正癸酸-棕榈酸-硬脂酸三元脂肪酸复合相变材料的热性能

以癸酸(CA)、棕榈酸(PA)和硬脂酸(SA)为原料,通过超声法制备了三元脂肪酸复合相变材料。由二元相图确定CA-PA的二元配比,由三元相图确定CA-PA-SA的三元配比,由DSC和FT-IR测试其化学性质和热性能。FTIR表明共混复合相变材料中3种脂肪酸是通过分子间作用力结合在一起;DSC表明共混复合相变材料的相变温度为25.59℃、相变焓176.98J·g-1,由二元和三元相图可以看出,相变温度都是先降低后升高,表现出低共熔物特征;通过500次热循环测试,作为相变材料脂肪酸三元低共熔物具有良好的热稳定性和化学稳定性。根据上面的结论得出CAPA-SA复合相变材料有合适的相变温度和相变潜热,适合做蓄热低温材料。     

脂肪酸相变储能材料热循环行为的试验研究

研究了一些脂肪酸作为相变材料的热稳定性。选用的脂肪酸为化学纯的癸酸、月桂酸、肉豆蔻酸和棕榈酸,其融化温度在30~60℃之间。利用差示扫描量热(DSC)技术测定了经过56、112、200和400次反复热循环的相变材料的融化温度和融化潜热,加速热循环试验结果表明:随着热循环次数的增加,相变材料的融化初始温度和融化潜热的变化很小,并且是没有规律的。但是,考虑相变材料的使用约为1年的热循环,在脂肪酸的热性能方面,这些材料作为潜热存储材料具有很好的热稳定性。     

碳/SiO_2纳米纤维膜基定形相变材料的制备及性能

研究首先制得二元脂肪酸低共熔物,然后将用静电纺丝法制备不同SiO2含量的、并对其进行炭化的PAN/SiO2纳米纤维膜作为支撑材料,吸附二元脂肪酸低共熔物制得碳/SiO2纳米纤维膜基定形相变材料(CSNPCM),利用扫描电子显微镜(SEM)、差示扫描量热仪(DSC)等对制备出的定形相变材料的形貌结构和储热性能进行分析和表征。随着SiO2含量的增加,定形相变材料对二元脂肪酸低共熔物的吸附容量有所降低。SEM结果表明,二元脂肪酸低共熔物均匀地包埋、分散在多孔纳米纤维膜的三维网络结构中。DSC测试结果表明,SiO2的加入降低了定形相变材料的相变潜热,对其相变温度无太大影响。     

PET基定形相变复合纤维的制备

采用静电纺丝技术成功制备了以5种脂肪酸二元低共熔混合物(LA-MA、LA-SA、MA-PA、MA-SA、PA-SA)为固液相变材料,聚对苯二甲酸乙二酯(PET)为支撑材料的定形相变复合纤维。研究了不同种类的脂肪酸二元低共熔物对复合相变纤维的形貌结构、储热性能以及力学性能的影响。研究结果表明这5种定形相变复合纤维的表面均呈现褶皱的形貌特征,同时纤维直径也明显增大。热分析结果表明当改变纤维中脂肪酸二元低共熔物的种类时,复合相变纤维的熔化温度和熔化焓值均随之而变化,其中熔化温度最低为33.23℃,最高为52.82℃,熔化焓值最低为62.75kJ/kg,最高为94.76kJ/kg。力学性能测试结果表明,由于脂肪酸二元低熔物的加入复合相变纤维的拉伸强度减小,断裂伸长率增大。     

CA-LA-MA-PA-SA/PAN/MWNTs-COOH相变复合纤维膜的结构与热性能

以脂肪酸五元低共熔物(CA-LA-MA-PA-SA)为固-液相变材料,以聚丙烯腈/羧基化多壁碳纳米管(PAN/MWNTs-COOH)复合纤维膜为支撑载体,其中PAN/MWNTs-COOH的质量比例为95/5和90/10,通过物理吸附法制备CA-LA-MA-PA-SA/PAN/MWNTs-COOH定形相变复合纤维膜。系统分析了复合纤维膜的形态结构、相变温度和焓值、储放热速率。SEM观察结果表明CA-LAMA-PA-SA五元低共熔物被成功地吸附到静电纺PAN/MWNTs-COOH复合纤维膜的多孔网络结构中。DSC测试结果表明制备的纤维膜的相变融化温度和焓值约为19℃和121～129kJ/kg。传热测试结果表明添加MWNTs-COOH后复合纤维膜的储热和放热效率得到显著提高。     

有机复合相变材料性能研究

为了获得适用于建筑领域的相变材料(PCM)和相变温度,以脂肪酸类十酸(CA)、十二酸(LA)、十四酸(MA)、十六酸(PA)、十八酸(SA)和脂肪醇类十二醇(DE)、十四醇(TD)为原料,采用熔融共混法制备了一系列有机复合相变材料。采用步冷曲线法测量了PCM相变过程的相变特性。结果表明:酸-酸和酸-醇二元体系以及酸-酸-酸三元体系均存在共晶温度。LA与SA质量比为2∶1左右时,共晶温度为30.6℃;酸-酸-酸三元体系具有比二元体系略低的共晶温度;酸-醇二元体系则具有更低的共晶温度,LA与TD质量比为3∶4左右时,共晶温度为23.1℃;DE作为添加剂可降低CA的结晶温度,当添加DE的质量分数为5%左右时,结晶温度为28.3℃,适用于建筑领域。     

脂肪酸三元体系相变材料固-液相变动力学研究

为有效地控制脂肪酸贮能材料的相变过程,利用差示扫描量热法(DSC)研究了癸酸(CA)-肉豆蔻酸(MA)-硬脂酸(SA)、CA-MA-棕榈酸(PA)、CA-PA-SA三元低共熔物体系的热力学性能,确定最低共熔混合物的组成、相变温度和相变潜热。运用Kissinger动力学方法计算CP-MA-SA、CP-MA-PA、CP-PA-SA三元低共熔混合物固-液相变过程的相变活化能及反应级数。结果表明:活化能为257.46~353.40kJ/mol,反应级数为1左右,动力学参数为脂肪酸三元体系在民用建筑的应用提供了重要依据。     

棕榈酸-十六醇/二氧化硅相变储能材料的低热固相合成与表征

以棕榈酸-十六醇(PA-HD)低共熔物为相变材料,硅酸钠为硅源,通过低热固相化学合成方法制备出棕榈酸-十六醇/二氧化硅相变储能材料(PA-HD/SiO2)。利用FT-IR,ESEM,DSC,融化-凝固曲线测试对材料的结构、形貌和性能进行表征。结果表明:当相变材料与硅酸钠质量比为2∶1时可实现相变材料的有效包覆,PA-HD/SiO2相变焓值和相变温度分别为102.35J·g-1和53.69℃,该定形复合相变材料具有良好的传热性能,因为包覆作用,使得相变材料的相变温度有所升高。     

沉积Ag纳米层改善定型相变复合纤维膜的传热性能

以癸酸(CA)、月桂酸(LA)和肉豆蔻酸(MA)为原料制备了新型的脂肪酸三元低共熔物(CA-LA-MA),并将其作为固-液相变材料,以沉积2 h银(Ag)纳米颗粒的静电纺聚丙烯腈(PAN)纳米纤维膜为支撑材料,通过物理吸附法制备了新型的CA-LA-MA/PAN和CA-LA-MA/PAN/Ag定型相变复合纤维膜。研究了磁控溅射Ag纳米层对定型相变复合纤维传热性能的影响。结果表明,沉积Ag纳米层后定型相变复合纤维膜的储热和放热时间分别缩短了31%和25%。制备的CA-LA-MA/PAN/Ag定型相变复合纤维膜的融化温度和结晶温度分别为19.87℃和11.63℃,融化焓值和结晶焓值分别为123.1 kJ/kg和121.5 kJ/kg。     

纳米石墨粉改善定形相变复合纤维膜的储热和放热速率EI北大核心CSCD

采用静电纺丝法制备了负载不同含量纳米石墨粉(NG)的聚丙烯腈(PAN)基复合纤维膜作为支撑材料,以癸酸-月桂酸-肉豆蔻酸(CA-LA-MA)三元低共熔物为固-液相变材料,通过物理吸附法制备CA-LA-MA/PAN/NG定形相变复合纤维膜。分别采用傅里叶变换红外光谱仪、扫描电子显微镜、差示扫描量热仪和传热测试装置对定形相变复合纤维膜的化学性能、形貌结构、储热性能、热能储存和释放速率进行深入分析。研究结果表明,CA-LA-MA三元低共熔物成功地被吸附到PAN基复合纤维膜中。制备的定形相变复合纤维膜的相变融化温度约为19℃,相变焓值约为114～131kJ/kg。由于添加了具有高导热系数的NG使定形相变复合纤维膜的热能储存和释放效率明显提高了43%和42%。     

Enantioselective determination of anteiso fatty acids in food samples

Anteiso fatty acids (aFAs)-long-chain carboxylic acids with a methyl branch on the (n - 2)-carbon-are among the most simple fatty acids that are chiral. The most frequently occurring aFAs in food are 12-methyltetradecanoic acid (a15:0) and 14-methylhexadecanoic acid (a17:0), structures where the asymmetric carbon is more than 10 carbons separated from the polar head group. Previously, only enantioseparation of 4-methyl-substituted carboxylic fatty acids has been reported by gas chromatography. Here we present the first direct partial enantioresolution of synthesized racemic a15:0-a17:0 on a capillary column coated with 50% heptakis(6-O-tert-butyldimethylsilyl-2,3-di-O-methyl)-beta-cyclodextrin diluted in OV1701. Synthesized (S)-(+)-enantiomers were used to demonstrate that the elution order was (R)- prior to (S)-enantiomers. Using this system, food samples (butter, goat's milk fat, suet, human milk, seal oil, cod liver oil) known to contain aFAs were analyzed. Prior to the enantioselective gas chromatography, unsaturated fatty acids were preseparated by urea complexation, silver ion high performance liquid chromatography (Ag+-HPLC), or both from food samples. The fractions of the food samples enriched with methyl-branched fatty acids were then analyzed by GC/MS in the SIM mode. The measurements confirmed that the (S)-enantiomer of a15:0 (ee >96%), a16:0, and a17:0 (ee >90%, respectively) dominated in all samples. While the (R)-enantiomers could not be identified in samples from ruminants and human milk, their presence could be established in cod liver and seal oil (ee <86%).     

Electrogenerated chemiluminescence derivatization reagents for carboxylic acids and amines in high-performance liquid chromatography using tris(2,2'-bipyridine)ruthenium(II)

2-(2-Aminoethyl)-1-methylpyrrolidine and N-(3-aminopropyl)pyrrolidine (NAPP) were found to be selective and sensitive derivatization reagents for carboxylic acid by high-performance liquid chromatography (HPLC) with electrogenerated chemiluminescence detection using tris(2,2'-bipyridine)ruthenium(II). Free fatty acids and ibuprofen were used as model compounds of carboxylic acids, and the derivatization conditions were optimized with myristic acid as a representative of free fatty acids. All the fatty acids tested were reacted with NAPP to produce highly sensitive derivatives under the mild reaction conditions of room temperature for 30 min in acetonitrile containing 2-bromo-1-ethylpyridinium tetrafluoroborate and 9-methyl-3,4-dihydro-2H-pyrido[1,2-a]pyrimidin-2-one. The chemiluminescence intensities were similar for all fatty acids. The derivatives obtained from 10 free fatty acids were completely separated by reversed-phase chromatography under isocratic elution conditions. The on-column detection limits (signal-to-noise ratio of 3) with proposed HPLC separation and chemiluminescence detection were 70 and 45 fmol for myristic acid and ibuprofen, respectively. The free fatty acids in human plasma were successfully determined using the present method. Histamine, a model compound of primary amines, was also determined after precolumn derivatization with 3-(diethylamino)propionic acid at room temperature for 60 min in acetonitrile containing N,N'-dicyclohexylcarbodiimide and 3,4-dihydro-3-hydroxy-4-oxo-1,2,3-benzotriazine with the detection limit of 70 fmol.     

Microstructure Characteristics of the Eutectics of Die Cast AM60B Magnesium Alloy

Under the cold-chamber high pressure die casting (HPDC) process, samples were produced with AM60B magnesium alloy to investigate the microstructure characteristics of the eutectics, especially focusing on the constitution, morphology and distribution of the eutectics over cross section of the castings. Attentions were also paid to study the effect of heat treatment on the eutectics in the die castings. Based on experimental analysis using optical microscopy (OM), X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS), it was determined that fully divorced eutectics consisting of α-Mg and β-Mg17Al12 appeared at the grain boundary of the primary α-Mg in the as-cast microstructure. Islands and networks of β-Mg17Al12 phase were observed in the central region of the castings, while the β-Mg17Al12 phase revealed a more dispersed and granular morphology on the surface layer. The two phases ratio β/α in the central region of the castings was approximately 10%, which was higher than that on the surface layer. Besides, the defect bands contained a higher percentage of the eutectics than the adjacent regions. After aging treatment (T6), only α-Mg phase was detected by XRD in the AM60B magnesium alloy, though a small amount of precipitated β-Mg17Al12 phase was observed at the grain boundary. In contrast to the microstructure of die cast AZ91D magnesium alloy under the same T6 heat treatment, no discontinuous precipitation of the β-Mg17Al12 phase was observed in AM60B magnesium alloy die castings.     

Enhancing Mechanisms of Saturated Fatty Acids on the Permeations of Indomethacin and 6-Carboxyfluorescein through Rat Skins

Effects of saturated straight-chain fatty acids at various chain lengths (C₈-C₁₈) on the permeation of indomethacin, a relatively lipophilic compound and 6-carboxyfluorescein, a hydrophilic compound were examined using rat skins in in vitro. Furthermore, the disordering degrees of intercellular lipid domain in stratum corneum, which were treated by preparation containing saturated fatty acids were measured by FT-IR method using excised rabbit ear skins. Capric acid (C₁₀), lauric acid (C₁₂) and myristic acid (C₁₄) within series of saturated fatty acids (0.07 M) showed the enhancing effects on the skin permeations of indomethacin and 6-CF. The permeation enhancing effects by these saturated fatty acids (C₈-C₁₈) except for capric acid (C₁₀), were relative to the degrees of wavenumber shift in the frequency of the asymmetric CHbond stretching absorbance (2920 cm^-1) on FT-IR spectra of the fatty acid treated stratum corneum. Therefore, the perturbation increase of lipid domain in stratum corneum by these fatty acids probably was the cause of the enhanced effects of permeation of indomethacin and 6-CF. On the other hand, capric acid appears to enhance the permeations of these two drugs by separate mechanisms.     

Poloxamer 407 as a Thermogelling and Adhesive Polymer for Rectal Administration of Short-Chain Fatty Acids

Objectives: The purpose of the study was to gel a rectal solution of short-chain fatty acids to decrease the loss of active materials in the colonic lumen and thereby optimize their absorption. Methods: Five thermogels were prepared with poloxamer 407 at concentrations ranging from 17% to 20%. Their viscosities were measured at room temperature and 37°C, and their gelling temperatures were determined. The adhesive properties of each gel were assessed in vitro at 37°C. Short-chain fatty acid release was studied using Guyot cells. Results: From the threshold concentration of 17.5%, the solutions, Newtonian at room temperature (50-80 mPa · s), gelled at 37°C. The higher the concentration, the higher the viscosity (1750 to 49,000 mPa · s), the lower the gelling temperature (27.6°C to 23.4°C), and the stronger the work of adhesion (2.2 to 4.5 mJ). Short-chain fatty acid release from the 18% polymer gel was decreased by 60% compared to the rectal solution. Conclusion: The 18% poloxamer 407 concentration provided a solution that was liquid at room temperature, that gelled at 37°C, possessed adhesive properties, and controlled short-chain fatty acid release.     

Rapid identification of long-chain polyunsaturated fatty acids in a marine extract by HPLC-MS using data-dependent acquisition

The collision-induced dissociation (CID) of a range of deprotonated fatty acid standards was studied using linear ion trap mass spectrometry. Neutral losses of 78, 98, and 136 Da were consistently observed for fatty acids with five or more double bonds. Comparison of the MS/MS spectra of docosahexaenoic acid (DHA) and universally (13)C-labeled DHA allowed the molecular formulas for these neutral losses to be determined as C(6)H(6), C(5)H(6)O(2), and C(8)H(8)O(2). Knowledge of fatty acid fragmentation processes was then applied to identify fatty acids from a sea anemone, Aiptasia pulchella, and dinoflagellate symbiont, Symbiodinium sp. extract. Using HPLC-MS, fatty acids were separated and analyzed by tandem mass spectrometry in data-dependent acquisition mode. Neutral loss chromatograms for 78, 98, and 136 Da allowed the identification of long-chain fatty acids with five or more double bonds. On the basis of precursor ion m/z ratios, chain length and degree of unsaturation for these fatty acids were determined. The application of this technique to an Aiptasia sp.-Symbiodinium sp. lipid extract enabled the identification of the unusual, long-chain fatty acids 24:6, 26:6, 26:7, 28:7, and 28:8 during a single 40 min HPLC-MS analysis.     

清溪乌鳖油脂肪酸的气相色谱-质谱联用分析

采用气相色谱-质谱法对清溪乌鳖油脂中脂肪酸组成进行分析。共检测到22种脂肪酸,其中单不饱和脂肪酸6种,多不饱和脂肪酸9种,饱和脂肪酸7种。清溪乌鳖富含ω-3脂肪酸,含量达16.69%。此外清溪乌鳖油中9-十八碳烯酸（油酸）和9-十六碳烯酸（棕榈油酸）的含量也较高。本研究为清溪乌鳖油在生物制药和营养保健品领域的开发应用提...     

Electrogenerated chemiluminescence derivatization reagent, 3-isobutyl-9,10-dimethoxy-1,3,4,6,7,11b-hexahydro-2H-pyrido[2,1-a]isoquinolin-2-ylamine,for carboxylic acid in high-performance liquid chromatography using tris(2,2'-bipyridine)ruthenium(II)

3-Isobutyl-9,10-dimethoxy-1,3,4,6,7,11b-hexahydro-2H-pyrido[2,1-a]isoquinolin-2-ylamine (IDHPIA) was found to be a selective and highly sensitive derivatization reagent for carboxylic acid by high-performance liquid chromatography (HPLC) with electrogenerated chemiluminescence detection using tris(2,2'-bipyridine)ruthenium(II). Free fatty acids and phenylbutylic acid were used as model compounds of carboxylic acids, and the derivatization conditions were optimized with myristic acid. Under the mild reaction conditions of room temperature for 45 min in acetonitrile containing 2-bromo-1-ethylpyridinium tetrafluoroborate and 9-methyl-3,4-dihydro-2H-pyridol1,2-a]pyrimidin-2-one, all the fatty acids tested were reacted with IDHPIA to produce highly sensitive derivatives. The chemiluminescence intensity was essentially the same for all fatty acids. The derivatives obtained from 10 free fatty acids were completely separated by reversed-phase chromatography under isocratic elution conditions. The on-column detection limit (signal-to-noise ratio of 3) with proposed HPLC separation and chemiluminescence detection was 0.5 and 0.6 fmol for myristic acid and phenylbutylic acid, respectively. IDHPIA was 100-fold more sensitive than previously developed reagents (Morita, H.; Konishi, M. AnaL Chem. 2002, 74, 1584-1589). The free fatty acids in human serum were successfully determined using the present method.