磺化四-(p-羟基苯基)间苯二酚杯[4]芳烃的合成及应用

利用间苯二酚与对羟基苯甲醛采用一步法合成四-(p-羟基苯基)间苯二酚杯[4]芳烃,通过红外、核磁表征产物结构。利用浓硫酸在四-(p-羟基苯基)间苯二酚杯[4]芳烃上引入磺酸基,制备了水溶性良好的磺化四-(p-羟基苯基)间苯二酚杯[4]芳烃,并对磺化四-(p-羟基苯基)间苯二酚杯[4]芳烃在山羊酸皮鞣制中的工艺条件进行优化。结果表明:磺化四-(p-羟基苯基)间苯二酚杯[4]芳烃具有鞣性,最优鞣制工艺为鞣制p H值4.5,鞣剂用量10%,鞣制温度35℃。最优鞣制工艺鞣制后坯革的收缩温度达到70.9℃,增厚率为38.18%,抗张强度为27.57N/mm2,撕裂强度达到75.02N/mm。     

新型偶氮染料的合成及其染色性能研究

以杯[4]芳烃、苯佐卡因、三卡因和盐酸普鲁卡因为原料,通过芳胺的重氮化-偶合反应合成了3个新型的偶氮基杯[4]芳烃衍生物6a、6b、6c,收率分别为83%、81%、83%。经IR、~1H NMR和元素分析进行结构表征。通过紫外可见光谱考察了偶氮基杯[4]芳烃衍生物在溶液不同pH条件下的光谱性质,并通过上染曲线、得色深度、色牢度研究其染色性能。结果表明,随着pH的增大,偶氮基杯[4]芳烃衍生物6a、6b、6c发生偶氮-醌腙异构互变,最大吸收峰红移;化合物在碱性条件下的染色效果比酸性条件好,其中化合物6a的上染率高达78%,表面得色深度为2.798,耐干、湿摩擦色牢度和耐皂洗色牢度均为4级,是一种较好的分散染料。     

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。     

超声辅助合成油脂基双亲性超分子北大核心CSCD

为充分利用油脂精炼过程中的皂脚,实现绿色油脂资源的高值化利用,以油酸钠为原料,超声辅助快速合成具有端环氧基的油酸缩水甘油酯,然后以端环氧基油酸缩水甘油酯为原料,与4-叔丁基杯[4]芳烃在酸性条件下发生开环反应,利用超声辅助快速合成兼具长链烷基疏水基和羟基亲水基的油脂基双亲性超分子。通过单因素实验研究了4-叔丁基杯[4]芳烃与端环氧基油酸缩水甘油酯物质的量比、超声时间、超声温度和超声功率对产物得率的影响,并采用FTIR和NMR进行产物结构表征。结果表明:油脂基双亲性超分子最佳合成条件为4-叔丁基杯[4]芳烃与端环氧基油酸缩水甘油酯物质的量比1∶6、超声时间150 min、超声温度50℃、超声功率100 W,在此条件下产物得率高达94%,该法比传统回流搅拌合成方法需要的反应时间更短,副产物更少;产物结构中含有醚氧键、羟基、长链烷基、不饱和双键和苯基,赋予超分子亲水和亲脂的双亲性能。     

5种甾醇的热裂解及其与主流烟气中B[a]P释放量的关系

采用热裂解和热重分析仪,研究了胆甾醇、豆甾醇、β-谷甾醇、麦角固醇和菜油甾醇的热裂解产生多环芳烃及其热失重行为,同时将胆甾醇、豆甾醇、β-谷甾醇和麦角固醇添加到卷烟中以验证甾醇添加量与多环芳烃释放量的关系。结果表明:①5种甾醇类化合物在高温、缺氧的环境下热裂解易于生成多环芳烃,尤其是低环数多环芳烃,5种甾醇的热裂解产物及其分布特点类似。以豆甾醇为例,其热裂解产物中萘及其衍生物占总量的35.44%;②5种甾醇只有一个热失重阶段,在300~400℃区间基本分解完全,推测裂解反应在热裂解过程中占主导因素;③卷烟中甾醇的添加量与主流烟气中苯并[a]芘(B[a]P)释放量呈明显正相关,其中,豆甾醇对B[a]P释放量的贡献最显著,两倍于卷烟中豆甾醇原含量的添加量,卷烟样品的B[a]P释放量增加了17.8%。     

水溶性杯芳烃研究进展及在鞣制中的应用北大核心

介绍了水溶性杯芳烃的结构、性质,综述了其合成方法及应用的研究进展,提出水溶性杯芳烃衍生物可以作为一种新型皮革鞣剂应用于制革鞣制过程。一方面,水溶性杯芳烃下缘含有大量配位活性较高的酚羟基,且经衍生化后可引入羧基、氨基等官能团,可与胶原纤维中的胍基、羟基、羧基、肽基发生相互作用,对皮革胶原起到鞣制作用;另一方面,杯芳烃空腔可以与铬发生π-π堆积作用、阳离子-π作用、氢键作用等,杯芳烃外缘上的磺酸基、羧基等可以与铬配位,从而固定铬鞣。故可以将杯芳烃用于制革少铬鞣过程,减少铬盐用量,有效降低废液中的铬含量。     

水溶性杯芳烃研究进展及在鞣制中的应用

介绍了水溶性杯芳烃的结构、性质,综述了其合成方法及应用的研究进展,提出水溶性杯芳烃衍生物可以作为一种新型皮革鞣剂应用于制革鞣制过程。一方面,水溶性杯芳烃下缘含有大量配位活性较高的酚羟基,且经衍生化后可引入羧基、氨基等官能团,可与胶原纤维中的胍基、羟基、羧基、肽基发生相互作用,对皮革胶原起到鞣制作用;另一方面,杯芳烃空腔可以与铬发生π-π堆积作用、阳离子-π作用、氢键作用等,杯芳烃外缘上的磺酸基、羧基等可以与铬配位,从而固定铬鞣。故可以将杯芳烃用于制革少铬鞣过程,减少铬盐用量,有效降低废液中的铬含量。     

含硫杯[4]芳烃银系配合物在织物上的抗菌性能

为提高银系抗菌剂的稳定性,用银的络合离子替代银离子,将杯芳烃应用在纺织品抗菌整理中。利用含硫杯[4]芳烃具有可修饰性和对银离子有很好的络合作用等特点,制备了一系列新型杯芳烃银系配合物,并证明其对大肠埃希菌ATCC25922、铜绿假单胞菌ATCC27853、金黄色葡萄球菌ATCC29213和白色念珠菌ATCC10231有良好的抗菌性能。将杯芳烃含银配合物作为抗菌剂整理到棉织物上,整理后的棉织物经10次水洗后,对大肠埃希菌ATCC25922、金黄色葡萄球菌ATCC29213和白色念珠菌ATCC10231仍有良好的抗菌效果。     

静电纺杯芳烃纤维的制备及其对Pt(Ⅳ)选择性吸附性能

为选择性吸附贵金属离子,设计并合成5,17-二氨基-26,28-(1’,8’-二氧杂-4’,5’-二硫杂正辛烷基)-杯[4]芳烃单体,通过酰胺化法合成杯芳烃聚酰胺酸纺丝液,用静电纺丝法制备杯芳烃聚酰胺酸纤维,再对杯芳烃聚酰胺酸纤维进行热酰亚胺化,制备出杯芳烃聚酰亚胺纤维。采用红外光谱和扫描电镜对纤维进行表征,并研究了纤维对Pt（Ⅳ）、Ag (Ⅰ) 、Au (Ⅰ)的选择性吸附性能。结果表明,自制杯芳烃已成功引入到杯芳烃聚酰亚胺纤维中,纤维直径为（400 ± 40） nm,它仅对Pt（Ⅳ）有很强的选择性吸附作用,吸附行为符合Langmuir等温吸附模型,纤维对Pt（Ⅳ）饱和吸附量为3.1 mmol /g。选择性吸附的原因是Pt（Ⅳ）最外层电子排布为5d6,未占满,Pt（Ⅳ）可进入纤维中杯芳烃下缘r的1,8 -二氧杂-4,5 -二硫杂正辛烷基的空腔中,并接受O、S的电子,形成配位吸附。     

离子液体杂多酸盐催化剂对间苯二酚和苯乙烯傅克反应的催化性能

在功能化离子液体结构中引入了体积较大的杂多酸阴离子磷钨酸盐,制备了5种离子液体杂多酸盐催化剂[MimPS]H2PW12O40、[MimPS]2HPW12O40、[MimPS]3PW12O40、[PyPS]3 PW12 O40和[TeaPS]3 PW12 O40,并对催化剂进行了表征.通过催化间苯二酚和苯乙烯的傅克反应生...     

Inclusion of bisphenols by a self-assembled monolayer of thiolated calix[6]arene on a gold surface

The molecular recognition of various kinds of bisphenols (BPs) by a self-assembled monolayer (SAM) of thiolated calix[6]arene on a gold electrode was examined using cyclic voltammetry (CV). Based on the inhibitory effect of BPs on the inclusion of hydroquinone (HQ) as a probe bythe surface-confined calix[6]arene, the association constants (Kassoc) of BPs with the immobilized calix[6]arene were estimated. The Kassoc values for BPs with the SAM of thiolated hexasodium calix[6]arenehexasulfonic acid (thioSCX6) were much smaller than those in the free calix[6]arene derivative systems reported previously. The order of the Kassoc values for BPs with thioSCX6 was bisphenol A (BPA) > bisphenol S (BPS) > bisphenol B (BPB) > bisphenol F (BPF). The Kassoc values for BPA and BPS with thioSCX6 were larger than that for BPB, despite the larger hydrophobicity of BPB than that of BPA and BPS. This is probably because the inclusion phenomena in this system are not simply driven by the hydrophobic interaction, but are significantly affected by several steric and structural factors with immobilization of the host. Those are (1) a decrease in flexibility of the SCX6 cavity by the formation of SAM, (2) a decrease in inclusion ability of the SCX6 by the presence of Au surface just beneath it, and (3) a repulsion of hydrophobic guests bythe presence of sulfonate groups at the top of the SAM. Moreover, the association phenomena (adsorption and desorption processes) of a bisphenol with the SCX6 SAM were examined directly by using localized surface plasmon resonance spectroscopy.     

Structural determination of subsidiary colors in commercial Food Green No. 3 (fast green FCF, FD & C Green No. 3).

HPLC analysis revealed that eight subsidiary colors existed in commercial Food Green No. 3 (fast green FCF, FD & C Green No. 3). Among them, four subsidiary colors C, F, G, and H were isolated by using preparative HPLC and their structures were determined by MS and NMR. They were the disodium salt of 2-[[4-[N-ethyl-N-(3- sulfophenylmethyl)amino]phenyl][4-[N-ethyl-N-(4- sulfophenylmethyl)amino]phenyl]methylio]-4-hydroxybenzenesulfonic acid (abbreviated as m,p-G-3), the sodium salt of 2-[[(4-N-ethylamino)phenyl][4-[N-ethyl-N-(3- sulfophenylmethyl)amino]-phenyl]methylio]-4-hydroxybenzenesulfonic acid [abbreviated as HSBA-(EA) (m-EBASA)], the sodium salt of 2-[[(4-N-diethylamino)phenyl][4-[N-ethyl-N-(3- sulfophenylmethyl)amino]phenyl]-methylio]-4-hydroxybenzenesulfonic acid [abbreviated as HSBA-(di-EA) (m-EBASA)], and the sodium salt of 2-[[4-[N-ethyl-N-(phenylmethyl)amino]phenyl][4-[N-ethyl-N-(3- sulfophenylmethyl)-amino]phenyl]methylio]-4-hydroxybenzenesulfonic acid [abbreviated as HSBA-(EBA)(m-EBASA)], respectively. HSBA-(di-EA) (m-EBASA) was a subsidiary color newly found in commercial Food Green No. 3.     

[EMIM]+[BF4]-对乙醇-水体系相平衡的影响

[EMIM]^＋[BF4]^-是一种离子液体,本研究用改进的Othmer汽液平衡釜测定了101．3kPa下[EMIM]^＋[BF4]^-摩尔分率x3=0．1,0．2的乙醇-水-[EMIM]^＋[BF4]^-体系的汽液平衡数据,并用NRTL模型进行了关联,结果平均偏差为0．967％。实验表明：[EMIM]^＋[BF4]^-可以消除乙醇-水体系的共沸点,可以作为萃取精馏分离乙醇-水体系的溶剂。     

BIOSYNTHESIS OF BENZALDEHYDE, BENZYL ALCOHOL AND BENZYL BENZOATE FROM BENZOIC ACID IN CRANBERRY (VACCINIUM MACROCARPON)

The aroma complex of cranberry contains benzaldehyde, benzyl alcohol and benzyl benzoate as major components, and [7-¹⁴C] benzoic acid was converted into benzaldehyde, benzyl alcohol, benzyl benzoate, and minor amounts of other benzyl and benzoate esters in tissue slices of ripe cranberry. Hydrolysis of the benzyl benzoate indicated that label was about equally distributed between benzoic acid and benzyl alcohol. [7-¹⁴C] benzaldehyde was converted in tissue slices into benzyl alcohol and benzyl benzoate, and hydrolysis of the ester indicated that only the alcohol moiety was labeled. Incubation of cranberry tissue slices with [7-¹⁴C] benzyl alcohol yielded primarily benzyl benzoate, and only the alcohol portion of the ester was labeled. All biosynthetic products were identified by radio chromatographic analysis and by preparation of derivatives, and the direct incorporation of precursors into biosynthetic products was demonstrated by chemical degradation studies. These results strongly suggest that, in the biosynthesis of benzyl benzoate, benzoic acid is first reduced to benzaldehyde, followed by reduction of the aldehyde to benzyl alcohol which is subsequently esterified. None of the aforementioned transformations of [¹⁴C] benzoic acid and its derivatives could be demonstrated in tissue slices from unripe (green) cranberry, suggesting that development of the ability to synthesize volatile benzenoid compounds is associated with ripening.     

Simultaneous analysis of glyphosate and glufosinate in vegetables and fruits by GC-FPD

A rapid analytical method for residues of the herbicide, glyphosate [N-(phosphonomethyl)glycine], glufosinate [DL-homoalanine-4-yl(methyl)phosphinic acid] and glufosinate metabolite (MPPA: 3-methylphosphinicopropionic acid) in vegetables and fruits was developed by improving the bulletin method of glufosinate. 50 mL of solution extracted with water (corresponding to 2 g of the sample) was loaded on a column packed with 5 mL of anion exchange resin and then the trapped glyphosate, glufosinate and MPPA were eluted with 60 mL of 50% acetic acid. After derivatization with trimethyl orthoacetate, the derivatives were purified and separated on a Florisil cartridge column. The determination of the derivatives was performed with GC-FPD. The detection limits for glyphosate, glufosinate and MPPA were 0.01 microgram/g, 0.01 microgram/g and 0.005 microgram/g, respectively. The recoveries from fortified samples were 83.5-89.8% for glyphosate, 77.9-92.2% for glufosinate and 75.0-87.2% for MPPA.     

Chemical activation of piperidine by formaldehyde and formation of lysine-specific Maillard reaction products

Piperidine is considered as a lysine-specific Maillard reaction product that can be formed from free lysine through decarboxylation and deamination reactions or through cyclization of pent-4-en-1-amine, the counterpart of acrylamide from lysine. Due to the importance and reactivity of piperidine its further interaction products in glucose/lysine model system was investigated. A useful strategy based on Py-GC/MS analysis was developed using an isotope labelling technique to identify reaction products incorporating piperidine moieties. Products simultaneously possessing five lysine carbon atoms (C2′–C6′) and the Nε-amino group from lysine in addition to glucose carbon atoms were targeted using specifically labelled precursors such as [¹⁵Nα]Lysine·2HCl, [¹⁵Nε]Lysine·2HCl, [U-¹³C₆]Lysine·2HCl, [¹³C-6]Lysine·2HCl and [U-¹³C₆]Glucose. Detailed labelling studies using specifically ¹³C-enriched sugars have shown that the piperidine can form reactive 1-methylidenepiperidinium ion with formaldehyde, which is able to undergo further aldol addition reactions to form compounds, such as 3-(piperidin-1-yl)propanal and 3-(pyridin-1(4H)-yl)propanal. Furthermore, these studies have also demonstrated that oxidation of piperidine into di- and tetrahydropyridine derivatives can generate reactive eneamine moieties capable of nucleophilic attack at carbonyl groups and formation of pyridine derivatives.     

UPLC-MS/MS法测定食品接触材料中的成核剂

建立了高效液相色谱-串联质谱法(UPLC-MS/MS)测定食品接触材料及制品中(1R,2R,3S,4S)-rel-二环[2.2.1]庚-2,3-二羧酸二钠盐迁移量的方法。样品中的(1R,2R,3S,4S)-rel-二环[2.2.1]庚-2,3-二羧酸二钠盐在一定温度、时间接触的状态下会迁移到食品模拟物中。以T3色谱柱进行分离,甲醇-5 mmol/L甲酸铵为流动相洗脱,采用电喷雾离子源(ESI),多反应监测(MRM)负离子模式进行扫描,测定迁移到食品模拟物中的目标物。结果表明,(1R,2R,3S,4S)-rel-二环[2.2.1]庚-2,3-二羧酸二钠盐的色谱分离良好,在5.00~100μg/L浓度范围内与其峰面积均呈线性关系。该方法对水基、酸性食品、酒精类食品模拟液和油基模拟物的定量限均为5.0μg/L,重复性试验的相对标准偏差为0.73%~1.5%(n=6),加标回收率为80.5%~103%。该方法快速可靠、准确简便,适用于食品接触材料及制品中(1R,2R,3S,4S)-rel-二环[2.2.1]庚-2,3-二羧酸二钠盐的检测。     

Absorption of N-phenylpropenoyl-L-amino acids in healthy humans by oral administration of cocoa (Theobroma cacao)

Besides flavan-3-ols, a family of N-phenylpropenoyl-L-amino acids (NPAs) has been recently identified as polyphenol/amino acid conjugates in the seeds of Theobroma cacao as well as in a variety of herbal drugs. Stimulated by reports on their biological activity, the purpose of this study was to investigate if these amides are absorbed by healthy volunteers after administration of a cocoa drink. For the first time, 12 NPAs were quantified in human urine by means of a stable isotope dilution analysis with LC-MS/MS (MRM) detection. A maximum amount was found in the urine taken 2 h after the cocoa consumption. The highest absolute amount of NPAs excreted with the urine was found for N-[4'-hydroxy-(E)-cinnamoyl]-L-aspartic acid (5), but the highest recovery rate (57.3 and 22.8%), that means the percentage amount of ingested amides excreted with the urine, were determined for N-[4'-hydroxy-(E)-cinnamoyl]-L-glutamic acid (6) and N-[4'-hydroxy-3'-methoxy-(E)-cinnamoyl]-L-tyrosine (13). In order to gain first insights into the NPA metabolism in vivo, urine samples were analyzed by LC-MS/MS before and after beta-glucuronidase/sulfatase treatment. As independent of the enzyme treatment the same NPA amounts were found in urine, there is strong evidence that these amides are metabolized neither via their O-glucuronides nor their O-sulfates. In order to screen for caffeic acid O-glucuronides as potential NPA metabolites, urine samples were screened by means of LC-MS/MS for caffeic acid 3-O-beta-D-glucuronide and 4-O-beta-D-glucuronide. But not even trace amounts of one of these glucuronides were detectable, thus excluding them as major NPA metabolites and underlining the importance of future investigations on a potential O-methylation or reduction of the N-phenylpropenoyl moiety in NPAs.