基于植物油中脂肪酸烷基酯含量变化鉴别废弃油脂

采用固相萃取柱净化,气相色谱-质谱联用法测定了6种植物油中脂肪酸烷基酯(包括脂肪酸甲酯和脂肪酸乙酯)的含量,并研究其在植物油煎炸、废弃及废弃油脂精炼等环节中的变化。结果发现,6种植物油中脂肪酸烷基酯的含量均低于30 mg/kg,而植物油在废弃过程中可能会形成大量脂肪酸乙酯,生成量与油脂是否烹饪及废弃物中乙醇含量有关。脂肪酸烷基酯在脱色工艺中不能被去除,但在脱臭中可被去除。因此,可以通过测定植物油中脂肪酸烷基酯含量发现废弃油脂,为废弃油脂的鉴别工作提供新的思路。     

Enzymatic Synthesis of 1‐Alkyl‐2‐hydroxy‐sn‐glycero‐2,3‐cyclic‐phosphate Using a Novel Lysoplasmalogen‐Specific Phopholipase D

Many phospholipase Ds (PLDs) are known to catalyze transphosphatidylation as well as hydrolysis of phospholipids. Transphosphatidylation of lysoplasmalogen (LyPls)‐specific phospholipase D (LyPls‐PLD), which catalyzes hydrolysis of ether lysophospholipids such as LyPls and 1‐hexadecyl‐2‐hydroxy‐sn‐glycero‐3‐phosphocholine (Lyso‐PAF), still remains unclear. This study aims to reveal the transphosphatidylation activity of LyPls‐PLD, that is, the production of cyclic ether lysophospholipid. The enzymatic reaction is conducted in a buffer system, and the reaction products of a novel LyPls‐PLD from Thermocrispum sp. are investigated using mass spectrometry (MS). MS analyses demonstrate the reaction products to consist of 100% 1‐hexadecyl‐2‐hydroxy‐sn‐glycero‐2,3‐cyclic‐phosphate (cLyPA) and choline from Lyso‐PAF; however, 1‐alkenyl‐2‐hydroxy‐sn‐glycero‐2,3‐cyclic‐phosphate from 1‐O‐1′‐(Z)‐octadecenyl‐2‐hydroxy‐sn‐glycero‐3‐phosphocholine and 1‐O‐1′‐(Z)‐octadecenyl‐2‐hydroxy‐sn‐glycero‐3‐phosphoethanolamine is not produced. These results are expected to help in elucidating the catalytic mechanism of LyPls‐PLD, that is, the rate‐limiting step, and indicate LyPls‐PLD to be useful for the one‐pot synthesis of cLyPA. Practical Applications: A novel phospholipase D, LyPls‐PLD, can exclusively synthesize cLyPA from Lyso‐PAF using a one‐step enzymatic reaction without an organic solvent. cLyPA could be expected to show bioactivities similar to those of cyclic phosphatidic acid, which promotes normal cell differentiation, hyaluronic acid synthesis, antiproliferative activity in fibroblasts, and inhibitory activity toward cancer cell invasion and metastasis.     

The Effect of Branched-Chain Fatty Acid Alkyl Esters on the Cold-Flow Properties of Biodiesel

Biodiesel (fatty acid methyl esters [FAME]) is produced from various fats, oils, and greases (FOG) using catalytic transesterification with methanol. These fuels have poor cold-flow properties depending on the fatty acid (FA) composition of the parent FOG. Improving the cold-flow properties of biodiesel will enhance its prospects for use during cooler months in moderate temperature climates. This work is a study on the use of skeletally branched-chain alkyl esters (BCAE) composed of the isopropyl, n-butyl, and 2-ethylhexyl esters of iso-oleic acid isomers (iPr-iOL, nBu-iOL, and 2EH-iOL). These BCAE additives were tested in blends with linear-FAME (L-FAME) derived from soybean oil (SME), lard (LME), tallow (TME), and sewage scum grease (SGME). Binary L-FAME/SME admixtures were also studied. Admixtures were tested for the effects of the additives on cloud point (CP), pour point (PP), and kinematic viscosities at standard (ν⁴⁰ = 40 °C) and low temperatures (T_L) = CP + 5 °C (ν^L). Although the BCAE additives were more effective than SME, relatively large additive concentrations (y_Add) were needed to depress CP and PP by more than 2 °C. Admixtures with high concentrations of BCAE additive had ν⁴⁰ > 6.0 mm² s⁻¹, the maximum limit in ASTM fuel specification D 6751. While the iPr-iOL and nBu-iOL additives may be blended at concentrations up to y_Add = 0.50, 2EH-iOL should not exceed y_Add = 0.28 in LME, 0.31 in SGME, 0.35 in TME, or 0.41 in SME to avoid driving the admixture out of specification. Some anomalies observed in the results at low y_Add for SGME/BCAE admixtures were speculated to have been affected by the low-temperature rheology of SGME.     

Intensity enhancement of photoluminescent polyesters by photocrosslinking

A series of polyesters with alkylated triazole heterocyclic rings at the branches were designed and synthesized via the polycondensation reaction. The synthesized polyesters were examined with various spectroscopic methods such as Fourier transform IR, ¹H NMR and ¹³C NMR. The alkyl chain length at the branch was found to affect the thermal stability of the polyesters, which decreased with longer alkyl chain. These polyesters possessed an aggregation‐induced emission enhancement characteristic evidenced by the transformation of the clear solutions in tetrahydrofuran with weak greenish blue emission to cloudy solutions with enhanced blue emission when water was added to promote aggregation. Furthermore, enhancement in the photoluminescence intensity was observed when the polyesters underwent photocrosslinking upon UV irradiation and appeared as self‐assembled aggregates. The formation of aggregates in the water ? tetrahydrofuran solutions and after photocrosslinking was confirmed via TEM analysis. The SEM images showed that the photocrosslinked polyesters were highly porous which may enhance the π ? π stacking interaction that improved the photoluminescence intensity. © 2015 Society of Chemical Industry     

Synthesis and polymerizations of novel bisphosphonate‐containing methacrylates derived from alkyl α‐hydroxymethacrylates

The synthesis and polymerizations of four novel bisphosphonate‐containing monomers are reported. The monomers were synthesized from reaction of ethyl and tert‐butyl α‐bromomethacrylates with 3,3‐bis(diethoxyphosphoryl)propanoic acid or with tetraethyl 4‐hydroxybutane‐1,1‐diyldiphosphonate. Their thermal bulk polymerizations, photopolymerizations and copolymerizations with poly(ethylene glycol) methyl ether methacrylate were investigated. The homopolymerizations resulted in polymers with values of 25 000–83 000 g mol^?1; the copolymerizations yielded soluble polymers with 22–34% incorporation of the new monomers; the photopolymerizations gave some structure–reactivity correlation; and one of the homopolymers, upon hydrolysis of its bisphosphonate groups, could interact with hydroxyapatite. © 2013 Society of Chemical Industry     

Solvent-Assisted Crystallization of Fatty Acid Alkyl Esters from Animal Fat

An easy and efficient method for the separation of saturated and unsaturated fatty acid mono alkyl esters, prepared from animal fat, was developed. The most efficient separation was achieved by the use of solvents such as methanol and acetone at low temperatures. The dilution of the alkyl esters with 10 times the amount of solvent (10:1 v/w) and storage of the mixture for 4 h at ?22 °C could be defined as optimum conditions. After filtration of the saturated fraction at the corresponding temperature very pure fractions were obtained. For fatty acid methyl esters deriving from tallow, with an initial content of saturated fatty acids of almost 50 %, a saturated ester fraction with only 5 % unsaturated fatty acids and an unsaturated ester fraction with about 9 % of saturated fatty acids could be obtained. The solvent easily could be recovered by distillation. In addition fatty acid ethyl, 1‐propyl, 2‐propyl, 1‐butyl, tert‐butyl and 3‐methyl‐1‐butyl esters were prepared and separated into saturated and unsaturated fractions. All fractions were analyzed according to the fatty acid compositions and showed similar or slightly worse results compared to the methyl esters. The cold filter plugging points of the unsaturated fractions were measured, showing the lowest value for the unsaturated methyl ester fraction at ?26 °C. The fractionation with the use of solvents is an easy tool in order to obtain fatty acid alkyl esters with excellent cold temperature behavior out of animal fat.     

一步法合成十二烷基葡萄糖苷反应过程研究

以正十二醇和葡萄糖为原料一步法制备十二烷基葡萄糖苷,研究了不同反应条件(催化体系、催化剂用量、温度、醇糖比等)对反应过程转化率和选择性的影响,提出了此反应过程的物理模型。研究结果表明,合成十二烷基葡萄糖苷的反应主要由生成十二烷基葡萄糖苷的主反应和生成多糖的副反应组成。十二醇与葡萄糖反应生成烷基葡萄糖苷的主反应属于液相反应机理,首先葡萄糖溶解于十二醇中,然后与十二醇发生均相反应,碳正离子与十二醇的反应是整个反应的控制步骤。反应过程中,反应体系中部分固相葡萄糖处于熔融状态,能捕捉液相中的催化剂,生成多糖副产物。不同反应条件下的实验结果表明,此反应机理能很好地描述反应过程,为此反应过程的动力学研究提供了理论基础。     

不同方法测定两种表面活性剂的临界胶束浓度

采用电导法及表面张力法分别测定了十二烷基硫酸钠(阴离子表面活性剂)和十二烷基三甲基氯化铵(阳离子表面活性剂)的临界胶束浓度,两种实验方法测得十二烷基硫酸钠的临界胶束浓度约为7.0×10-3mol·dm-3,十二烷基三甲基氯化铵的临界胶束浓度约为1.60×10-2mol·dm-3,两种方法所得结果一致。     

Visible Light‐Initiated C(sp3)?Br/C(sp3)?H Functionalization of α‐Carbonyl Alkyl Bromides through Hydride Radical Shift

A new visible light‐initiated 1,5‐hydride radical shift strategy has been developed to enable the one‐step functionalization of both a C(sp³) Br bond and a C(sp³) H bond adjacent to the same carbon atom. This visible light photoredox catalysis offers a mild and straightforward access to diverse five‐membered carbocyclic ring‐fused polycyclic hydrocarbons with high turnover numbers (TONs; up to 4.93×10³) and broad substrate scope.