Epoxidation of Unsaturated Fatty Acid Methyl Esters in the Presence of SO_3H-functional Brφnsted Acidic Ionic Liquid as Catalyst

The epoxidation of unsaturated fatty acid methyl esters(FAMEs)by peroxyacetic acid generated in situ from hydrogen peroxide and acetic acid was studied in the presence of SO3H-functional Brnsted acidic ionic liquid (IL)[C3SO3HMIM][HSO4]as catalyst.The effects of hydrogen peroxide/ethylenic unsaturation ratio,acetic acid concentration,IL concentration,recycling of the IL catalyst,and temperature on the conversion to oxirane were studied.The kinetics and thermodynamics of unsaturated FAMEs epoxidation and the kinetics of oxirane cleavage of the epoxidized FAMEs by acetic acid were also studied.The conversion of ethylenic unsaturation group to oxirane, the reaction rate of the conversion to oxirane,and the rate of hydrolysis(oxirane cleavage)were higher by using the IL catalyst.

Boosted Biodegradability and Tribological Properties of Mineral Base Oil by Methyl Diethanolamine Fatty Acid Esters

Methyl diethanolamine fatty acid esters, viz. methyl diethanolamine octanoate and methyl diethanolamine oleate,were prepared. Their impacts on the biodegradability and tribological properties of mineral base oil 400 SN were evaluated by a tester for fast evaluating the biodegradability of lubricants and by a four-ball tester, respectively. The results showed that methyl diethanolamine octanoate and methyl diethanolamine oleate both could markedly promote the biodegradation of the oil and improved its tribological properties. The improvement of biodegradability was attributed to the enhanced growth and quantity of microbes by methyl diethanolamine fatty acid esters. The worn surfaces were analyzed by a scanning electron microscope(SEM) equipped with an energy dispersive spectrometer(EDS) and an X-ray photoelectron spectroscope(XPS). The results indicated that the enhancement of friction-reducing and anti-wear properties of the mineral oil was attributed to the formation of complicated boundary lubrication films composed of species such as Fe_2O_3, Fe_3O_4 and organic nitrogen-containing compounds with a structure of –C-N-or R-NH_2.

Synthesis and Crystal Structure of 4-(4,6-dimethoxyl -pyrimidin-2-yl)-3-thiourea Carboxylic Acid Methyl Ester

The title compound 4-（4,6-dimethoxylpyrimidin-2-yl）-3-thiourea carboxylic acid methyl ester was synthesized by the reaction of 2-amino-4,6-dimethoxyl pyrimidine, potassium thiocyanate and methyl chloroformate in ethyl acetate. Single crystals suitable for X-ray measurement were obtained by recrystallization with the solvent of dimethyl formamide at the room temperature. The structure was characterized by elemental analysis and IR and determined by X-ray diffraction analysis＇ Crystallographic data： C9H12N4O4S, Mr = 272.29, monoclinic, space group C2/m with a = 1.6672（3）, b = 0.66383（12）, c = 1.1617（2） nm, β = 109.275（2）°, V = 1.2136（4） nm^3, Dc = 1.490 g/cm^3,μ = 0.281 mm^-1, F（000） = 568, Z = 4, R1 = 0.0341and wR2 = 0.1042.

Effects of Yttrium Doping on the Performance of Ru-Based Catalysts for Hydrogenation of Fatty Acid Methyl Ester

The highly dispersed supported ruthenium-yttrium (Ru-Y) bimetallic catalysts were prepared by impregnation method and their catalytic performance for hydrogenation of ester was fully investigated. The catalyst was characterized by X-ray diffraction and field emission scanning electron microscopy. The results show that the average particle diameter of the bimetallic crystallites was less than 10 nm. The effects of the reaction temperature, the hydrogen pressure, the amount of catalyst and the proportion of yttrium in catalyst on the hydrogenation of ester were studied. The experimental results show that the introduction of yttrium not only changed the chemical and textural properties of ruthenium-based catalyst but also controlled the formation of Ru-Y alloy. The Ru-Y catalyst (Ru-2%Y/TiO2) exhibited high catalytic activity and good selectivity towards the higher alcohols. Under optimal reaction conditions of 240°C and 5 MPa hydrogen pressure, the conversion of palm oil esters was above 93.4% while the selectivity towards alcohol was above 99.0%.

Electrospray Ionization Mass Spectra of Amino Acid Methyl Ester 5′-Phosphoramidates of 2′,3′-Isopropylideneuridine

Amino acid methyl ester phosphates were synthesized and determined by using positive-ion mode dectrospmy ionization mass spectrometry（ESIMS） in combination with multistage tandem mass spectrometry. The fragmentation pathways were investigated, and it was observed that most fragment ions contained the phosphoryl group. It was interesting to observe that the fragmentation pathways of the protonated molecule show some differences when compared with those of the sodium ion adduct. The methoxy group of amino acid methyl ester can migrate from the carbonyl group to the phosphoryl group in the sodium ion adduct.

Ternary Liquid-Liquid Equilibrium for Systems of Fatty Acid Methyl Ester(Methyl Palmitate/Methyl Stearate)+Ethanol+Glycerol at Atmospheric Pressure

Liquid-liquid equilibrium data of two ternary systems methyl palmitate+ethanol+glycerol and methyl stearate+ethanol+glycerol at(318.2 and 333.2)K and atmospheric pressure were measured. The values of distribution coefficient and selectivity were calculated, which indicates that glycerol can be separated from fatty acid ester by using ethanol as an extraction solvent. The consistency of the isothermal tie-line data were checked by the Othmer-Tobias equation. The correlation coefficients R2 are higher than 0.993,9 for all the fitted curves. The NRTL activity coefficient model was applied to the correlation of the measured tie-line data. The root mean square deviation(RMSD)values are less than 0.007 for all the systems, which shows a good predictive capability of this model for such systems.

Study on the Total Synthesis of 3-Oxo-9β-Acetoxyilicic Acid─The Synthesis of 9β-Acetoxy-3(4),11(13)-Dien-5αH,7αH-12-Eudesmanoic Acid Methyl Ester

The synthesis of 99-acetoxy-3(4), 11(13)-dien-5αH 7αH-12-eudesmanoic acid methyl ester (2) was achieved from oxycarvone. The key step is the p-toluenesulfonhydrazide assisted reductiv rearrangement reaction

Synthesis and Crystal Structure of 2-[(4-Methoxy- 6-methylthio-2-pyrimidinyl)aminocarbonyl- aminosulfonyl] Benzoic Acid Methyl Ester

The title compound 2-[(4-methoxy-6-methylthio-2-pyrimidinyl)aminocarbonyl- aminosulfonyl]benzoic acid methyl ester (C15H16N4O6S2, Mr = 412.44) was obtained by the reaction of (4-methoxy-6-methylthio-2-pyrimidinyl)amine with 2-methoxylcarbonylbenzene-sulfonylisocya- nate. The crystal is of monoclinic, space group P21/c with a =11.169(3), b = 9.508(3), c = 17.690(5) ? b = 91.593(5), Z = 4, V = 1877.9(10) 3, Dc = 1.459 g/cm3, F(000) = 856, m(MoKa) = 0.324 mm-1, R = 0.0690 and wR = 0.1368 for 3301 observed reflections (I > 2s(I)). The N(1)H…N(3) and N(2)H…O(4) hydrogen bonds can be observed. In the molecule the phenyl plane(I), pyrimi- din-2-yl-urea bridge plane(Ⅱ) and ester plane(Ⅲ) form three conjugated systems.

Two New Phenolic Carboxylic Acid Esters from Opuntia vulgaris

Two new phenolic carboxylic acid esters n-butyl eucomate(1) and methyl eucomate (2) and six known compounds eucomic acid(3), 3-β-acetyl-taraxerol (4), friedelin(5),lupenone(6),methyl linoleate(7) and methyl oleate(8) were isolated from the stems of Opuntia vulgaris Mill(Cactaceae). Their structures were determined on the basis of spectral methods. Compounds 3,4,6,7,8 were isolated for the first time from this plant.

Recent Development on Zero-Phosphate Spray Dried Detergent Powders Incorporated with Palm C16 Methyl Ester Sulfonates

Palm C16 methyl ester sulphonate （C16MES）is an anionic surfactant that has the potential as active ingredient in the production of laundry detergent powders. Although C16MES has been successfully applied in the production of high-density laundry detergent powders （HDDP）, it coulingd not be employed directly as it is in the spray drying process for the production of low-density laundry detergent powders （LDDP） without compromising the detergency and other significant properties. This research paper highlights the pilot-scale experimental study, which performed to produce phosphate-free laundry detergent （PFD） powders incorporated with binary anionic surfactants of C16MES and linear alkyl benzene sulphonic acid （LABSA）. Past laboratory experiments revealed that PFD powders resulted from C16MES/LABSA of 50：50 ratio and of pH 7-8 have good detergency stability upon one-week of continuous heating in an oven at 50~C with 85% relative humidity. Based on these laboratory results, subsequent experiments were carded in a 5 kg/hr capacity co-current pilot spray dryer using PFD formulations comprising six different ratios of C16MES/LABSA （0：100, 20：80, 40：60, 80：20 and 100：0） under the same pH condition. Three PFD formulations were selected for further evaluation based on their characteristics in the spray drying process. The cleaning properties and particle properties of the resulting spray dried detergent powders from these selected formulations were analyzed. Based on the overall evaluation, C16MES/LABSA in 40：60 ratio was selected as the ideal PFD formulation. Further tests confirmed that spray dried detergent powder （SDDP） from the ideal formulation has high level of biodegradability （60% in 13 d）, low eco-toxicity properties （LC50 of 11.3 mg/L） and moderate flowability charactedsUcs （Hausner ratio of 1.27 and Carr＇s index of 21.3）.

The Synthesis of Some Novel N-[α-(Isoflavone-7-O-) Acetyl]Amino Acid Derivatives

A series of novel N-[α-(isoflavone-7-O-)acetyl] amino acid methyl esters were prepared from the efficient and regioselective alkylation of isoflavones with chloroacetyl amino acid derivatives under mild condition.

Effect of alpha-lipoic acid supplementation on blood pressure, renal oxidant-antioxidant status and renal damage in spontaneously hypertensive rats

Objective:To investigate the effect of alpha-lipoic acid(ALA)supplementation on systolic blood pressure(SBP),renal oxidant-antioxidant status and renal damage in spontaneously hypertensive rats(SHR)and SHR administered with Nω-nitro-L-arginine methyl ester(L-NAME).Methods:Male rats were divided into four groups(SHR,SHR+ALA,SHR+L-NAME,SHR+ALA+L-NAME).The respective group of rats was administered with ALA(100 mg/kg/day)from age 4 weeks to 28 weeks and L-NAME(25 mg/kg/day)from age 16 weeks to 28 weeks.SBP was measured every two weeks and twenty four hour urine was collected at 4 weeks,16 weeks and 28 weeks for estimation of protein,creatinine and N-acetyl-e end of 28 weeks,rats were sacrificed and blood and kidneys colα-Dglucosaminidase.At thlected for assessment of blood creatinine,kidney thiobarbituric acid reactive substances,protein carbonyls,superoxide dismutase,catalase,glutathione peroxidase,glutathione reductase,glutathione S-transferase,glutathione disulfide,glutathione,total antioxidant status and nitric oxide as well as histopathological examination.Results:ALA supplementation significantly reduced SBP of SHR and SHR+L-NAME rats when compared to their respective non-supplemented groups.Renal oxidant status markers including thiobarbituric acid reactive substances and protein carbonyls were significantly reduced on SHR and SHR+L-NAME rats supplemented with ALA at 28 weeks as well as ALA supplementation significantly increased renal antioxidants including superoxide dismutase,catalase,glutathione peroxidase,glutathione S-transferase,glutathione and glutathione/glutathione disulfide ratio at 28 weeks.No significant change in nitric oxide levels was observed between the ALA supplemented and non-supplemented groups.Renal dysfunction was ameliorated on ALA supplementation as evidenced by significant reduction in urine protein levels,N-acetyl-α-D-glucosaminidase activity and significant increase of creatinine clearance in SHR and SHR+L-NAME at 28 weeks.Renal histopathological examination showed that ALA supplementation prevented vascular damage in SHR and ameliorated glomerular damage in SHR+L-NAME at 28 weeks.Conclusions:ALA has hypotensive and renoprotective effects on both SHR and SHR+LNAME,which could be due to its ability to ameliorate oxidative stress in the kidneys.

Determination of the Fatty Acid Profile of Breast Milk from Nursing Mothers in Bungoma County, Kenya

The fatty acid profile in breast milk of nursing mothers who participated in a Cohort for Vitamin A (COVA) study at the fourth and ninth month of lactation was investigated. Breast milk samples were collected by manual expression and stored at - 20°C until analysis. The fat was extracted from the milk and methylated using the American Oil Chemists’ Society (AOCS) Official Methods with modifications. The separation, identification and quantification of the fatty acid methyl esters was performed by gas chromatography coupled with mass spectrometry (GC-MS). Fat contents of human milk increased significantly between the fourth and ninth month of lactation 0.38 and 1.21 mg·mL-1 respectively;P 0.05) than the average percent of the total unsaturated FAs (48.93%). Similarly, at the 9th month the percentage average of the total saturated fatty acids (15.18%) was significantly lower (P < 0.05) than the average percent of the total unsaturated FAs (31.05%). The results obtained in this study demonstrated that the fat content in breast milk significantly increased in the 9th compared to the 4th month of lactation. The fatty profile was also significantly different with the omega 6 being the dominant at the 9th month compared with the omega - 9 being dominant at the 4th month of lactation.

Production of biodiesel from palm fatty acid distillate using sulfonated-glucose solid acid catalyst:Characterization and optimization

A palm fatty acid distillate （PFAD） has been used for biodiesel production. An efficient sulfonated-glucose acid catalyst （SGAC） was prepared by sulfonation to catalyze the esterification reaction. The effect of three variables i.e. methanol-to-PFAD molar ratio, catalyst amount and reaction time, on the yield of PFAD esters was studied by the response surface methodology （RSM）. The optimum reaction conditions were： 12.2：1 methanol-to- PFAD molar ratio, 2.9% catalyst concentration and 134 rain of time as predicted by the RSM. The reaction under the optimum conditions resulted in 94.5% of the free fatty acid （FFA） conversion with 92.4% of the FAME yield. The properties of the PFAD esters were determined according to biodiesel standards.

In Situ Transesterification of Wet Marine and Fresh Water Microalgae for Biodiesel Production and Its Effect on the Algal Residue

This article reports a high yielding technique of synthesizing zirconium dodecyl sulphate (“ZDS”) for in situ transesterification of Nannochloropsis occulata and Chlorella vulgaris for fatty acid methyl ester (FAME) production. ZDS produced a significantly higher FAME yield in N. occulata than in C. vulgaris (p = 0.008). The varying performance of ZDS in the two species could be due to their different cell wall chemistries. Sodium dodecyl sulphate (SDS) in H2SO4 for FAME enhancement from the two species was also studied. Treatment with SDS in H2SO4 increased the FAME production rate in both species. Residual protein content after the in situ transesterification in C. vulgaris and N. occulata reduced respectively by 6.5% and 10%. The carbohydrate content was reduced by 71% in C. vulgaris and 65% in N. occulata. The water tolerance of the process when using H2SO4, with or without SDS, was evaluated by hydrating the two species with 10% - 30% distilled water (w/w dry algae). The FAME concentration began to diminish only at 30% water content in both species. Furthermore, the presence of a small amount of water in the biomass or methanol increased the lipid extraction efficiency, improving the FAME yield, rather than inhibiting the reaction.

催化剂酸碱性与催化酯醛缩合性能的关系

以γ-Al_(2)O_(3)和SiO_(2)为载体,采用浸渍法引入不同含量Na^(+)、K^(+)和Cs+碱金属离子,制备了一系列酯醛气相缩合催化剂。利用XRD、BET、NH3-TPD和CO_(2)-TPD对催化剂的结构和表面酸、碱性进行了表征,并以丙酸甲酯与甲醛为原料,考察了其催化酯醛气相缩合反应性能。结果表明,在0.2 MPa、370℃和质量空速为1.2 h^(-1)的条件下,以10%(以载体SiO_(2)质量为基准,下同)Cs/SiO_(2)为催化剂时,丙酸甲酯转化率最高(41.03%),甲基丙烯酸甲酯选择性为99.20%。在有丰富碱活性中心的前提下,催化剂表面弱碱性位点含量与其催化酯醛气相缩合反应性能呈正相关关系,催化剂表面酸性位点和中强碱性位点的存在会导致催化剂催化活性和选择性的降低。

NiMoRe/HZSM-5催化剂的制备及其催化脂肪酸甲酯加氢脱氧

使用浸渍法制备了5 kg NiMoRe/HZSM-5催化剂,结合X射线衍射(XRD)、扫描电子显微镜(SEM)、电感耦合等离子原子发射光谱(ICP-OES)等表征手段对催化剂进行理化性质分析,并对该催化剂用于硬脂酸甲酯加氢脱氧反应的最佳条件进行探究。研究结果表明:相比3种商用催化剂,NiMoRe/HZSM-5中金属Ni具有较小颗粒,且分散均匀,BET比表面积(S_(BET))更大,为239.1 m^(2)/g,具有更好的催化活性。在温度260℃、0.3 g催化剂用量、反应时间4 h、初始H 2压力3 MPa的最优反应条件下,原料转化率和烷烃选择性均为100%,且催化剂稳定性较佳,第5次循环原料转化率仍高达96.1%,加氢脱氧(HDO)反应的选择性(S HDO/DCO),即HDO反应与脱羧脱羰(DCO)反应的比值由1.2降至0.56。将催化剂NiMoRe/HZSM-5用于脂肪酸甲酯无溶剂条件下的加氢脱氧反应放大实验后进行中试,采用2.8 L固定床对25 kg脂肪酸甲酯进行连续加氢性能评价,经过15循环后脂肪酸甲酯的转化率达到98%。

丙磺酸型碗状碳微球制备及在餐厨废油酯交换反应中的性能研究

以碗状碳微球(BHC)为载体,合成了以烷基为磺酸基键合位点的丙磺酸型碗状碳微球(PA-CBHC-Si)。X射线光电子能谱仪、扫描电子显微镜和傅里叶变换红外光谱分析表明,三步改性分别逐步丰富BHC表面羧基(—COOH)、巯基(—SH)、磺酸基(—SO_(3)H)官能团含量,且改性过程保留了载体的原始形貌。PA-CBHC-Si的酸密度高达8.5mmol/g,活性中心—SO_(3)H于300℃开始分解,具有良好的热稳定性。PA-CBHC-Si可作为煎炸废油与甲醇酯交换反应的催化剂,醇油摩尔比为16∶1,剂油比为0.02的催化体系于130℃反应4h,脂肪酸甲酯产率为84.53%。

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%。

气相色谱法测定调制羊奶粉中37种脂肪酸

建立了气相色谱法(Gas Chromatography,GC)同时测定调制羊奶粉中37种脂肪酸的分析方法。样品经氨水水解,用乙醚-石油醚混合液(1∶1,v/v)提取,提取物经2%氢氧化钠-甲醇溶液皂化,15%三氟化硼-甲醇溶液甲酯化,正庚烷提取后用GC测定。37种脂肪酸在各自的质量浓度范围内线性关系良好(R2>0.995),方法检出限为0.002~0.006 g/100 g,方法定量限为0.01~0.03 g/100 g。质控样的平均加标回收率为83.3%~108.5%,相对标准偏差为0.9%~5.6%(n=6)。该方法操作简便、准确可靠,用于测定市场购买的16组调制羊奶粉,结果发现市售调制羊奶粉中脂肪酸的组成及含量存在差异。