10-Undecenoic acid-based polyol esters as potential lubricant base stocks

败酱草化学成分研究刘洋成;刘伟;陈刚;项峥;陈长兰【摘要】研究白花败酱草的化学成分, 以95％乙醇溶液提取白花败酱草, 依次采用石油醚、二氯甲烷、正丁醇对提取物进行萃取.正丁醇提取物分别采用硅胶柱色谱、ODS柱色谱以及葡聚糖凝胶色谱等技术进行分离, 然后应用半制备型高效液相色谱进行纯化, 共得到7个化合物.通过核磁共振技术, 结合相关文献对比后确定全部化合物结构.分别为Caffeic acid ethyl ester (1), Caffeic acid n-butyl ester (2), Apigenin (3), Luteolin (4), Menthalignin (5), Methyl 2- (4-hydroxyphenyl) acetate (6), trans-Ferulic acid (7).其中化合物1～3, 6, 7均为首次从该植物中分离得到.%To study the constituents of Patrinia villosa Juss. P. villosa Juss. was extracted with 95％ ethanol. Then the extractionwasextracted by petroleum ether, dichloromethane and n-butanol, respectively. The n-butanol extraction was separated by silica gel colum chromatography, ODS column chromatography and sephadex LH-20 column chromatography.Then the compounds were purified by semi-preparative HPLC. 7 compounds including Caffeic acid ethyl ester (1), Caffeic acid n-butyl ester (2), Apigenin (3), Luteolin (4), Menthalignin (5), Methyl 2- (4-hydroxyphenyl) acetate (6), trans-Ferulic acid (7). were identified by NMR technology and references. Compound 1 ～ 3, 6, 7 were isolated from Patrinia Juss for the first time.【期刊名称】《哈尔滨商业大学学报（自然科学版）》【年(卷),期】2019(035)002【总页数】4页(P138-140,170)【关键词】白花败酱草;化学成分;纯化;分离;结构鉴定【作者】刘洋成;刘伟;陈刚;项峥;陈长兰【作者单位】辽宁大学药学院,沈阳 110036;辽宁大学药学院,沈阳 110036;沈阳药科大学中药学院,沈阳 110016;辽宁大学药学院,沈阳 110036;辽宁大学药学院,沈阳 110036【正文语种】中文【中图分类】R284白花败酱草(Patrinia villosa Juss.)为败酱科败酱属多年生草本植物攀倒甑的干燥全草[1].其性味苦、寒、无毒；具有散瘀消肿，活血排脓等功效.败酱草在临床上主要用于治疗阑尾炎、痢疾、肝炎、扁桃体炎、痈肿疮毒等症[2].近年来，本课题组对白花败酱草的化学成分进行深入的研究并分离得到了大量单体成分[3-10].同时，对败酱草的无机元素及挥发性成分也做了系统的研究[11-12].在前期研究的工作基础上，本实验继续对白花败酱草95%乙醇提取部位的化学成分进行研究，通过柱色谱以及及半制备HPLC等技术手段进行分离纯化，采用核磁共振波谱分析得到了7个单体化合物，分别为Caffeic acid ethyl ester (1), Caffeic acid n-butyl ester (2),_Apigenin (3), Luteolin (4), Menthalignin (5), Methyl 2-(4-hydroxyphenyl)acetate (6), trans-Ferulic acid (7)(图1).其中化合物1～3，6，7均为首次从该植物中分离得到.图1 单体化合物分子式1 仪器与材料高效液相色谱仪(HITACHI,检测器UV Monitor)；YMC ODS-A制备色谱柱(10 × 250 mm, 5 μm, YMC公司)；核磁共振波谱仪(Buker公司，TMS做内标).柱色谱硅胶(200～300目)购自中国青岛海洋化工厂；葡聚糖凝胶LH-20购自北京绿百草科技发展有限公司；ODS柱色谱填料购自美国Welch公司.实验所需有机溶剂均购自天津科密欧化学试剂有限公司；白花败酱草购自河北祁新中药颗粒饮片有限公司.2 提取与分离白花败酱草干燥全草15 kg，粉碎后以6倍95%乙醇回流提取3次，减压浓缩得到浸膏约1 400 g.将浸膏用适量的水分散，分别用等体积石油醚、二氯甲烷、正丁醇依次萃取3次，减压浓缩回收萃取溶剂得石油醚层162.6 g，乙酸乙酯层203.4 g，正丁醇层349.2 g.将正丁醇层萃取物经过硅胶柱层析色谱，二氯甲烷-甲醇为洗脱溶剂进行梯度系统，经ODS色谱柱分离后，依次用体积分数为20%、40%、60%、80%及100%的甲醇梯度洗脱.其中体积分数为40%(39.5 g)和60%(38.7 g)甲醇部分再通过流动相系统为CH2Cl2-MeOH的硅胶色谱柱分离，体积分数从100;0-0;100进行梯度洗脱，得到流分Fr.4及Fr.6.最后将两部分流分经过反复葡聚糖凝胶LH-20柱色谱分离，ODS色谱结合半制备液相分离纯化出化合物1(14.6 mg)，2(2.3 mg)，3(3.4 mg)，4(6.3 mg)，5(11.0 mg)，6(4.3 mg)，7(10.5 mg).3 结构鉴定化合物1：无色方晶.1H-NMR (400 MHz, DMSO-d6): 7.46 (1H, d, J = 16.0 Hz, H-7), 7.04 (1H, d, J = 2.0 Hz, H-2), 7.00 (1H, dd, J = 2.0, 8.0 Hz, H-6), 6.75 (1H, d, J = 8.0 Hz, H-5), 6.25 (1H, d, J = 16.0 Hz, H-8), 4.15 (2H, q, J = 7.2 Hz, H-10), 1.24 (3H, t, J = 7.2 Hz, H-11). 13C-NMR (100 MHz, DMSO-d6):125.5(C-1), 114.8(C-2), 145.5(C-3), 148.3(C-4), 115.7(C-5), 121.3(C-6),144.9(C-7), 113.9(C-8), 166.5 (C-9), 59.7 (C-10), 14.2 (C-11). 以上数据与文献报道数据基本一致[13]，鉴定为Caffeic acid ethyl ester.化合物2：白色针晶.1H-NMR (400 MHz, DMSO-d6): 7.46 (1H, d, J = 16.0 Hz, H-7), 7.04 (1H, br. s, H-2), 7.00 (1H, d, J=8.4 Hz, H-6), 6.75 (1H, d, J = 8.4 Hz, H-5), 6.25 (1H, d, J = 16.0 Hz, H-8), 4.11 (2H, t, J = 6.4 Hz, H-10), 1.61 (2H, m, H-11), 1.36 (2H, sex, J = 7.2 Hz, H-12), 0.90 (3H, t, J = 7.2 Hz, H-13).13C-NMR (100 MHz, DMSO-d6): 125.5 (C-1), 114.8 (C-2), 145.5 (C-3), 148.3 (C-4), 115.7 (C-5), 112.3 (C-6), 144.9(C-7), 113.9(C-8), 166.6 (C-9), 63.4 (C-10), 30.3 (C-11), 18.6 (C-12), 13.5 (C-13). 以上数据与文献报道数据基本一致[14]，鉴定为Caffeic acid n-butyl ester.化合物3：黄色粉末.1H-NMR (400 MHz, DMSO-d6): 7.92 (1H, d, J = 8.8 Hz, H-2’), 7.92 (1H, d, J = 8.8 Hz, H-6′), 6.92 (1H, d, J = 8.8 Hz, H-3′), 6.92 (1H, d, J = 8.8 Hz, H-5′), 6.78 (1H, s, H-3), 6.48 (1H, d, J = 2.0 Hz, H-8), 6.19 (1H, d, J = 2.0Hz, H-6). 13C-NMR (100 MHz, DMSO-d6): 164.1 (C-2), 102.3 (C-3), 181.8 (C-4), 157.3 (C-5), 98.8 (C-6), 163.7 (C-7), 93.9 (C-8), 161.4 (C-9), 103.7 (C-10), 121.1 (C-1′), 128.4 (C-2′, 6′), 115.9(C-3′, 5′), 161.1(C-4′). 以上数据与文献报道数据基本一致[15]，鉴定为Apigenin.化合物4：黄色粉末.1H-NMR (400 MHz, DMSO-d6): 7.41(1H, br. s, H-6′),7.39 (1H, brs,H-2′), 6.89 (1H, d,J = 8.0 Hz, H-5′), 6.58 (1H, s, H-3), 6.44 (1H, br. s, H-8), 6.19 (1H, brs,H-6). 13C-NMR (100 MHz, DMSO-d6): 164.2 (C-2), 102.9 (C-3), 181.6 (C-4), 157.3 (C-5), 98.8 (C-6), 163.9 (C-7), 93.8 (C-8), 161.5 (C-9), 103.7 (C-10), 121.5 (C-1′), 113.4 (C-2′), 145.7 (C-3′), 149.7 (C-4′), 116.0 (C-5′), 119.0 (C-6′). 以上数据与文献报道数据基本一致[16]，鉴定为Luteolin.化合物5：深绿色无定型粉末.1H-NMR (400 MHz, DMSO-d6): 8.08 (1H, s, H-7), 7.62 (1H, s, H-8′), 7.45 (1H, d, J = 9.0 Hz, H-6), 7.22 (1H, s, H-5), 7.21 (1H, s, H-6′), 6.58 (1H, s, H-3′). 13C-NMR (100 MHz, DMSO-d6): 126.6(C-1), 123.0(C-2), 136.1(C-3), 140.9(C-4), 119.6(C-5), 121.1(C-6), 127.0(C-7), 127.1(C-8), 167.6(C-9), 110.1(C-1′), 144.8(C-2′), 103.9(C-3′), 148.0(C-4′), 142.5(C-5′), 108.2(C-6′), 126.4(C-7′), 110.8(C-8′).以上数据与文献报道数据基本一致[17]，鉴定为Menthalignin.化合物6：无色油状.1H-NMR (400 MHz, CH3OH-d6): 7.10 (2H, d, J = 8.13 Hz, H-3), 7.10 (2H, d, J = 8.13 Hz, H-5), 6.76 (2H, d, J = 8.13 Hz, H-2), 6.76 (2H, d, J = 8.13 Hz, H-6), 3.70 (3H, s, H-9), 3.56 (2H, s, H-7). 13C-NMR (150MHz, DMSO-d6): 125.0 (C-1), 130.8 (C-2), 115.7 (C-3), 156.8 (C-4), 115.7 (C-5), 130.8 (C-6), 40.0 (C-7), 172.6 (C-8), 52.1 (C-9). 以上数据与文献报道数据基本一致[18]，鉴定为Methyl 2-(4-hydroxyphenyl)acetate.化合物7：黄色针状晶体.1H-NMR (400 MHz, CH3OH -d6): 7.63 (1H, d, J = 15.9 Hz, H-7), 7.20 (1H, d, J = 1.7 Hz, H-2), 7.09 (1H, dd, J = 8.2, 1.7 Hz, H-6), 6.84 (1H, d, J = 8.2 Hz, H-5), 6.34 (1H, d, J = 15.9 Hz, H-8), 3.92 (3H, s, -OCH3).13C-NMR (100 MHz, CH3OH-d6): 127.0 (C-1), 110.8 (C-2), 149.7 (C-3), 148.5 (C-4), 115.6 (C-5), 123.2 (C-6),146.1 (C-7), 115.3 (C-8), 170.2 (C-9), 55.6 (-OCH3). 以上数据与文献报道数据基本一致[19]，鉴定为trans-Ferulic acid.参考文献：【相关文献】[1] 中国科学院中国植物志编辑委员会.中国植物志[M].北京：科学出版社，2004.[2] 彭金咏, 范国荣, 吴玉田. 白花败酱草黄酮类成分的高速逆流色谱快速制备[J]. 中国药学杂志, 2006, 41(13):977-979.[3] XIANG Z, CHEN N, XU Y, et al. New Flavonoid from Patrinia villosa (Thunb.)Juss. [J]. Pharmaceutical Biology，2016,54(7):1219-1222.[4] XIANG Z, ZHAO S S, ZHAO Y, et al. Chemical Constituents from Patrinia villosa (Thunb.)Juss. [J]. Latin American Journal of Pharmacy，2017, 36 (12): 2425-2430.[5] YAN XJ, LIU W, ZHAO Y, et al.A new biphenylneolignan from leaves of Patrinia villosa (Thunb.)Juss. [J]. Pharmacognosy Magazine，2016，12: 1-3.[6] YANG Y F, MA H M, CHEN G, et al. A new sesquiterpene lactone glycoside and a new quinic acid methyl ester from Patrinia villosa [J]. Journal of Asian Natural Products Research，2016, 18(10): 945-951.[7] 阎新佳, 郑威, 温静, 等. 白花败酱草的木脂素类化学成分研究 [J]. 中国药学杂志, 2017, 52(13). 1126-1131.[8] 项峥, 阎新佳, 温静, 等. 白花败酱草的化学成分研究 [J]. 中国药学杂志, 2017, 52(3): 185-187.[9] 阎新佳, 郑威, 温静, 等. 白花败酱草的化学成分研究 [J]. 中草药，2017，48(2)：247-251.[10] 包永睿, 阎新佳, 王帅, 等. 白花败酱草的化学成分研究 [J]. 中药材, 2017, 40(2): 347-349.[11] LI W L, YANG X X, WANG S, et al. Species classification and bioactive ingredients accumulation of BaiJiangCao based on characteristic inorganic elements analysis by inductively coupled plasma-mass spectrometry (ICP-MS)and multivariate analysis [J]. Pharmacognosy Magazine，2015，44(11): 756-763.[12] 刘伟, 贾绍华, 项峥. GC-MS法检测白花败酱草与黄花败酱草挥发性成分[J]. 哈尔滨商业大学学报：自然科学版, 2016, 32(1):6-10.[13] 丁盈, 蒋梅香, 周应军,等. 桑叶降糖活性成分研究[J]. 中国药物化学杂志, 2007, 17(6):386-389.[14] XU J, LI X, ZHANG P, et al. Antiinflammatory constituents from the roots of Smilax bockii warb[J]. Archives of Pharmacal Research, 2005, 28(4):395-399.[15] MESELHY M R. Constituents from Moghat, the Roots of Glossostemon bruguieri (Desf.)[J]. Molecules, 2003, 8(8):614-621.[16] 陈封政, 向清祥, 李书华. 孑遗植物桫椤叶化学成分的研究[J]. 西北植物学报, 2008,28(6):1246-1249.[17] 徐凌玉, 李振麟, 蔡芷辰,等. 薄荷化学成分的研究[J]. 中草药, 2013, 44(20):2798-2802.[18] 曲鹏, 刘培培, 付鹏,等. 黄河三角洲耐盐真菌Penicillium chrysogenum HK14-01的次生代谢产物[J]. 微生物学报, 2012, 52(9):1103-1112.[19] SEKI T, MORIMURA S, TABATA S, et al. Antioxidant activity of vinegar produced from distilled residues of the Japanese liquor shochu[J]. J. Agric. Food Chem., 2008,56(10):3785-3790.。

聚乙二醇改性水溶性壳聚糖对蛋白药物的释放作用王春1，扶雄2，杨连生2（1.广东石油化工学院化学与生命科学学院，广东茂名 525000）（2.华南理工大学轻工与食品学院，广东广州 510640）摘要：本文采用离子交联的方法，研究制备了聚乙二醇（PEG）修饰的水溶性壳聚糖（WSC）药物载体。

以牛血清蛋白（BSA）作为模型蛋白药物，对纳米粒子的物理化学性质作了初步检测。

由于分子间的竞争作用，PEG的修饰在一定程度上降低了WSC纳米粒子的药物负载能力。

体外释放实验表明PEG修饰的纳米粒子在一定程度上加快了BSA的释放，但仍具有较好的缓释性能。

关键词：水溶性壳聚糖；聚乙二醇；纳米粒子；牛血清蛋白；蛋白质释放文章篇号：1673-9078(2011)8-885-886PEG Modified Water-soluble Chitosan Nanoparticles for Drug DeliveryW ANG Chun1, FU Xiong2, YANG Lian-sheng2(1.Chemistry and Life Science College, Guangdong University of Petrochemical Technology, Maoming 525000, China)(2.College of Light Industry and Food Sciences, South China University of Technology, Guangzhou 510640, China)Abstract: PEG modified WSC nanoparticles were prepared based on ionic gelation and the capability of PEG modified water-soluble chitosan (WSC) was used as carriers to load and delivery drug. As a model protein drug, bovine serum albumin (BSA) was incorporated into the nanoparticles. Physicochemical of characterizations of WSC nanoparticles was determined preliminarily. PEG introduction might decrease loading capability of nanoparticles due to the competition effect between BSA and PEG. And in vitro release demonstrated that PEG modification could increase release of loading protein drug but the nanoparticles displayed a good release performance still.Key words: water-soluble chitosan (WSC); PEG; nanoparticle; BSA; protein delivery聚乙二醇(PEG)是一种被广泛应用于生物医用材料的高分子，它和水溶性壳聚糖（WSC）一样具有生物相容性好、无毒无副作用、并可生物降解等特点。

收稿日期:2003-02-20基金项目:江西省自然科学基金资助项目(001109)作者简介:王幸聪(1977-),女,江西景德镇人,硕士研究生,主要从事有机合成研究.文章编号:1000-5862(2003)04-0295-03聚合物负载苯亚硒酸试剂促进过氧化氢氧化肟转变成羧酸酯王幸聪,　桑晓燕,　刘晓玲(江西师范大学化学学院,江西南昌　330027)摘要:在30%双氧水和醇组成体系中,聚合物负载的苯亚硒酸试剂可有效地促进过氧化氢氧化肟转变成羧酸酯;相应伯醇和仲醇的羧酸酯的产率中等到良好,但在含叔醇的体系中没有相应的羧酸酯生成.聚合物负载的苯亚硒酸试剂无需处理即可循环使用,其活性无明显下降.关键词:聚合物负载的苯亚硒酸;氧化反应;过氧化氢;肟;羧酸酯中图分类号:O 632.4 文献标识码:A在工业和实验室中氧化反应应用广泛,如将烯烃氧化为环氧化合物、二酸,将醇氧化为醛,醛氧化为酸等.过氧化氢是一种廉价、温和且对环境友好的绿色氧化剂,其反应后的副产物只有水.但使用过氧化氢的氧化反应常常需要在催化剂存在下进行[1].苯基亚硒酸/过氧化氢组成的催化氧化体系已广泛应用于烯烃的环氧化反应和酮的Baeyer -Villiger 反应[2～4]、烯丙醇[5]、硫醚[6]、醛[7]以及酚类化合物[8]的氧化反应当中;邻硝基苯亚硒酸催化过氧化氢氧化肟转变成羧酸酯的研究也有报道[9].但芳基亚硒酸毒性较大、价格较贵.如能将其键合于载于聚合物载体上,即可减少或消除其毒性.T aylor 等[10]首次报道了聚苯乙烯负载的苯亚硒酸试剂的合成和催化过氧化氢选择性地将醇氧化为醛或酮的研究,但在合成聚合物负载的苯亚硒酸时使用了大大过量的HgO 和SeO 2,而且反应时间很长,合成不方便,且存在重金属污染问题.我们在烯丙基醚或烯丙基酯的固相合成中[11],中间体烷基硒醚树脂氧化-消除所得到的残余树脂经证实为聚苯乙烯负载的苯亚硒酸树脂,方便易得,而且可望实现残余树脂的回收利用.为此,我们尝试用前面得到的副产物———聚苯乙烯负载苯亚硒酸树脂,在30%双氧水和醇组成的体系中,促进肟转变成羧酸酯的反应.R 1CH NOH +R 2OH●θSeO 2HH 2O 2R 1C OOR 21　实验部分1.1　主要仪器和试剂　Shimadzu IR -435型红外光谱仪;JOE L PMX60型核磁共振仪(C DCl 3为溶剂,T MS 为内标);化合物的熔点用显微熔点仪测定,温度未经校正;聚苯乙烯负载亚硒酸(1.24mm ol Se/g )为固相合成烯丙基醚或烯丙基酯[11]过程中的副产物,白色固体,元素分析(Se ,9.85%),其红外光谱吸收峰为:3406,3509,3025,2922,2849,2496,1600,1493,1452,1070,1023,969,912,758,699,541cm -1,与文献[12]一致;其余起始原料为市售试剂或本实验室自制.1.2　肟的制备　参考文献[9]的方法,将无水醋酸钠(0.62g )加入到醛(5.0mm ol )的甲醇(30m L )溶液中,随后加入盐酸羟氨(0.52g ,7.5mm ol ),混合物加热回流4h ,趁热过滤,冷却析出固体,粗产品重结晶得到纯品,经熔点和分析确定其结构.对无法结晶析出的肟,则用二氯甲烷萃取,无水硫酸镁干燥,蒸发溶剂,第27卷第4期2003年8月　江西师范大学学报(自然科学版)JOURNA L OF J I ANG XI NORM A L UNI VERSITY Vol.27No.4　Aug.2003692江西师范大学学报(自然科学版)2003年粗产品再以正己烷和苯(5/1,V/V)结晶得到纯品.1.3　聚苯乙烯负载的苯亚硒酸促进H2O2将肟氧化成羧酸酯　将肟(5mm ol)溶解于相应醇(25m L)中,加入聚苯乙烯负载苯亚硒酸树脂0.1g(0.124mm ol)和30%的双氧水(1.5m L,17.7mm ol).反应混合物经搅拌回流,T LC检测至几乎无肟的斑点时结束反应.过滤,树脂用适量的醇洗涤,树脂回收循环使用.滤液经减压蒸出过量的醇,残渣溶于二氯甲烷(10m L)中,加入饱和的碳酸氢钠溶液,分液,水洗,用无水硫酸镁干燥,蒸干溶剂得粗产物,经重结晶或薄层分析得到纯品.2　结果与讨论苯基亚硒酸也具有一定的氧化性;不加入双氧水,苯亚硒酸树脂、醇和肟组成的体系在常温下反应48h,羧酸酯的产率只有20%左右.不加入苯亚硒酸树脂,双氧水、醇和肟组成的体系即使常温搅拌几天或加热回流72h,反应也不发生;但加入适量的苯亚硒酸树脂,常温下反应48h,产率可达60%左右.进一步优化反应条件,将反应混合物回流反应,薄层分析检测至肟基本消失,常规处理,得到产物羧酸酯.当使用伯醇或仲醇时,相应羧酸酯的产率中等到良好(表1),但在含叔醇的体系中没有相应的羧酸酯生成.该反应的历程可能是苯亚硒酸树脂催化过氧化氢将肟氧化成相应的羧酸或通过其它中间体,其反应机理还有待于进一步研究.表1　苯亚硒酸树脂促进过氧化氢氧化肟转变成羧酸酯的实验结果Entry R1R2产　物反应时间(h)产率(%)a1C6H5CH3a5802C6H5CH2CH3b5813C6H5CH3(CH2)2c8834C6H5CH(CH3)2d8835C6H5CH2C6H5b e12686p-CH3C6H4CH3f4867p-ClC6H4CH3g5838p-NO2C6H4CH3h5879PhCH2CH3i47810CH3(CH2)2CH3j875a.分离后的产率;b.当使用苄醇时反应温度为100℃.需要指出的是,反应后的树脂,经醇洗涤后可再次使用,循环使用的树脂活性无明显变化(见表2),5次使用后的苯亚硒酸树脂的硒含量为9.54%,硒损失仅为3.15%.表2　苯亚硒酸树脂重复使用的实验结果(R1=C6H5,R2=CH3)使用次数12345产率(%)7980807979 苯甲酸甲酯(a)9:Oil;1H NMRδ:8.10～7.90(m,2H),7.38～7.40(m,3H),3.81(s,3H);IR(film)ν:3032,2875,1722,1600,1450,1310,1250,1105cm-1.max苯甲酸乙酯(b)9:Oil;1H NMRδ:8.10～7.85(m,2H),7.15～7.45(m,3H),4.50(q,2H),1.20(t, 3H);IR(film)νmax:3031,2872,1718,1602,1584,1367,1315,1277,1108,710cm-1.苯甲酸丙酯(c)9:Oil;1H NMRδ:8.02～7.95(m,2H),7.15～7.55(m,3H),4.20(t,2H),1.61～1.80 (m,2H),1.20(t,3H);IR(film)νmax:3030,2874,1716,1600,1585,1370,1314,1275,1108,699 cm-1.苯甲酸异丙酯(d )13:Oil ;1H NMR δ:8.12～7.92(m ,2H ),7.10～7.55(m ,3H ),5.10～5.40(m ,1H ),1.33(d ,6H );IR (film )νmax :3030,2875,1715,1600,1584,1375,1265,900,705cm -1.苯甲酸苄酯(e )9:Oil ;1H NMR δ:8.10～7.80(m ,2H ),7.05～7.48(m ,8H ),5.20(s ,2H );IR (film )νmax :3033,2985,1717,1601,1585,1498,1269,1109,710cm -1.对甲基苯甲酸甲酯(f)13:m.p .33～34℃(lit.32～34℃);1H NMR δ:7.89(d ,2H ),7.15(d ,2H ),3.81(s ,3H ),2.30(s ,3H );IR (film )νmax :3030,2965,1726,1605,1435,1378,1265,1175,1080,745cm -1.对氯苯甲酸甲酯(g)13:m.p.43～44℃(lit.42～44℃);1H NMR δ:7.95(d ,2H ),7.35(d ,2H ),3.80(s ,3H );IR (film )νmax :3032,2955,1725,1595,1485,1448,1278,1075,1010,750cm -1.对硝基甲酸甲酯(h)9:m.p.94～95℃(lit.94～95℃);1H NMR δ:8.25(d ,2H ),7.65(d ,2H ),3.90(s ,3H );IR (film )νmax :3035,2978,1716,1600,1520,1445,1345,1270,1110,725cm -1.苯乙酸甲酯(i )9:Oil ;1H NMR δ:8.05～7.90(m ,2H ),7.35～7.42(m ,3H ),3.81(s ,3H ),3.50(s ,2H );IR (film )νmax :3030,2878,1730,1600,1455,1375,1255,1105cm -1.丁酸甲酯(j )9:Oil ;1H NMR δ:3.45(s ,3H ),2.01(t ,2H ),1.35～1.45(m ,2H ),0.88(t ,3H );IR(film )νmax :2967,2879,1742,1437,1361,1260,1198,1097,1050,997,880cm -1.3　结论聚苯乙烯负载的苯亚硒酸试剂,在含醇的体系中有效地促进了过氧化氢将肟直接氧化为相应的羧酸酯.聚苯乙烯负载的苯亚硒酸树脂可循环使用,提高了原子经济性,克服了非固载化苯基亚硒酸毒性较大、不易回收利用等缺点.参考文献:[1]Fukudome M ,Fujioka T ,Y uan D Q ,et al.Selective sulfonylation of one of the 21different hydroxyl groups of m ono -altro -β-cyclodextrin[J ].T etrahedron Lett ,2001,42(2):293-295.[2]G rieco P A ,Y okoyama Y,G ilman S ,et anoselenium chemistry ,epoxidation of olefins with benzeneseleninic acid and hydrogen per 2oxide[J ].J Org Chem ,1977,42(11):2034-2036.[3]H ori T ,Sharpless K B.Synthetic applications of arylselenenic and arylseleninic acids ,conversion of olefins to allylic alcohols and epoxides[J ].J Org Chem ,1978,43(9):1689-1697.[4]G rieco P A ,Y okoyama Y,G ilman S ,et al.C onversion of ketones into lactones with Benzeneseleninic acid and hydrogen peoxide (Ben 2zeneperoxyseleninic acid ):a new reagent for the Baeyer -Villiger reaction[J ].J Chem S oc ,Chem C ommun ,1977,(23):870-871.[5]K uwajima I ,Shimizu M ,Urabe H.Oxidation of alcohols with t -butyl hydroperoxide and diaryl diselenide[J ].J Org Chem ,1982,47(5):837-842.[6]K rantz A ,Laureni J.Characterization of matrix -is olated antiaromatic three -membered heterocycles ,preparation of the elusive thiirene m olecule[J ].J Am Chem S oc ,1981,103(3):486-496.[7]Choi J K,Chang Y K,H ong S Y.Catalytic oxidation of aldehydes to carboxylic acids with hydrogen peroxide as oxidant [J ].T etrahedron Lett ,1988,29(16):1967-1970.[8]Barton D H R ,Magnus P D ,R osen feld M N.Oxidation of phenols to hydroxycyclohexadienones using diphenylseleninic anhydride [J ].J Chem S oc ,Chem C ommun ,1975,(8):301.[9]Said S B ,Skarzewski J ,Miochowski J.Oxidative conversion of aldoximes into carboxylic acid esters[J ].Synth C ommun ,1992,22(13):1851-1862.[10]T aylor R T ,Flood L A.P olystyrene -bound phenylseleninic acid :catalytic oxidations of olefins ,ketones and aromatic systems[J ].J Org Chem ,1983,48(26):5160-5164.[11]Sheng S R ,Huang X.Synthesis of allylic esters and ethers using polymer -supported selenium bromide[J ].J Chem Res ,2002,(4):184-185.(下转第371页)792第4期王幸聪,等:聚合物负载苯亚硒酸试剂促进过氧化氢氧化肟转变成羧酸酯A N ote on the Metric Function Confirmed by a Fixed Point and aSmooth Surface CompactZH ONGJian -hua(Dept of M aths ,G uangdong Education Institute ,G uangdong G uang zhou ,510310,China )Abstract :In this paper a new metric function is presented.With this function ,we discuss the critical tangent points of this function and degenerative one ,and extend the relative results in paper of LI U Ru -yan.The geometry meaning for the choice of fixed points indicated.K ey w ords :metric function ;critical tangent point ;degenerative critical tangent point ;critical point(责任编辑:王金莲)(上接第297页)[12]Zundel G.Application of selenium chemistry[J ].Angew Chem ,Int Ed Engl ,1969,8:499.[13]McDonald C ,H olcomb H ,K ennedy K,et al.N -iodosuccinimide -mediated conversion of aldehydes to methyl es 2ters[J ].J Org Chem ,1989,54(5):1213-1215.Polymer -Supported Phenylseleninic Acid Promoted the Oxidation ofAldoximes to C arboxylic Acid Esters with H ydrogen PeroxideW ANG X ing -cong ,　S ANG X iao -yan ,　LI U X iao -ling(Institute of Chemistry Sciences ,Jiangxi N ormal University ,Nanchang 330027,China )Abstract :Aromatic and aliphatic aldoximes could be efficiently converted into the corresponding carboxylic acid esters by treatment aldoximes with an alcoholic s olution of 30%hydrogen peroxide in the presence of catalytic am ounts of polystyrene -bound phenylseleninic acid.Primary and secondary alcohols give m oderate to g ood yields ,but with tertiary alcohols no esterification was observed.The recovered phenylseleninic acid resin could be in subsequent used with no fur 2ther treatment and no significant loss of reactivity.K ey w ords :polystyrene -supported phenylseleninic acid ;oxidation ;hydrogen peroxide ;aldoxime ;ester(责任编辑:刘显亮)173第4期钟建华:由定点与光滑紧致曲面所确定的距离函数的一个注记。

特产研究163Special Wild Economic Animal and Plant ResearchDOI：10.16720/ki.tcyj.2023.093人参皂苷治疗骨性关节炎的研究进展郭校妍1，张伟东1，张扬1※（吉林大学药学院，吉林长春130021）摘要：人参在防治关节软骨损伤退变及参与体外培养软骨细胞修复关节软骨缺损中具有较好治疗前景。

人参皂苷作为人参的主要药理活性成分，在治疗骨性关节炎的进程中发挥关键作用。

人参皂苷根据不同的结构被分为不同的类型，各类型均含有多种人参皂苷单体成分，其治疗骨性关节炎的机制也各不相同。

本文对不同人参皂苷单体治疗骨性关节炎的研究进行梳理和总结，探讨其治疗骨性关节炎的潜在可能性和作用机制，为后期临床应用提供依据。

关键词：骨性关节炎；人参皂苷；信号通路中图分类号：R285文献标识码：A文章编号：1001-4721（2023）03-0163-06Research Progress of Ginsenosides in the Treatment of OsteoarthritisGUO Xiaoyan1,ZHANG Weidong1,ZHANG Yang1※（School of Pharmaceutical Sciences,Jilin University,Changchun130021,China）Abstract:Ginseng has pharmacological effects such as anti-inflammatory,antioxidant,antidepressant,anti-Alzheimer's and anti-athero-sclerosis.Current studies have found that it has good therapeutic prospects in preventing degeneration of articular cartilage damage and parti-cipating in in vitro culture of chondrocytes to repair articular cartilage defects.Ginsenosides,as the main pharmacological active component of ginseng,also play an important role in the process of treating osteoarthritis.Ginsenosides can be classified into different types because of their different structures,and each type contains a variety of ginsenoside monomer components with different mechanisms for the treatment of osteoarthritis.In this paper,we review the research progress of different ginsenoside monomers in the treatment of osteoarthritis,and ex-plore their potential possibilities and mechanisms for the treatment of osteoarthritis,so as to provide a basis for later clinical application. Key words:osteoarthritis;ginsenosides;signaling pathway骨性关节炎（Osteoarthritis,OA）是一种退行性病变，系由于增龄、肥胖、遗传、劳损、创伤、关节先天性异常和关节畸形等诸多因素引起的关节软骨退化损伤、关节边缘和软骨下骨反应性增生。

卤代对羟基苯甲酸酯英语Halogenated Hydroxybenzoic Acid Esters.Halogenated hydroxybenzoic acid esters, commonly known as halogenated parabens, are a class of chemical compounds that are widely used as preservatives in cosmetics, personal care products, and food items. These esters are derived from hydroxybenzoic acid, which is naturally found in plants, and are halogenated, typically with chlorine or bromine, to enhance their antimicrobial properties.Applications and Uses.Halogenated hydroxybenzoic acid esters are primarily used as preservatives due to their ability to inhibit the growth of bacteria, fungi, and mold. They are commonly found in products such as lotions, creams, shampoos, conditioners, makeup, and other personal care items. Additionally, they are also used in food processing to preserve the freshness and shelf life of various foodproducts.Properties and Characteristics.The halogenation of hydroxybenzoic acid esters confers upon them several unique properties. Chlorine and bromine are highly reactive halogens that can easily replace the hydrogen atoms on the hydroxybenzoic acid esters, creating stable and water-soluble compounds. These halogenated esters are typically colorless or slightly yellow liquids with low volatility.The antimicrobial activity of halogenated hydroxybenzoic acid esters is attributed to their ability to disrupt the cellular membranes of microorganisms. The halogen atoms interact with the lipid bilayer of the cell membrane, causing it to become more permeable, which leads to the leakage of cellular contents and ultimately cell death.Types of Halogenated Hydroxybenzoic Acid Esters.There are several types of halogenated hydroxybenzoic acid esters, each with its own unique properties and applications. Some common examples include:1. Chloroparabens: Chlorinated derivatives of hydroxybenzoic acid esters are known as chloroparabens. These compounds are widely used as preservatives in cosmetics and personal care products due to their broad-spectrum antimicrobial activity. Common chloroparabens include methylparaben, ethylparaben, propylparaben, and butylparaben.2. Bromoparabens: Brominated derivatives of hydroxybenzoic acid esters are known as bromoparabens. These compounds are less common than chloroparabens but are also used as preservatives in some products due to their antimicrobial properties. Bromoparabens such as bromomethylparaben and bromopropylparaben are used in specific applications where additional antimicrobial activity is desired.Safety and Regulations.The use of halogenated hydroxybenzoic acid esters in cosmetics and personal care products is generally considered safe. However, there has been some concern regarding their potential impact on human health and the environment. Some studies have suggested that parabens may act as endocrine disruptors, interfering with the normal function of hormones in the body. However, these findings are still controversial, and more research is needed to confirm their potential health effects.In response to these concerns, some countries and regions have implemented regulations limiting the use of parabens in cosmetics and personal care products. Additionally, some consumers may choose to avoid products containing parabens due to their personal preferences or concerns about their potential health effects.Conclusion.Halogenated hydroxybenzoic acid esters, particularly chloroparabens, are widely used as preservatives incosmetics, personal care products, and food items due to their antimicrobial properties. While they are generally considered safe for use in these applications, there are concerns regarding their potential impact on human health and the environment. Ongoing research and regulatory efforts aim to ensure the safety of these compounds while also addressing consumer preferences and concerns.。

第32卷2004年6月 分析化学(FENXI HUAXU E )　研究报告Chinese Journal of Analytical Chemistry 第6期747～751邻氨基苯酚化学修饰试剂用于气相色谱/质谱分析花粉脂肪酸邹耀洪(常熟理工学院化学系,常熟215500)摘　要　采用邻氨基苯酚作为脂肪酸的化学修饰试剂,将羧基修改为含氮杂环,使在EI 源中避免链烯基中碳碳双键的移动。

以气相色谱/EI 质谱分析花粉脂肪酸,解析脂肪酸邻氨基苯酚化学修饰产物的EI 质谱图;讨论了烯酸中碳碳双键的定位规则;鉴定出巨日花粉12种脂肪酸,由C 12～C 24脂肪酸组成,不饱和脂肪酸的含量占73.94%,其中多不饱和脂肪酸含量占47.61%,多不饱和脂肪酸与饱和脂肪酸之比达1.85,还检出了在其他花粉中极为少见的人体必需脂肪酸152二十四烯酸(神经酸)。

关键词　气相色谱/质谱,花粉,脂肪酸,化学修饰,邻氨基苯酚2003207224收稿;2004201205接受1　引 言花粉是植物的雄性生殖细胞,蜂花粉是蜜蜂从植物花蕊内采集的花粉。

花粉营养丰富且含有多种生理活性成分,如多不饱和脂肪酸、黄酮类化合物及多糖等,具有抗衰老、抗菌、抗癌、降血脂及促进大脑发育等功能,可用于治疗心血管病、高血脂症、高血压、前列腺炎、关节炎等[1]。

花粉资源极为丰富,仅马尾松一年可产花粉三千万吨。

花粉虽已被用于制药、生产保健品和美容化妆品等,但始终处于低级利用阶段,其潜在的开发价值还没有得到充分重视,深度研究与利用尚未涉及。

如花粉的功能因子———多不饱和脂肪酸的研究至今仍是块处女地,虽有个别蜂花粉脂肪酸甲酯的GC/EIMS 分析的报道[2],但由于脂肪酸或其甲酯在EIMS 条件下碳碳双键可以移动,难以对不饱和脂肪酸中的碳碳双键进行正确定位[3],因而在研究各种植物花粉的脂肪酸以及花粉脂肪酸的精细结构与其功能的关系时存在着不定因素。

测定烯酸中的双键位置常用氧化断链法,但只适用于单不饱和脂肪酸[4]。

纤枝金丝桃化学成分研究作者：张涵，邓憬童，彭宇，韩庆迪，周献东，杨新洲来源：《广西植物》2022年第09期摘要：為了探究滇产植物纤枝金丝桃的物质基础，寻找活性化合物，该文用80%乙醇对纤枝金丝桃地上部分浸渍提取，应用HP-20大孔吸附树脂、硅胶、葡聚糖凝胶、半制备高效液相等色谱技术对纤枝金丝桃的化学成分进行分离纯化，根据波谱数据鉴定化合物的结构。

结果表明：（1）从纤枝金丝桃中分离得到15个化合物，分别鉴定为attenuatumione G （1）、uralodin B （2）、chipericumin C （3）、2，5-二羟基-1-甲氧基氧杂蒽酮（4）、1，7-二羟基氧杂蒽酮（5）、1，7-二羟基-4-甲氧基氧杂蒽酮（6）、槲皮苷（7）、芹菜素-7-O-β-D-葡萄糖苷（8）、芹菜素-7-O-β-D-（6″-O-乙酰基）-葡萄糖苷（9）、木犀草素（10）、槲皮素（11）、白桦脂酸（12）、白桦脂酸甲酯（13）、白桦脂酮酸（14）、β-谷甾醇（15）。

化合物1-14为首次从该植物中分离得到。

（2）采用MTT法对化合物1-14进行体外抗乳腺癌活性测试，结果仅显示化合物3、6、13对2种乳腺癌细胞株MCF-7和MDA-MB-231有一定的抑制作用，其IC50值为48.6～123.5 μg·mL-1。

该研究结果对综合开发利用纤枝金丝桃资源具有理论和应用意义。

关键词：金丝桃属，纤枝金丝桃，化学成分，多环多异戊烯基间苯三酚，细胞毒活性中图分类号： Q946文献标识码： A文章编号： 1000-3142（2022）09-1542-09Chemical components of Hypericum lagarocladumZHANG Han， DENG Jingtong， PENG Yu， HAN Qingdi， ZHOU Xiandong， YANG Xinzhou*（ School of Pharmaceutical Sciences， South-Central Minzu University， Wuhan 430074，China ）Abstract： The purpose of this paper was to study the material basis and to find the bioactive chemical components of Hypericum lagarocladum. The aerial part of this species was extracted with 80% ethanol， and then the crude extract was isolated and purified by HP-20 macroporous adsorption resin column chromatography （CC）， silica gel CC， Sephadex LH-20 CC and semi-preparative HPLC. The structures of isolated compounds were deduced by the spectroscopic data， as well as comparison with the previous literature data. The results were as follows：（1） Fifteen compounds were isolated from H. lagarocladum， and those compounds were identified as attenuatumione G （1）， uralodin B （2）， chipericumin C （3）， 2，5-dihydroxy-1-methoxyxanthone （4），1，7-dihydroxyxanthone （5），1，7-dihydroxy-4-methoxyxanthone （6）， quercitrin （7），apigenin-7-O-β-D-glucopyranoside （8）， apigenin-7-O-β-D-（6″-O-acetyl）-glucopyranoside （9）， luteolin （10）， quercetin （11）， betulinic acid （12）， betulinic acid methyl ester （13）， betulonic acid （14），and β-sitosterol （15）. Compounds 1-14 are isolated from H. lagarocladum for the first time. （2） In vitro cytotoxicites of compounds 1-14 were evaluated using MTT method against MCF-7 and MDA-MB-231 cell lines. And only compounds 3， 6 and 13 showed weak cytotoxicites with IC50 values ranging from 48.6 to 123.5 μg·mL-1. These research results provide scientific theoretical and applied implications of H. lagarocladum for its comprehensive development and utilization.Key words： Hypericum， Hypericum lagarocladum， chemical components， PPAPs，cytotoxicity藤黄科（Clusiaceae）金丝桃属（Hypericum）植物，大约460种，中国有64种（33特有种）。

PolydextroseINS: 1200CAS: [68424-04-4]DESCRIPTIONPolydextrose occurs as an off-white to light tan solid. It is a randomly bonded polymer prepared by the condensation of a melt that consists of approximately 90% D-glucose, 10% sorbitol, and 1% citric acid or 0.1% phosphoric acid on a weight basis. The 1,6-glycosidic linkage predominates in the polymer, but other possible bonds are present. The product contains small quantities of free glucose, sorbitol, and D-anhydroglucoses (levoglucosan), with traces of citric acid or phosphoric acid. It may be partially reduced by transition metal catalytic hydrogenation in an aqueous solution. It may be neutralized with any food-grade base and decolorized and deionized for further purification. It is very soluble in water.Function Bulking agent; humectant; texturizerPackaging and Storage Store in tight, light-proof containers.IDENTIFICATION• A. P ROCEDURESample solution: 100 mg/mLAnalysis: Add 4 drops of 5% aqueous phenol solution to 1 drop Sample solution, then rapidly add 15 drops of sulfuric acid.Acceptance criterion: A deep yellow to orange color appears.• B. P ROCEDURESample solution: 100 mg/mLAnalysis: While vigorously swirling (vortex mixer), add 1.0 mL of acetone to 1.0 mL of Sample solution. [N OTE: Retain this solution for Identification test C (below).]Acceptance criterion: The solution remains clear.• C. P ROCEDUREAnalysis: While vigorously swirling, add 2.0 mL of acetone to the retained solution from Identification test B.Acceptance criterion: A heavy, milky turbidity develops immediately.• D. P ROCEDURESample solution: 20 mg/mLSample: Add 4 mL of alkaline cupric citrate TS to 1 mL of Sample solution. Boilvigorously for 2 to 4 min. Remove from heat, and allow the precipitate (if any) tosettle.Acceptance criterion: The supernatant is blue or blue-green.ASSAY• P ROCEDUREStandard stock solution: 0.2 mg/mL -D-glucoseStandard solutions: 50, 40, 20, 10, and 5 µg/mL -D-glucose: made from Standard stock solutionSample stock solution: 1.0 mg/mLSample solution: 40 µg/mL: made from Sample stock solutionPhenol solution: Add 20 mL of water to 80 g of phenol.Analysis: On a daily basis, pipet 2.0 mL of each Standard solution and the Sample solution into separate, acetone-free, 15-mL screw-cap vials. Add 0.12 mL of thePhenol solution, and mix gently. Uncap each vial and rapidly add 5.0 mL of sulfuric acid. Immediately recap each vial, and shake vigorously. [CAUTION: Wear rubber gloves and a safety shield while adding sulfuric acid. ]Let the vials stand at room temperature for 45 min, then determine the absorbance of each sample at 490 nm in a suitable spectrophotometer, using a Phenol solution–sulfuric acid reagent blank in the reference cell. Repeat the procedure three times and obtain the mean absorbance value. For the standard curve, plot meanabsorbance values versus concentrations, in µg/mL, obtained from triplicateStandard solutions. Calculate the percent polymer by the formula:1.05[100(A Y)/(S × C) P G 1.11P L]1.05 = An experimentally derived correction factor to account for the polymer(which also contains a small amount of sorbitol) not giving the exact amountof color given by an equivalent amount of glucose monomersA = Sample absorbanceY = The y-intercept of the standard curveS = Slope (approximately 0.02) of absorbance versus glucose concentration,in g/mL, obtained from the standard curveC = Concentration (g/mL) of the Sample stock solution, adjusted for ash andmoistureP G = Percentage of glucose determined under the test for Monomers (below)P L = Percentage of levoglucosan determined under the test for Monomers(below)1.11 = Conversion factor from levoglucosan, which gives an equivalentamount of color to an equivalent weight of glucoseAcceptance criterion: NLT 90.0% polymer, calculated on the anhydrous, ash-free basisIMPURITIESChange to read:Inorganic Impurities• L EAD[N OTE: For this test, use reagent-grade chemicals with as low a lead content as ispracticable, as well as high-purity water and gases. Before use in this analysis,rinse all glassware and plasticware twice with 10% nitric acid and twice with 10%hydrochloric acid, and then rinse them thoroughly with high-purity water, preferably obtained from a mixed-bed, strong-acid, strong-base, ion-exchange cartridgecapable of producing water with an electrical resistivity of 12 to 15 megohms.] Apparatus: Use a suitable spectrophotometer (Perkin-Elmer Model 6000, orequivalent), a graphite furnace containing a L'vov platform (Perkin-Elmer ModelHGA-500, or equivalent), and an autosampler (Perkin-Elmer Model AS-40, orequivalent). Use a lead hollow-cathode lamp (lamp current of 10 mA), a slit width of0.7 mm (set low), the wavelength set at 283.3 nm, and a deuterium arc lamp forbackground correction.Lead nitrate solution: 100 µg of lead (Pb) ion/mL prepared as follows: Dissolve 159.8 mg of lead nitrate in 100 mL of water containing 1 mL of nitric acid. Dilute with water to 1000.0 mL, and mix. Prepare and store this solution in glass containers that are free from lead salts.Standard stock solution: 10 µg of lead (Pb) ion/mL: from Lead nitrate solution [N OTE: Prepare on the day of use.][N OTE: As an alternative to preparing the Lead nitrate solution and Standard stock solution NIST Standard Reference Material containing 10 mg of lead/kg, or equivalent may be used.]Standard solutions: 0.02, 0.05, 0.1, and 0.2 µg of lead (Pb) ion/mL: from Standard stock solutionMatrix modifier solution: 10 mg/mL of dibasic ammonium phosphateSample solution: Transfer 1 g of sample into a 10-mL volumetric flask, add 5 mL of water, and mix. Dilute to volume, and mix.Spiked sample solution: Prepare a solution as directed under Sample solution, but add 100 µL of the Standard stock solution, dilute to volume, and mix. This solution contains 0.1 µg of lead/mL.Analysis: With the use of an autosampler, atomize 10-µL aliquots of the four Standard solutions, using the following sequence of conditions:(1) Dry at 130 with a 20-s ramp period, a 40-shold time, and a 300-mL/min argon flow rate;(2) Char at 800 with a 20-s ramp period, a 40-sAtomize 10 µL of the Matrix modifier solution in combination with either 10 mL of the Sample solution or 10 µL of the Spiked sample solution under identicalconditions used for the Standard solutions .Plot a standard curve using the concentration, in µg/mL, of each Standard solution versus its maximum absorbance value compensated for background correction,and draw the best straight line. From the standard curve, determine theconcentrations, C S and C A , in µg/mL, of the Sample solution and the Spikedsample solution , respectively. Calculate the quantity, in mg/kg, of lead in thesample taken by the formula:10C S /Whold time, and a 300-mL/min argon flow rate;(3) Atomize at 2400 for 6 s with a 50-mL/min argon flow rate;(4) Clean at 2600 with a 1-s ramp period, a 5-s hold time, and a 300-mL/min argon flow rate; and(5) Recharge at 20 with a 2-s ramp period, a 20-s hold time, and a 300-mL/min argon flow rate.W = Weight (g) of sample takenCalculate the recovery by the formula:100[(C A C S )/0.1]0.1 = Amount of lead (µg/mL) added to the Spiked sample solutionAcceptance criterion: NMT 0.5 mg/kg• N ICKEL , Nickel Limit Test ,Method II , FCC 6 Appendix IIIB (for Hydrogenated Polydextrose)Acceptance criterion: NMT 2 mg/kgOrganic Impurities• 5-H YDROXYMETHYLFURFURAL AND R ELATED C OMPOUNDSSample solution: 10 mg/mLAnalysis: Read the absorbance of the Sample solution against a water blank at 283 nm in a 1-cm quartz cell in a spectrophotometer. Calculate the percent 5-hydroxymethylfurfural and related compounds by the formula:(0.749 × A)/C0.749 = A composite proportionality constant that includes the extinctioncoefficient and other molecular weight, unit, and volume conversionsA = Absorbance of the Sample solutionC = Concentration (mg/mL) of Sample solution, corrected for ash andmoistureAcceptance criterion: NMT 0.1%, calculated on the anhydrous, ash-free basis• M ONOMERSOctadecane solution: 0.5 mg/mL n-octadecane in pyridineStandard solution: Transfer 50 mg of -D-glucose1, 40 mg of anhydrous D-sorbitol, and 35 mg of D-anhydroglucoses, all accurately weighed, into a 100-mL volumetric flask; dissolve in and dilute to volume with pyridine.Silylated standard solution: Transfer 1.0 mL of Standard solution to a screw-cap vial, and add 1.0 mL of Octadecane solution and 0.5 mL of N-trimethylsilylimidazole. Cap the vial, and immerse it in an ultrasonic bath at 70 for 60 min.Sample solution: Transfer 20 mg of sample into a screw-cap vial, and add 1.0 mL of Octadecane solution, 1 mL of pyridine, and 0.5 mL of N-trimethylsilylimidazole. Cap the vial, and immerse it in an ultrasonic bath at 70 for 60 min. Chromatographic system, Appendix IIAMode: Gas chromatographyDetector: Flame-ionization detectorColumn: 250-cm × 2-mm (id) glass column, or equivalent, packed with 3% OV-1stationary phase on 100- to 120-mesh Gas Chrom Q, or equivalentTemperature:Column: 175Injection port: 210Detector: 230Injection volume: About 3 µLAnalysis: Initially, inject the Silylated standard solution into the gas chromatograph.Repeat twice, then inject duplicate portions of the Sample solution. [N OTE: Relative retention times (min) are: D-anhydroglucoses (levoglucosan), pyranose form (3.7);furanose form (not present in standard) (4.3); n-octadecane (5.1); -D-glucose (8.7);D-sorbitol (11.3); -D-glucose (13.3).] Calculate the percentage of each monomer by the formula:(R × W S)/(R S × W)R = Ratio of the area of the monomer peak to the area of the octadecanepeak in the sample injectionW S = Weight (mg) of the respective monomer in the Silylated standardsolutionR S = Mean ratio of the area of the monomer peak to the area of theoctadecane peak in the standard injectionsW = Weight (mg) of sample taken, adjusted for residue on ignition andmoistureAcceptance criteria:D -Anhydroglucoses: NMT 4.0%, calculated on the anhydrous, ash-free basisGlucose and Sorbitol: NMT 6.0%, calculated on the anhydrous, ash-free basis SPECIFIC TESTS• M OLECULAR W EIGHT L IMITMobile phase: Dissolve 35.0 g of sodium nitrate and 1.0 g of sodium azide in 100 mL of HPLC-grade water. Filter through a 0.45-µm filter into a 4-L flask. Dilute to volume with HPLC-grade water. Degas by applying an aspirator vacuum for 30 min. The resulting eluent is 0.1 N sodium nitrate containing 0.025% sodium azide.Standard solution: Transfer 20 mg each of dextrose 2; stachyose 2; and 5800, 23,700, and 100,000 molecular weight (MW) pullulan standards 2 into a 10-mL volumetric flask. Dissolve in and dilute to volume with Mobile phase . Filter through a 0.45-µm syringe filter.Sample solution: 5 mg/mL in Mobile phase , and filtered through a 0.45-µm filter Chromatographic system, Appendix IIAMode: High-performance liquid chromatographyDetector: Differential refractometerColumn: Waters Ultrahydrogel 250 A size-exclusion column, or equivalentColumn temperature: 45Detector cell temperature: 35f0.1Flow rate: 0.8 mL/min, reproducible to 0.5%Injection volume: 50 µLSetup: Use either a loop injector or suitable autosampler, a column heating block or oven and a computing integrator, or a computer data handling system withmolecular weight determination capabilities. Set the differential refractometer at a sensitivity of 4 ×106 refractive index units full scale, and set the plotter of theintegrator to 64 mV full scale. Noise attributable to the detector and electronicsshould be less than 0.1% full scale.Column equilibration:After installing a new column in the HPLC, pump Eluentthrough it overnight at 0.3 mL/min. Before calibration or analysis, increase the flowslowly to 0.8 mL/min over a 1-min period, then pump at 0.8 mL/min for at least 1 h before the first injection. Check the flow gravimetrically, and adjust it if necessary.Reduce the flow to 0.1 mL/ min when the system is not in use.Data system setup: Set the integrator or computerized data-handling system as its respective manual instructs for normal gel permeation chromatographicdeterminations. Set the integration time to 15 min.Column standardization: After equilibrating the HPLC system at a flow rate of 0.8 mL/min for at least 1 h, inject 50 µL of the Standard solution five times, allowing 15 min between injections. Record the retention times of the various components inthe Standard solution. Retention times for each component should agree within ±2 s. Insert the average retention time along with the molecular weight of eachcomponent into the calibration table of the molecular weight distribution software.System suitability: Check the regression results for a cubic fit of the calibrationpoints. They should have an R2 value of 0.9999+. Dextrose and stachyose should be baseline resolved from one another and from the 5800 MW pullulan standard.Elevated valleys are usually observed between the 5800, the 23,700, and the100,000 MW pullulan standards.Analysis: Inject 50 µL of the Sample solution, following the same conditions andprocedure as described under Column standardization. Using the Molecular Weight Distribution software of the data-reduction system, generate a molecular weightdistribution curve of the sample.Acceptance criterion: There is no measurable peak above a molecular weight of22,000.• P H, pH Determination, Appendix IIBSample solution: 100 mg/mLAcceptance criteria:Untreated Polydextrose: Between 2.5 and 7.0Neutralized or Decolorized Polydextrose: Between 5.0 and 6.0• R ESIDUE ON I GNITION (S ULFATED A SH), Method I, Appendix IICAcceptance criteria:Untreated Polydextrose: NMT 0.3%;Neutralized or Decolorized Polydextrose: NMT 2.0%• W ATER, Water Determination, Appendix IIBAnalysis: Determine as directed, but using pyridine instead of methanol in the titration vessel.Acceptance criterion: NMT 4.0%1 Available from NIST2 Available from Polymer Laboratories, Inc., Technical Center, Amherst Fields Research Park, 160 OldFarm Road, Amherst, MA 01002.Auxiliary Information— Please check for your question in the FAQs before contacting USP.。