新型高倍二肽甜味剂的制备与表征

N-{N-[3-甲基-3-(3,4-亚甲二氧基苯基)丁基]-α-L-天冬氨酰}-L-苯丙氨酸甲酯是一种新型纽甜类似物甜味剂。以3,4-亚甲基苯硼酸,3,3-二甲基丙烯酸为原料,经过Heck反应、酯化反应及DIBAL-H还原得到了3-甲基-3-(3,4-亚甲二氧基苯基)丁醛中间体。然后该中间体与阿斯巴甜在钯/碳催化作用下进行氢化还原氨化反应,成功制备了目标产物N-{N-[3-甲基-3-(3,4-亚甲二氧基苯基)丁基]-α-L-天冬氨酰}-L-苯丙氨酸甲酯。产物采用了核磁共振(NMR)、红外光谱(IR)和高分辨质谱(HRMS)等技术进行结构鉴定和分析,最后确证无误。经感官评定,测得其甜度约为蔗糖的3万倍。     

一种新型纽甜类似物甜味剂的合成及表征

为合成新型二肽类甜味剂,以甲醇、3,3-二甲基丙烯酸为初始原料,经Fischer酯化反应得到3,3-二甲基丙烯酸甲酯,再与2,5-二甲酚、甲烷磺酸发生Friedel-Crafts烷基化反应得到4,4,5,8-四甲基-3,4-二氢香豆素,产物以LiAlH_4为还原剂还原得到3-(2-羟基-3,6-二甲基苯基)-3-甲基丁醇,经2步保护反应分别保护醇羟基和酚羟基之后,用CH_3COOH脱掉叔丁基二甲基硅基(TBS)得到乙酰基保护的醇,用Dess-Martin periodinane氧化醇得到纽甜类似物的中间体3-(2-乙酰基-3,6-二甲基苯基)-3-甲基丁醛,最后将中间体与阿斯巴甜在硼氢化钠(Na BH_4)的还原胺化作用下合成高倍甜味剂纽甜类似物N-[N-[3-(2-乙酰基-3,6-二甲基苯基)-3-甲基丁基]-L-α-天冬氨酰]-L-苯丙氨酸1-甲酯。采用红外光谱(IR)、质谱(MS)以及核磁共振(NMR)对终产物进行结构鉴定和表征,结果确定其为目标终产物,并测得其甜度约为蔗糖的70 000倍。     

N-[N-3-（3-羟基-4-甲氧基苯基）丙基-L-α-天冬氨酸]-L-苯丙氨酸-1-甲酯的合成研究

以3-羟基-4-甲氧基苯甲醛和乙醛为初始原料,在-10℃、强碱性条件下反应生成3-羟基-4-甲氧基肉桂醛,然后将其与阿斯巴甜（APM）于0.7MPa氢压、35℃以及10%Pd/C催化剂的作用下还原烷基化,制得甜度高达蔗糖20000倍的纽甜类似物N-[N-3-（3-羟基-4-甲氧基苯基）丙基-L-α-天冬氨酸]-L-苯丙氨酸-1-甲酯,总产率达32.0%。     

玉米浆化学成分的分离纯化与结构鉴定

将玉米浆用4倍体积的甲醇进行醇沉，去除无机盐等强极性物质后，浓缩至小体积，用乙酸乙酯萃取，制得乙酸乙酯萃取物。利用硅胶柱色谱、HPLC等分离方法对玉米浆乙酸乙酯萃取物进行分离纯化，得到 23 个化合物。通过理化性质及波谱数据分析鉴定它们结构分别为对羟基苯丙酸（1）、3,4-二羟基-5-甲氧基苯丙酸甲酯（2）、R-2-羟基-3-苯基丙酸甲酯（3）、吲哚-3-乙酸甲酯（4）、2-羟基-3-甲基丁酸（5）、2-羟基-4-甲基戊酸（6）、3,4-二羟基苯丙酸甲酯（7）、二氢阿魏酸甲酯（8）、油酸（9）、对羟基苯乙酸（10）、三油酸甘油酯（11）、R-2-羟基-3-苯基丙酸（12）、环（缬-亮）二肽（13）、环（亮-亮）二肽（14）、环（苯丙-酪）二肽（15）、环（苯丙-缬）二肽（16）、环（亮-异亮）二肽（17）、环（苯丙-苯丙）二肽（18）、环（脯-亮）二肽（19）、尿嘧啶（20）、环（苯丙-甘）二肽（21）、环（苯丙-丙）二肽（22）、环（苯丙-丝）二肽（23）。这些化合物以环二肽、酚酸及其酯类为主，除化合物9以外，其余成分均为首次从玉米浆中分离得到。     

新型甜味剂N-[3-(3-羟基-4-甲氧基苯基)丙基]-阿斯巴甜的制备研究

为了制备新型高倍二肽甜味剂,从甜味机理出发,通过钯碳催化和阿斯巴甜分子选择性催化加氢反应方法,以3-羟基-4-甲氧基苯甲醛和乙醛为原料,研究制备新型高倍甜味剂N-[3-(3班基-4-甲氧基苯基)丙基]-阿斯巴甜.结果表明,所得产物由于在阿斯巴甜分子上引入了疏水基团"-OCH3","-OH",甜度大大提高,约为蔗糖的24000倍.     

二肽甜味素(蛋白糖)——新型甜味剂

<正> 二肽甜味素是由L—天门冬氨酸和L—苯丙氨酸组成的二肽化合物,化学名称a—L—天冬氨酰—L—苯丙氨酸甲酯(C_(14)H_(18)N_2O_5),俗称蛋白糖Aspartame(阿斯巴甜,简写APM),是低热卡高甜度美味营养保健型食品添加甜剂,已被联合国食品添加剂专家联席委员会(JECFA)确认为国际A(1)级     

低糖葛根饼干的研究

以小麦粉、葛根全粉、起酥油为主要原料,分别选择麦芽糖醇和N-[N-(3,3-二甲基丁基)-L-α-天冬氨酰]-L-苯丙氨酸-1-甲酯(纽甜)为甜味剂,采用饼干基本加工工艺,制作低糖葛根饼干。以感官评定为考察指标,确定低糖葛根饼干的最优配方。结果表明:小麦粉100g、起酥油38g、葛根全粉20g、麦芽糖醇10~12g或纽甜4mg、泡打粉0.8g、鸡蛋12g、食盐0.7g、水7ml时,饼干感官品质最佳,甜度适中,色泽呈棕黄色,口感酥脆,含糖量符合低糖国标的要求,与普通饼干相比,1kg小麦粉制作的饼干可减少2 MJ能量。     

国家卫生健康委员会关于(±)-1-环己基乙醇等食品添加剂新品种的公告

正根据《食品安全法》规定,审评机构组织专家对(±)-1-环己基乙醇等5种食品添加剂新品种和食品添加剂N-[N-(3,3-二甲基丁基)]-L-α-天门冬氨-L-苯丙氨酸1-甲酯(又名纽甜)等7种扩大使用范围、用量的品种安全性评估材料审查并通过。特此公告。附件:1.食品用香料新品种(±)-1-环己基乙醇2.壳聚糖酶等2种食品工业用酶制剂新品种3.食品营养强化剂新品种柠檬酸亚铁钠4.食品添加剂新品种L-苹果酸钠5.食品添     

加拿大一枝黄花化学成分的研究

目的分离和鉴定加拿大一枝黄花Solidago canadensis的化学成分。方法用色谱技术分离、纯化,通过理化常数和波谱分析鉴定化合物结构。结果从乙醇提取物中分离鉴定了7个化合物,分别为2-羟基-6-甲氧基苯甲酸(Ⅰ)、3-甲酰吲哚(Ⅱ)、3β,4α-二羟基-6β-当归酰-13Z-烯-15,16-克罗烷内酯(Ⅲ)、3β,4α-二羟基-6β-巴豆酰-13Z-烯-15,16-克罗烷内酯(Ⅳ)、α-菠菜甾醇(Ⅴ)、山柰酚(Ⅵ)和槲皮素(Ⅶ)。结论化合物Ⅱ为首次从该属植物中分离得到,化合物Ⅰ、Ⅲ～Ⅴ均为首次从该种植物中分离得到。     

阿斯巴甜(APM)

NutraSweet~R商标代表美国NutraSweet公司生产的高甜度甜味素,属名是阿斯巴甜(Aspartame)或(APM)。 阿斯巴甜为白色、无味结晶状粉末,是一种二肽化合物(以甲酯形式存在)。正式化学名称是α-L-天冬氨酸-L-苯丙氨酸甲酯(α-L- Aspartyl-L-Phenylalaninemethyl ester),分子量是294.31,分子结构式见图1。 人类的消化系统可将阿斯巴甜转变成它的组成成份——天门冬氨酸、苯丙氨酸及其甲酯,这些成份都存     

超高倍甜味剂N-[3-(3-羟基-4-甲氧基苯基)丙基]-阿斯巴甜的合成研究

开发安全,低成本,高甜度,性质稳定的甜味剂是食品工业的发展方向。文中从甜味机理出发,以3-羟基-4-甲氧基苯丙醛与阿斯巴甜为原料,通过钯碳催化,合成了N-[3-(3-羟基-4-甲氧基苯基)丙基]-阿斯巴甜。其中,由于疏水基团引入,甜度显著提高,约是蔗糖的23000倍,且合成工艺简单,产率高,为国内高倍甜味剂大型工业化提供了广阔前景。另外,文中还着重论述了重要中间体3-羟基-4-甲氧基苯丙醛制备,得率为49.8%,为开发新产品奠定了基础。     

Phenolic acid amides of phenolic benzylamines against UVA-induced oxidative stress in skin

UVA-radiation is suspected to be a main cause for extrinsic skin ageing in humans. Recent studies showed that topically administered molecular antioxidants are able to protect skin against UVA-generated oxidative stress. Therefore, new phenolic acid amides of phenolic benzylamines were synthesized as potential antioxidants by reaction of (if necessary protected) N-succinimidylesters of ferulic acid, sinapic acid, caffeic acid, 3-(4-hydroxy-3-methoxyphenyl)propanoic acid, 3-(3,4-dihydroxyphenyl)propanoic acid, 2-(4-hydroxy-3-methoxyphenyl)acetic acid and 2-(3,4-dihydroxyphenyl) acetic acid with different phenolic benzylamines in moderate to good yields. The radical scavenging activities of the compounds were determined by the DPPH (2,2-diphenyl-1-picrylhydrazyl) assay and by a superoxide radical anion trapping assay. Antioxidant activities in bulk lipids were tested by accelerated peroxidation with or without test compounds performed in the Rancimat apparatus. Stripped soybean oil and the skin sebum component squalene were used as lipids. The synthesized compounds were found to be efficient radical scavengers and antioxidants, especially the hydroxyphenylacetic amides and the hydroxydihydrocinnamic acid amides of polyhydroxybenzylamines, which are superior to the standards alpha-tocopherol and l-ascorbic acid. A topically applied 0.1% 1,3-butyleneglycol solution of N-(3,4-dihydroxybenzyl)-2-(4-hydroxy-3-methoxyphenyl)acetic acid amide 19 inhibits the UVA-induced sebum peroxidation in human skin significantly, by 39%.     

壳聚糖衍生物在活性染色中的应用

以壳聚糖为原料,合成了N-羟丙基十二烷基二甲基氯化铵壳聚糖(HDCC)和O-甲基丙烯酰胺-N-羟丙基十二烷基二甲基氯化铵壳聚糖(NMA-HDCC);研究了经壳聚糖(CTS),HDCC和NMA-HDCC预处理棉织物在活性染料无盐染色时的染色性能,如上染率、固色率、K/S值及色牢度性能,并与未预处理无盐染色及传统有盐染色进行对比。结果表明,对棉织物进行CTS,HDCC和NMA-HDCC预处理具有良好的促染作用,对提高活性染料的上染率和固色率有一定效果;CTS和HDCC能提高染色棉织物的K/S值,但色牢度较低;NMA-HDCC可与纤维素纤维形成共价键,能够显著提高染色织物的色牢度。     

Tyrosinase inhibitory effects and antioxidative activities of novel cinnamoyl amides with amino acid ester moiety

Nine cinnamoyl amides with amino acid ester (CAAE) moiety were synthesized by the conjugation of the corresponding cinnamic acids (cinnamic acid, 4-hydroxy cinnamic acid, ferulic acid and caffeic acid) with amino acid esters, and their inhibitory effects on the activities of mushroom tyrosinase were investigated, using l-3,4-dihydroxyl-phenylalanine (l-DOPA) as the substrate. Among these CAAE amides, ethyl N-[3-(4-hydroxy-3-methoxyphenyl)-1-oxo-2-propen-1-yl]-l-phenylalaninate (b₄) showed the strongest inhibitory activity; the IC₅₀ was 0.18 μM. The IC₅₀ values, inhibition types, inhibition mechanisms and kinetics of all these CAAE amides were evaluated. A structure–activity relationship (SAR) study found that the inhibitory effects were potentiated with the increasing length of hydrocarbon chains at the amino acid esters and also influenced by the substituents at the styrene groups. Furthermore, the hydroxyl radical scavenging and anti-lipid peroxidation activities of four CAAE derivatives were also investigated. Among these compounds, b₃ (ethyl N-[3-(3,4-dihydroxyphenyl)-1-oxo-2-propen-1-yl]-l-phenylalaninate) and b₄ exhibited potential antioxidant activities.     

虫草素的N-丙烯酰化的修饰

基于虫草素中的氨基稳定性问题,对其氨基修饰,并与磁性材料杂化。丙烯酰氯为酰化剂,三乙胺为缚酸剂,对虫草素进行衍生化反应,采用高分辨质谱、核磁共振波谱进行表征,合成新化合物N-丙烯酰虫草素,其与3-氨基丙基三乙氧基硅烷进行模板反应得到N-[1-氧代丙烷-3-(3-(三乙氧基硅基)丙基)氨基]虫草素,进而与氨基磁性材料(Fe3O4-NH2)发生aza-Michael反应,用x射线粉末衍射、磁滞回线、茚三酮比色法证明杂化成Fe3O4-NH2@N-丙烯酰虫草素。N-丙烯酰虫草素,既有抗菌性,又能与无机材料杂化,是一种潜在的活性中间体。     

New diarylheptanoids from the rhizome of Alpinia officinarum Hance

Three diarylheptanoids, officinaruminane A (1), officinaruminane B (2), 5(S)-acetoxy-7-(4-dihydroxyphenyl)-1-phenyl-3-heptanone (3), together with six known ones , (5R)-5-hydroxy-1-(4-hydroxyphenyl)-7-(4-hydroxy-3-methoxyphenyl)-3-heptanone (4),(5R)-5-hydroxy-1-(4-hydroxy-3-methoxyphenyl)-7-(4,5-dihydroxy-3-methoxyphenyl)-3-heptanone (5), 1-phenyl-7-(4-hydroxy-3-methoxyphenyl)-4E-en-3-heptanone (6), 1-(4-hydroxyphenyl)-7-(4-hydroxy-3-methoxyphenyl)-4E-en-3-heptanone (7), 1-phenyl-7-(4-hydroxyphenyl)- 4E- en-3-heptanone (8), and 3,6-furan-7-(4′′-hydroxy-3′′-methoxyphenyl)-1-phenylheptane (9), were isolated from the rhizomes of Alpinia officinarum Hance by column chromatography on silica gel, MPLC and preparative thin-layer chromatography (TLC). The structures of these compounds were elucidated on the basis of mass spectrometry, ¹H NMR, ¹³C NMR, HMQC and HMBC data. Among them, 1 is a diarylheptanoid with a pyridine ring, and 2 is a diarylheptane monoterpene.     

SDE和HS-SPME法与GC-MS/O联用分析阳江豆豉的香气活性化合物

采用同时蒸馏萃取法(SDE)和顶空-固相微萃取法(HS-SPME)结合气相色谱-质谱/嗅闻检测技术(GC-MS/O)深入研究阳江豆豉的香气成分,共鉴定出挥发性化合物174种。SDE法对高分子量、低挥发性物质,如呋喃酮、吡喃酮等,有良好的萃取效果;而HS-SPME法能萃取更多的高挥发性化合物,如小分子的酸和酯类。通过GC-O技术在两种方法的萃取物中共嗅闻到46个香气活性区域。其中9种共有化合物(2/3-甲基丁醛、2/3-甲基丁酸、3-甲硫基丙醛、苯乙醛、愈创木酚、3-羟基-2-甲基-4H-吡喃-4-酮和苯乙醇),以及香气强度较高(评分大于2.5分)的单方法检出化合物:SDE法4种(3-羟基-4,5-二甲基-2(5H)-呋喃酮、2-乙酰基-1-吡咯啉、2-丙烯基-3-甲基吡嗪和4-羟基-2,5-二甲基-3(2H)-呋喃酮)、SPME法1种(1-辛烯-3-醇),是阳江豆豉中的关键香气活性物质,对麦芽香、酸奶酪香、烤土豆香、花香、烟熏香、焦糖香和烤香等有贡献。     

抗癌药物拉帕替尼两个杂质的合成

目的合成抗癌药物拉帕替尼的两个杂质。方法以N-[3-氯-4-[(3-氟苄基)氧基]苯基]-6-碘喹唑啉-4-胺为起始原料,经Suzuki偶联反应,得到N-[3-氯-4-[(3-氟苄基)氧基]苯基]-6-[(5-甲酰基)呋喃-2-基]-4-喹唑啉胺,直接与还原剂NaBH(OAc)3反应,得到特定杂质N-[3-氯-4-[(3-氟苄基)氧基]苯基]-6-(5-羟甲基呋喃-2-基)-4-喹唑啉胺;起始原料经Suzuki反应后,与2-甲砜基乙胺反应,在NaBH(OAc)3作用下得粗品,经制备液相分离,得到另一特定杂质双[[5-[4-[[3-氯-4-[(3-氟苄基)氧基]苯基]氨基]喹唑啉-6-基]呋喃-2-基]甲基][2-(甲磺酰基)乙基]胺。结果两个目标物经质谱(MS),核磁共振氢谱(1H NMR)确证其化学结构。结论合成的两个杂质可作为拉帕替尼质量控制对照品,本工艺操作可行,原料易得。     

Relationship between nitrogen content in grapes and volatiles,namely heavy sulphur compounds,in wines

Ammonium salts were added to white grape musts, before alcoholic fermentation, in order to evaluate their influence on the heavy sulphur compound and aliphatic higher alcohol composition of resulting wines. Six grape musts were used (Trajadura, Pedernã, Loureiro, Azal Branco, Avesso and Alvarinho). Ammonium supplementation of Trajadura and Pedernã grape musts, with the highest nitrogen level, did not influence the content of heavy sulphur compounds and aliphatic higher alcohols in wines; however, the addition of ammonium salts to grape musts with low initial nitrogen content, such as Loureiro, Azal Branco and Avesso, led to a higher production of 1-propanol and a lower production of isoamyl alcohols and sulphur compounds, e.g. S-methyl thioacetate, 2-mercaptoethanol, acetic acid-3-(methylthio)propyl ester, 3-mercapto-1-propanol, 4-(methylthio)-1-butanol, 3-(ethylthio)-1-propanol, 3-methylthiopropionic acid and N-3-(methylthiopropyl)acetamide. For Alvarinho grape must, a decrease in sulphur compound concentrations in wines was only observed for 3-methylthiopropionic acid, acetic acid-3-(methylthio)propyl ester and 2-mercaptoethanol.     

Protective effects of curcumin and its analogues against free radical-induced oxidative haemolysis of human red blood cells

Curcumin (1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione, 1), is a yellow ingredient isolated from turmeric (curcumin longa). It has been shown to exhibit a variety of biological activities, including antioxidative activity. In order to find more active antioxidants with 1 as the lead compound, we synthesized curcumin analogues, namely 1-(4-hydroxy-3- methoxyphenyl)-7-(4-hydroxyphenyl)-1,6-heptadiene-3,5-dione (2), 1-(3,4-dimethoxyphenyl)-7-(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione (3), 1,7-bis(3,4-dimethoxyphenyl)-1,6-heptadiene-3,5-dione (4), 1-(3,4-dihydroxyphenyl)-7-(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione (5), 1,7-bis(3,4-dihydroxyphenyl)-1,6-heptadiene-3,5-dione (6), and 1,7-bis-(4-hydroxyphenyl)-1,6-heptadiene-3,5-dione (7), and evaluated their antioxidative activity. The in vitro oxidative haemolysis of human red blood cells (RBCs) was used as a model to study the free radical-induced damage of biological membranes and the protective effects of these curcumin analogues. It was found that these compounds, except 4, could effectively inhibit the free radical induced oxidative haemolysis of RBCs by H-atom abstraction from the phenolic groups. Compounds 5 and 6 which bear ortho-diphenoxyl functionality exhibited markedly higher anti-haemolysis activity than curcumin and other analogues, as well as than α-tocopherol (vitamin E).