitogen activated protein kinases (MAPKs), in HSC-T6 cells were detected using RT-PCR and Western blot, respectively. RESULTS CAPE inhibited the proliferation and activation of HSC-T6 cells cultured in vitro. CAPE increased the antioxidant levels and the translocation of Nrf2 from the cytoplasm to the nucleus in HSC-T6 cells. Moreover, the phosphorylation of MAPKs in cells decreased in response to CAPE. Interestingly, CAPE-induced oxidative stress in the cells was significantly attenuated by pretreatment with MAPKs inhibitors. CONCLUSION CAPE inhibits cell proliferation and up-regulates the antioxidant levels in HSC-T6 cells partly through the Nrf2-MAPKs signaling pathway.

Glycerin Monostearate Aggravates Male Reproductive Toxicity Caused by Di(2-ethylhexyl)Phthalate in Rats

Human beings are increasingly exposed to phthalates,which are a group of chemicals used to make plastics more flexible and harder to break,and simultaneously ingesting abundant food emulsifiers via daily diet.The purpose of this study was to investigate the effect of the food emulsifier glycerin monostearate(GMS)on male reproductive toxicity caused by di(2-ethylhexyl)phthalate(DEHP,one of the phthalates)and explore the underlying mechanism.Thirty male Sprague-Dawley rats were randomly divided into control group,DEHP group and DEHP+GMS group.Rats in the DEHP group and DEHP+GMS group were orally administered with 200 mg/kg/d DEHP with or without 20 mg/kg/d GMS.After 30 days of continuous intervention,it was found that the serum testosterone level was significantly lowered in DEHP group and DEHP+GMS group than that in control group(P<0.01).The serum testosterone level and the relative testis weight were significantly decreased in the DEHP+GMS group as compared with those in the DEHP group and control group(P<0.05).More spermatids were observed to be shed off in DEHP+GMS group than in DEHP group.The expression levels of cell cycle checkpoint kinase 1(Chkl),cell division cycle gene 2(Cdc2),and cyclin-dependent kinase 2(CDK2)were down-regulated in DEHP group,and this tendency was more significant in DEHP+GMS group(P<0.05 or P<0.01).There was no significant difference in the P-glycoprotein(P-gp)expression between DEHP group and control group.However,P-gp was markedly down-regulated in DEHP+GMS group(P<O.Ol).The results indicated that the food emulsifier GMS aggravated the toxicity of DEHP on male reproduction by inhibiting the cell cycle of testicular cells and the expression of P-gp in testis tissues.

Reactive extraction for intensifying 2-ethylhexyl acrylate synthesis using deep eutectic solvent [Im:2PTSA]

2-Ethylhexyl acrylate(2-EHA)is one of the most widely used acrylates in the polymer industry,which is synthesized via Fisher esterification that is limited by chemical equilibrium.To intensify the esterification process,in this work,reactive extraction concept is proposed,with halogen-free deep eutectic solvent(DES[Im:2PTSA])as dual solvent-catalyst that consists of imidazole(Im)and p-toluenesulfonamide(PTSA).The bifunctional effects of the DES[Im:2PTSA]are evaluated by thermodynamic analysis and experimental study.Favorable phase splitting is verified byσ-potential analysis predicted by COSMO-RS theory,combined with experiments,and the optimal acid-to-alcohol molar ratio is set to 1.2.The esterification kinetics is then experimentally determined and fitted using the molar-based and activity-based pseudo-homogeneous(PH)models,respectively.The activity-based PH model,that considers the bifunctional roles of the DES,proves to be more accurate with small RMSD of 0.0344.The stability of DES after recycling is validated to further confirm the industrial prospects of DES[Im:2PTSA]in 2-EHA production.

奥美沙坦酯联合骨化三醇治疗对早期2型糖尿病肾病患者炎症状态及肾间质纤维化的影响

目的研究奥美沙坦酯联合骨化三醇治疗对早期2型糖尿病肾病(T2DN)患者炎症状态及肾间质纤维化的影响。方法以回顾性分析为法,观察对象为2020年1月至2022年1月入四川大学华西医院的100例早期T2DN患者,根据不同治疗方法分为研究组(n=50)与对照组(n=50)。研究组联用奥美沙坦酯、骨化三醇治疗,对照组单用奥美沙坦酯治疗,持续用药8周。比较两组患者治疗前后炎症指标[C反应蛋白(CRP)、降钙素原(PCT)]、肾间质纤维化指标[血清同型半胱氨酸(Hcy)、血管内皮生长因子(VEGF)、转化生长因子β1(TGF-β1)]、血糖指标[糖化血红蛋白(HbA1c)、餐后2 h血糖(2 hPG)、空腹血糖]水平、肾功能指标[肾小球滤过率(GFR)、血尿素、血肌酐]水平与治疗后总有效率、不良反应(恶心呕吐、头晕头痛、发热、胃肠道反应)发生率。结果治疗8周后,两组患者的CRP、PCT、Hcy、VEGF、TGF-β1、HbA1c、2 hPG、空腹血糖、血尿素、血肌酐水平较治疗前明显下降,GFR较治疗前明显升高,差异均有统计学意义(P<0.05);研究组患者的CRP、PCT、Hcy、VEGF、TGF-β1、HbA1c、2 hPG、空腹血糖、血尿素、血肌酐水平为(14.36±2.04)mg/L、(1.21±0.08)μg/L、(13.79±1.72)μmol/L、(346.91±23.82)pg/mL、(152.97±18.92)pg/mL、(5.81±0.65)%、(8.36±1.24)mmol/L、(6.18±1.06)mmol/L、(4.27±1.08)mmol/L、(71.28±11.15)μmol/L,较对照组[(16.32±2.26)mg/L、(1.44±0.11)μg/L、(19.34±2.48)μmol/L、(394.36±25.11)pg/mL、(169.04±19.75)pg/mL、(6.42±0.76)%、(10.28±1.39)mmol/L、(7.81±1.12)mmol/L、(5.61±1.16)mmol/L、(78.41±12.37)μmol/L]更低,GFR为(93.85±8.62)mL·min^(-1)·1.73 m^(-2),较对照组[(86.29±8.93)mL·min^(-1)·1.73 m^(-2)]更高,差异均有统计学意义(P<0.05)。研究组患者的治疗总有效率为98.00%,明显高于对照组(84.00%),差异有统计学意义(P<0.05)。两组患者恶心呕吐、头晕头痛、发热、胃肠道反应发生率比较,差异无统计学意义(P>0.05)。结论奥美沙坦酯联合骨化三醇治疗早期T2DN患者的效果显著,可抑制患者炎症反应及肾脏纤维化,改善血糖及肾功能,且无明显副作用,安全性高。

Potassium iodide catalyzed reductive dehalogenation ofα-halo-ketones using Hantzsch ester diethyl 1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylate as reductant

In the presence of diethyl 1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylate（DHP） and a catalytic amount of potassium iodide,severalα-halo ketones were easily reduced to the corresponding ketones in acetone media.The procedure presented here showed several merits such as short reaction time,practical experimental and isolated procedure,and excellent yields of products.

Synthesis, Crystal Structure and Inhibition of N-2-Thiophenesulfonyl-α-L-phenylalanine Ethyl Ester on K562 Cell Proliferation

The title compound N-2-thiophenesulfonyl-a-L-phenylalanine ethyl ester has been synthesized. Complete assignments were achieved by IR, MS, ^1H NMR and single-crystal X-ray diffraction analyses. Using MTT assay, the inhibitory rate of the title compound on K562 cells （chronic myeloid leukemic cells） was measured and the result of preliminary bioassay showed that the title compound possesses antiproliferation effects on K562 cells. In order to investigate the relationship between structure and activity of the target compound, we report its crystal structure and biological behavior in the present paper. Crystallographic data： C15H17NO4S2, Mr = 339.42, monoclinic, space group P21, flack = -0.15（12）, a = 5.7916（10）, b = 11.5078（19）, c = 12.924（2） A, β = 97.781（3）°, Z = 2, V = 853.4（2） A^3, De = 1.321 g/cm^3, F（000） = 356, -7≤h≤7, -10≤k≤14, -15 ≤ l≤15, R = 0.0628, wR = 0.1540 and μ（MoKa） = 0.327 mm^-1. The molecule comprises a benzene and a thiofuran rings, and the intramolecular N（1）-H（1A）…O（1） makes a five-membered ring of O（1）--C（6）-C（5）--N（1）--H（1A）.