TR-ESR Investigation on Reaction of Vitamin C with Excited Triplet of 9,10-phenanthrenequinone in Reversed Micelle Solutions

Time-resolved electron spin resonance has been used to study quenching reactions between the antioxidant Vitamin C （VC） and the triplet excited states of 9,10-phenanthrenequinone （PAQ） in ethylene glycol-water （EG-H2O） homogeneous and inhomogeneous reversed micelle solutions. Reversed micelle solutions were used to be the models of physiological environment of biological cell and tissue. In PAQ/EG-H2O homogeneous solution, the excited triplet of PAQ （3PAQ＊） abstracts hydrogen atom from solvent EG. In PAQ/VC/EG-H2O solution, 3pAQ＊ abstracts hydrogen atom not only from solvent EG but also from VC. The quenching rate constant of 3pAQ＊ by VC is close to the diffusion-controlled value of 1.41 × 108 L/（mol.s）. In hexadecyltrimethylammonium bromide （CTAB）/EG-H2O and aerosol OT （AOT）/EG- H2O reversed micelle solutions, 3pAQ＊ and VC react around the water-oil interface of the reversed micelle. Exit of 3pAQ＊ from the lipid phase slows down the quenching reaction. For Triton X-100 （TX-100）/EG-H2O reversed micelle solution, PAQ and VC coexist inside the hydrophilic polyethylene glycol core, and the quenching rate constant of 3pAQ＊ by VC is larger than those in AOT/EG-H2O and CTAB/EG-H2O reversed micelle solutions, even a little larger than that in EG-H2O homogeneous solution. The strong emissive chemically induced dynamic electron polarization of As＇- resulted from the effective TM spin polarization transfer in hydrogen abstraction of 3pAQ＊ from VC.

Molecular Properties of 9,10-Phenanthrenequinone and Benzil

9,10-Phenanthrenequinone（PQ） and benzil are important a-diketones. This manuscript explains the first comparison of PQ and benzil molecular properties. We have used 1H NMR, 13C NMR, 1H-IH COSY, HMBC, HMQC, UV-Vis absorption and emission, CV and TGA experiments to study PQ and benzil that provided the following novel results. （1） The 1H NMR（CDC13） of PQ show δ 8.19（H1）, 8.02（H4）, 7.72（H3）, 7.47（H2） instead of an earlier reported 8.25（H4）, 8.08（H1）, 7.80（H2）, 7.55（H3）; （2） in the 13C NMR（CDCl3）, the C9/C10（C=O） signal of PQ appears upfield（6 180.3） compared to C9/Cl0（C=O） signal of benzil（6 194.5）, which shows higher electrophilic character（more attractive for nucleophiles） of C9/C10（C=O） of benzil; （3） the first 2max for the UV-Vis absorption and emission of PQ are blue-shifted compared to benzil despite increased conjugation attributed to the different symmetries（C2v for PQ and C2h for Benzil） of the two molecules; （4） the emission spectrum of benzil is broader compared to that of PQ due to slower relaxation of the excited state; （5） The CV study shows that PQ and benzil are good electron acceptors and PQ shows a better reduction process than benzil due to an extra ring that provides stability for the reduced species（mono or diradical anions）; （6） TGA shows the higher thermal stability of PQ than benzil attributed to the presence of phenanthrene unit in PQ.

基于9,10-二氢蒽强化的掺氮活性炭催化松木热解制备烷氧基酚研究

本研究以核桃壳基掺氮活性炭(NAC)为催化剂、以9,10-二氢蒽(DHA)为供氢剂,开展了松木选择性热解制备烷氧基酚研究,探究了氨水质量分数对NAC理化性能的影响,揭示了DHA/松木比、热解温度、NAC/松木比对烷氧基酚生成的调控机制。结果表明,合适的氨水质量分数能够改善NAC孔隙结构及活性位点分布,当氨水质量分数为15%时,所制备NAC对烷氧基酚的生成促进效果最佳;当DHA/松木比为1、热解温度为550℃、NAC/松木比为3时,烷氧基酚产率最大,为5.27%,明显高于纯松木直接催化热解时烷氧基酚产率(1.74%)。

A novel surfactant N-hydroxy-9,10-epoxy group-octadecanamide:Part II.Its synthesis and application in flotation separation of spodumene and albite

A novel hydroxamic acid,N-hydroxy-9,10-epoxy group-octadecanamide(N-OH-9,10-O-ODA),was synthesised by modifying the structure of oleic acid.The carboxyl group of oleic acid was converted into an N-hydroxy amide group,and an epoxy group was introduced into its structure.N-OH-9,10-O-ODA was used as a novel collector in the flotation separation of spodumene from one of its associated gangue minerals,specifically albite.N-OH-9,10-O-ODA exhibits remarkable selectivity,with a stronger affinity for collecting spodumene particles compared to albite particles.Zeta potential measurements and X-ray photoelectron spectroscopic analysis reveal that the adsorption quantity of N-OH-9,10-O-ODA on spodumene surface is comparable to that on albite surface.First-principles calculations demonstrate the diverse adsorption configurations of N-OH-9,10-O-ODA on surfaces of spodumene and albite,leading to its distinct collecting abilities for spodumene and albite particles.

土壤中9-芴酮和9,10-蒽醌的分析方法及赋存形态

为探究含氧多环芳烃(oxygenated polycyclic aromatic hydrocarbon,OPAHs)在土壤中的赋存形态特征,以9-芴酮和9,10-蒽醌为OPAHs模式物,建立了其在不同基质中的提取及测定方法,分析了其在土壤中30 d内的赋存形态。结果表明:以甲醇-二氯甲烷(1∶1,V/V)溶液为萃取剂,采用超声-高效液相色谱法提取测定土壤中的9-芴酮和9,10-蒽醌,回收率为102.4%~104.2%。以二氯甲烷为萃取剂,通过液液萃取-高效液相色谱法测定水相及生物有效态相(羟丙基-β-环糊精)中的9-芴酮和9,10-蒽醌,回收率分别为87.2%~87.8%和78.7%~86.3%。采用连续提取方法,研究了这2种OPAHs在土壤中30 d内的形态分布,各形态9-芴酮和9,10-蒽醌含量之和的顺序为难解吸态>粗胡敏素结合态>干酪根结合态>生物有效态>胡敏酸结合态>富里酸结合态>矿物结合态。可提取态(生物有效态与难解吸态加和)为主要存在形态(58.0%),结合态亦占有相当大的比例(42.0%),有机质结合态较矿物结合态含量占比更高。土壤中9-芴酮和9,10-蒽醌在前15 d生物有效性降低较快,后15 d趋缓,9-芴酮较9,10-蒽醌生物有效性下降更快。

N-9,10-蒽醌-2-甲酰基苯丙氨酸治疗大鼠痛风性关节炎的作用及机制

目的探究N-9,10-蒽醌-2-甲酰基苯丙氨酸(NAY)对尿酸钠(MSU)所致痛风性关节炎(GA)大鼠的作用及机制。方法将雄性SD大鼠随机分为7组,每组8只,即正常组、模型组、NAY低(20 mg·kg^(-1))、中(40 mg·kg^(-1))、高剂量组(80 mg·kg^(-1))、秋水仙碱组(0.8 mg·kg^(-1))和别嘌呤醇组(10 mg·kg^(-1)),通过关节腔内注射MSU晶体建立大鼠急性GA模型,各组灌胃给药5 d,给药第3天造模。将原代培养的大鼠腹部巨噬细胞分成空白组、模型组、NAY组、MCC950组和联合给药组。软尺测量大鼠踝关节周长并计算大鼠关节肿胀度;检测大鼠血清尿酸(UA)、肌酐(CRE)和尿素氮(BUN)含量;HE染色观察大鼠踝关节滑膜组织病理切片;检测各组血清、关节滑膜和细胞上清液中肿瘤坏死因子-α(TNF-α)和白介素-1β(IL-1β)的含量;并检测各组关节滑膜和细胞中NOD样受体热蛋白结构域相关蛋白3(NLRP3)、凋亡相关斑点样蛋白(ASC)和半胱氨酸天冬氨酸蛋白酶-1(caspase-1)的蛋白表达。结果动物实验发现,与模型组相比,NAY给药组在造模12、24和48 h均可不同程度改善GA大鼠踝关节肿胀度,且NAY各个剂量组均显著降低GA大鼠血清UA、CRE和BUN水平,同时显著降低GA大鼠血清中TNF-α和IL-1β水平及GA大鼠关节滑膜中炎症因子TNF-α和IL-1β水平,而NAY能显著降低GA大鼠关节滑膜中NLRP3、ASC和caspase-1的蛋白表达,HE染色结果显示NAY可减轻GA模型大鼠踝关节滑膜组织炎性细胞浸润,改善细胞形态。细胞实验发现,NAY、MCC950和联合给药组均可显著提高MSU诱导大鼠巨噬细胞活力,降低上清液TNF-α和IL-1β的含量,并显著降低模型组NLRP3、ASC和caspase-1蛋白表达,但是联合给药组与MCC950组相比,上述指标没有显著性差异。结论NAY可在体内和体外有效预防MSU晶体诱导的GA,机制可能与其降尿酸和抑制NLRP3炎症小体表达有关。

连续流反应器中油酸无溶剂合成9,10-二羟基硬脂酸

为改善现有9,10-二羟基硬脂酸合成存在的反应不连续、反应时间过长等问题,以油酸为原料,过氧化氢为氧化剂,在连续流反应器中合成9,10-二羟基硬脂酸,对催化剂进行了筛选,并对合成工艺条件进行单因素实验优化。结果表明,9,10-二羟基硬脂酸,合成的最佳工艺条件为以磷钨酸为催化剂、不使用溶剂、30%过氧化氢与油酸物质的量比3∶1、反应温度60℃、催化剂用量10%(以油酸质量计)、反应时间23.6 min,在此条件下油酸转化率为91.2%,9,10-二羟基硬脂酸选择性为82.6%。该方法解决了传统间歇釜式反应器中制备9,10-二羟基硬脂酸时反应时间长、工艺烦琐等问题,且绿色环保。

9,10-位不对称取代蒽类蓝光材料的合成工艺

以1/2-萘硼酸与9,10-二溴萘为初始原料,利用Suzuki反应合成了蓝色发光材料9-(2-萘基)-10-[4-(1-萘基)苯基]蒽,采用^(1)H NMR进行了定性分析,考察了关键工艺参数对两步核心反应的影响规律。结果表明:采用Pd(PPh_(3))_(4)为催化剂、2-萘硼酸与9,10-二溴蒽摩尔比为1.15∶1时,9-溴-10-(2-萘基)蒽合成收率可达70%;以Pd-132为催化剂、甲苯/水体系反应时,终端材料9-(2-萘基)-10-[4-(1-萘基)苯基]蒽的收率达89%。

腌腊肉制品中13-HODE、9,10-DHODE、9,10-EPODE、9,10,13-THODE的HPLC-MS/MS检测

采用高效液相色谱-串联质谱法对腌腊肉制品中13-羟基-9,11-十八碳二烯酸（13-hydroxy-9,11-octadecadienoic acid,13-HODE）、9,10-二羟基-12-十八碳烯酸（9,10-dihydroxy-12-octadecenoic acid,9,10-DHODE）、9,10-环氧-12-十八碳烯酸（9,10-epoxyoctadec-12-enoic acid,9,10-EPODE）及9,10,13-三羟基-11-十八碳烯酸（9,10,13-trihydroxy-11-octadecenoic acid,9,10,13-THODE）进行检测。腌腊肉制品中13-HODE、9,10-DHODE、9,10-EPODE、9,10,13-THODE用甲醇提取,经固相萃取柱去净化浓缩,然后以0.1%甲酸与乙腈为流动相,在XBridge色谱柱上进行梯度分离,采用电喷雾源负离子多反应监测模式进行分析。结果表明,13-HODE、9,10-DHODE、9,10-EPODE、9,10,13-THODE分别在质量浓度为0.05-2.0、0.01-0.5、0.05-1.0、0.01-0.5μg/mL的范围内具有较好的线性关系（R2〉0.999）;检出限分别为0.120、0.008、0.200、0.016μg/g;不同添加水平的平均回收率分别为95.1%、85.2%、86.8%、86.2%。对26种腌腊肉制品含量分析表明,所有样本都含有13-HODE、9,10-DHODE、9,10,13-THODE,含量分别在1.4-100.7、0.1-3.9、0.4-10.2μg/g范围内,21种样本中含有9,10-EPODE,含量范围为0.8-6.9μg/g。结果表明,腌腊肉制品中存在目标分析物的异构体,羟基脂肪酸实际含量可能大大高于检测的量。

4种9,10-二氢菲类化合物的体外抗肿瘤活性及机制

目的研究4种9,10-二氢菲类化合物对4种人癌细胞的增殖抑制作用及其作用机制。方法采用MTT法测定它们对人肝癌细胞株HepG2,人非小细胞肺癌细胞株NCI-H460,人乳腺癌细胞株MCF-7,人神经胶质瘤细胞株SF-268的增殖抑制作用;采用流式细胞仪技术和蛋白质电泳技术检测它们对HepG2细胞的细胞周期以及细胞周期蛋白表达的影响。结果9,10-二氢菲类化合物对HepG2细胞的增殖有一定的抑制作用;其中4,5-二羟基-2-甲氧基-9,10-二氢菲可能通过下调周期蛋白CyclinB1的表达将HepG2细胞阻滞在G2/M期。结论9,10-二氢菲类化合物通过将HepG2细胞阻滞在G2/M期从而对其增殖产生了一定的抑制作用。

Highly Sensitive and Selective Amperometric Sensor for Iodate Based on 9,10-Phenanthrenequinone Derived Graphene

We reported on a new amperometric sensor for the sensitive and selective determination of iodate in table salt. The iodate sensor was constructed by the integration of a novel nanocomposite which was made from 9,10-phenanthrenequinone（PQ） and graphene（GP） with a glassy carbon electrode（GCE）. The synthesized graphene and the nanocomposite were well characterized by X-ray diffraction（XRD）, transmission electron microscopy（TEM）, Fourier transform infrared（FTIR） spectroscopy and Raman spectroscopy. We fully studied the electrochemical beha- vior and kinetic characteristics of the PQ/GP nanocomposite at GCE. The PQ/GP electrode shows a good electrochemical catalytic activity towards the reduction of iodate, which makes itself a sensitive and selective electrochemical sensor for iodate. The iodate sensor displays a high sensitivity（1.04 p.A.tamol.L-1）, a low detection limit（1.0X 10-8 mol/L）, a rapid response（less than 2 s）, and a broad linear range（from 5.0X 10-8 mol/L to 6.0X 10-3 mol/L ）. In addition, the sensor is interference free. The practical application of the proposed sensor was tested by the detection of iodate in table salt.

10-(异丙基-2-醇)-9,10-二氢-9-氧杂-10-膦杂菲-10-氧化物的合成

以9,10-二氢-9-氧杂-10-膦杂菲-10-氧化物(DOPO)和丙酮为原料,合成10-(异丙基-2-醇)-9,10-二氢-9-氧杂-10-膦杂菲-10-氧化物。考察了原料摩尔比、反应温度和反应时间对产物收率的影响。结果表明,较优工艺条件为:n(丙酮)∶n(DOPO)=12∶1,反应温度为50℃,反应时间为30 min时,DOPO的转化率为99%,目标产物收率为90%。

miR-493-5p在反式-7,8-二羟-9,10-环氧苯并芘诱导恶变细胞中的功能研究

目的:探讨在反式-7,8-二羟-9,10-环氧苯并芘(anti-BPDE)诱导转化的人支气管上皮细胞(16HBE-T)中低表达的mir-493-5p在化学致癌物致癌过程中的作用。方法:运用实时荧光定量PCR(qRT-PCR)验证miR-493-5p成熟体在16HBE-T和非转化对照细胞(16HBE-N)的表达水平。瞬时转染miRNA的模拟物,改变16HBE-T中miR-493-5p的表达,检测转染后16HBE-T细胞的增殖能力。结果:16HBE-N细胞中mir-493-5p的表达水平是16HBE-T的0.28倍,在16HBE-T组过表达mir-493-5p后实验组细胞增殖能力下降。结论:mir-493-5p表达水平的改变对细胞的增殖能力有影响,在anti-BPDE恶性转化细胞中低表达的mir-493-5p可能发挥着类抑癌基因的作用。

蓝光材料9，10-二(β-萘基)蒽的合成与光谱分析

采用还原β-萘基锂与蒽醌的加成物制备了有机电致蓝光材料9,10-二(β-萘基)蒽(ADN)。通过红外、核磁共振对其结构进行了表征。利用紫外可见吸收光谱、循环伏安法和荧光光谱等研究了其HOMO、LUMO能级及发光性能。紫外可见吸收光谱有2个吸收带,其中E带有2个吸收峰,波长分别为232nm、260nm;B带有3个吸收峰,其波长分别为359nm、377nm、398nm,ADN的吸收带边为420nm,计算其能级差为2.95eV。采用398nm的激发光激发,荧光发射峰值波长为426nm,半峰宽为56nm,有很好的蓝光色纯度。通过循环伏安法测得其氧化峰电位为1.28 V,推算出ADN的HOMO能级为5.60 eV,LUMO能级为2.65 eV。

Two New Organic Supramolecular Complexes Based on 2,3,6,7-Tetrahydroxyl-9,10-dimethyl-9,10-dihydro-9,10-ethanoanthracene and 4,4′-Bipyridine or 4,4′-Bipyridinylethane

Two new organic supramolecular cocrystal complexes C18H18O4·C10H8N2（I） and C18H18O4·C12H10N2（II）（C18H18O4 = 2,3,6,7-tetrahydroxyl-9,10-dimethyl-9,10-dihydro-9,10-ethanoanthracene（LH4）, C10H8N2 = 4,4＇-bipyridine（bpy） and C12H10N2 = 4,4＇-bipyridinylethane（bpe）） have been obtained by mixing LH4 with corresponding bpy or bpe ligand. The two complexes have been determined by X-ray crystal structure analysis, elemental analysis and IR analysis. Compound I crystallizes in the orthorhombic Pnma with a = 9.7078（4）, b = 22.4974（10）, c = 20.6272（9） V = 4505.0（3）3, Mr = 454.51, Dc. = 1.340 g·cm^-3, μ = 0.09 mm-1, F（000） = 1920, Z = 8, R = 0.0503 and wR = 0.1360. Compound II crystallizes in monoclinic C2/c with a = 29.944（6）, b = 9.820（2）, c = 22.643（5） , V = 5048.4（18）3, Mr = 480.54, Dc. = 1.265 g cm^–3, μ = 0.084 mm^–1, F（000） = 2032, Z = 8, R = 0.0548 and wR = 0.1600. X-ray single-crystal structure analysis shows that two-dimensional（2D） layer supramolecular structures are formed through hydrogen bonds and π-π interactions in the two complexes. IR analysis also indicates that there are only associated hydroxyl groups in the two complexes.

反式-9,10-二氢-9,10-二(1-萘基)-9,10-菲二醇的包合现象与晶体结构

按文献方法合成了一个螯形主体分子 ,反式 9,10 二氢 9,10 二 (1 萘基 ) 9,10 菲二醇。研究发现该主体可以和一些含氮杂环化合物形成一定比例的晶体包合物。用X 射线衍射分析二环己胺包合物的晶体结构表明 ,包合物中主客体之间存在OH…N氢键相互作用 ,客体分子包合在主体分子形成的空腔中。

晶体包合物反式-9,10-二氢-9,10-二(1-萘基)-9,10-菲二醇·二环己胺的结构研究

制得了晶体包合物反式_9,10_二氢_9,10_二 (1_萘基 )_9,10_菲二醇·二环己胺 ,通过熔点测定 ,IR ,粉末XRD对其进行了表征 ,用1 HNMR测定其分子摩尔比为 1∶2 ,X_射线衍射结果表明晶体属于正交晶系 ,空间群为Pnca,晶胞参数 :a =1 6 714(3) ,b=1 6 875 ,c=1 72 2 4(3)nm ,V =4 85 80 (15 )nm3 ,Z =8。

反式-9,10-二氢-9,10-二对甲苯基-9,10-菲二醇包结性能的研究

合成了主体分子反式 9,1 0 二氢 9,1 0 二对甲苯基 9,1 0 菲二醇 (1 ) ,它可以和苯、喹啉形成晶体包结物 ,通过m p 、IR、粉末XRD对它们进行了表征 ,通过1HNMR积分计算包结物主客体物质的量比分别为 :n1∶n苯 =3∶2 ;n1∶n喹啉 =1∶1。

9,10-二(苯亚甲基-硫亚甲基)蒽的合成及其对Cu^(2+)的识别

In this paper,9,10-bis（benzenemethylene-sulfurmethylene）anthracene derived from the starting material anthracene was synthesized and characterized by IR,1H NMR.The result of molecular recogntion test showed that this host molecule had strong complexation to Cu2+.The mechanism of recognition was discussed.

9,10-二氢菲-9,10-二醇衍生的新型手性配体的设计、制备和应用(英文)

报道了一系列衍生自 9,10 二氢菲 9,10 二醇的新型手性配体设计。