蒸馏法-液液萃取-气相色谱-串联质谱法测定葡萄酒中挥发性酚类物质的含量北大核心CSCD

提出了蒸馏法-液液萃取-气相色谱-串联质谱法(GC-MS/MS)测定葡萄酒中挥发性酚类物质含量的方法。取100 mL葡萄酒样品(液温20℃)于500 mL蒸馏瓶中,连接冷凝管进行蒸馏,收集馏出液100 mL。取馏出液20 mL于50 mL离心管中,加入20μL内标溶液(25.0 mg·L^(-1)3,4-二甲基苯酚的乙醇溶液),涡旋振荡5 min,混匀。加入氯化钠使之饱和(氯化钠质量浓度为360 g·L^(-1)),用10 mL二氯甲烷进行萃取(5 mL/次×2次),每次萃取振荡5 min,超声10 min,离心5 min。合并的有机相用3.0 g无水硫酸钠除水后,于35℃氮吹至1 mL。采用GC-MS/MS测定所得溶液中14种挥发性酚类物质的含量。结果表明,14种挥发性酚类物质的质量浓度与内标质量浓度的比值在一定范围内跟对应的峰面积比值呈线性关系,检出限(3S/N)为0.5~9.2μg·L^(-1)。按照标准加入法进行回收试验,回收率为87.3%~107%,测定值的相对标准偏差(n=6)为0.70%~5.6%。     

微溶剂萃取-气相色谱-质谱法测定水中邻苯二甲酸二(2-乙基己基)酯

取水样25mL,加入无水硫酸钠3.0g,加入环己烷2.0mL,振荡萃取3min。移取萃取了邻苯二甲酸二(2-乙基己基)酯(DEHP)的上层有机相2.0μL注入HP-5毛细管柱(30m×0.32mm,0.25μm)色谱分离后进行质谱测定。DEHP的质量浓度在50.0μg.L-1以内与其峰面积呈线性关系,方法的检出限(3S/N)为0.052μg.L-1。分析了早、中、晚不同时间的天津市自来水,并用标准加入法做回收试验,测得回收率在97.0%～109.4%之间,测定值的相对标准偏差(n=6)均小于2.5%。     

固相萃取-毛细管气相色谱法测定中草药及其土壤中多种有机氯农药残留量

建立了中草药及其土壤中多种有机氯农药残留量的固相萃取-毛细管气相色谱(SPE-CGC)分析方法,并对7种中草药及其土壤中多种有机氯农药残留量的相关性进行了初步研究。样品以正己烷-丙酮用超声波提取,Florisil(1 g)固相萃取小柱快速净化提取物。采用SPB-5弹性石英毛细管柱分离样品,GC-ECD检测7种中草药及其土壤中的13种有机氯农药的残留量。方法的线性范围为1.26×10-10~2.24×10-7g/mL;检出限为6.4×10-11~6.1×10-10g/mL;加样平均回收率为87.3%~104.4%(RSD为1.1%~7.0%)。     

聚乙二醇双水相萃取光度法测定铬(Ⅵ)

通过研究二苯碳酰二肼(DPC)-铬(Ⅵ)配合物在聚乙二醇(PEG)2000-Na2SO4双水相中的显色和萃取分离条件,建立了集萃取分离和测定Cr6+于一身的双水相萃取光度分析方法。对双水相体系中PEG溶液、Na2SO4和二苯碳酰二肼的用量以及溶液酸度进行了优化,探讨了共存离子对Cr6+萃取测定的影响。实验表明,在0.16mol/L的H3PO4溶液中,二苯碳酰二肼与Cr6+形成的配合物被萃取到PEG相,最大吸收波长为545nm,表观摩尔吸光系数为4.3×104L.mol-1.cm-1。Cr6+的质量浓度在0.05～13.0μg/mL的范围内符合比尔定律,最低检出限为0.029μg/mL,5μg/mL标准溶液的相对标准偏差为1.3%。本方法用于测定含铬工业废水中的Cr6+,结果与原子吸收光谱法测定值相符,不同水平的回收率为96.7%～99.8%。     

固相微萃取-气相色谱-质谱法测定血中痕量毒鼠强

血样中的毒鼠强用固相微萃取法分离.取2 mL血样加水稀释至15 mL,插入聚丙烯酸酯萃取纤维头30 min,取出萃取头用水洗提2～3次后,在仪器的前进样口加热除去残留的水分,然后将萃取头插入仪器的进样口进行热解吸,并测定其含量.此方法的检出限(3S/N)为1.1 μg·L-1.在毒鼠强质量浓度为100μg·L-1的水平上测定了方法的相对标准偏差(n=6)为4.03%.     

牛大力总黄酮提取工艺及不同萃取物的抗氧化活性研究

为了考察牛大力乙醇提取物中总黄酮的含量及抗氧化活性。通过L16(45)正交实验,超声波辅助提取牛大力中总黄酮,得到最佳工艺,再测试乙醇提取物和四个萃取物对羟基自由基(.OH)和DPPH自由基(DP-PH.)的清除效果。最佳工艺为:φ(EtOH)=75%、m(牛大力,g)∶V(EtOH,mL)=1∶25、温度60℃、时间60min,该条件下,牛大力总黄酮得率可达2.14mg.g-1。其中,牛大力乙醇提取物中氯仿萃取物中黄酮含量最高,为5.52mg.g-1;而且氯仿萃取物对DPPH.的清除效果最好,其半数抑制浓度(IC50)为40.97μg.mL-1;乙酸乙酯萃取物对羟基自由基的清除效果最好,其IC50值为90.5μg.mL-1。牛大力乙醇提取物中石油醚、氯仿、乙酸乙酯萃取物都有很好的抗氧化活性,且稳定性、重复性好。     

亚甲蓝和天青A与AuCl-4离子缔合物的溶剂萃取导数-同步荧光光度法同时测定

在酸性介质中,亚甲蓝(MB)和天青A(AA)与AuCl-4形成离子缔合物,被1,2-二氯乙烷萃取后,以Δλ=20 nm进行同步荧光扫描并采用一阶导数处理,2个缔合物分别在683和608 nm附近出现峰值并能很好分开,且荧光强度分别与MB或AA浓度呈良好的线性关系,可用于2种吩噻嗪衍生物亚甲蓝和天青A的同时测定,检出限分别为7.9×10-9和1.78×10-8 g/mL,其线性范围分别为3.0×10-8～4.8×10-6和6.0×10-8～5.8×10-6 g/mL. 研究了离子缔合物的组成和光谱特征,适宜的反应条件及影响因素. 用于尿样和azureⅡ中亚甲蓝和天青A的同时测定,结果令人满意.     

固相微萃取-气相色谱法测定鱼肉中五氯酚

经匀浆的鱼肉样品置于20 mL顶空瓶中,加入氯化钠3.0 g,水1 mL及pH 2.0硫酸溶液9 mL,于40℃超声萃取30 min。将顶空瓶放入带固相微萃取装置的Combi PAL全自动进样器中,于90℃温度下加热20 min后,用85μm聚丙烯酸酯萃取头固相微萃取10 min,于280℃热解3 min,用HP-5毛细管柱分离后,用气相色谱法(电子捕获检测器)测定五氯酚的含量。五氯酚的线性范围在0.05~100μg.L-1之间,方法的检出限(3S/N)为0.02μg.L-1。在3个浓度水平(1.0,5.0,50.0μg.kg-1)上对方法的回收率进行试验,测得回收率在81.2%~89.4%之间,测定值的相对标准偏差(n=6)在4.2%~7.1%之间。     

固相萃取-分散液液微萃取-柱前衍生法测定水样中痕量雌激素

建立了碳纳米管的固相萃取-分散液液微萃取-柱前荧光衍生化(SPE-DLLME-PFD)测定水体中痕量雌三醇(E3)、双酚A(BPA)、17α-乙炔基雌二醇(EE2)及17β-雌二醇(E2)的高效液相色谱方法.采用中心复合设计和响应曲面法分析并优化SPE、DLLME及PLD条件,最佳条件为210 mL水样以2.0 mL/min的流速过固相萃取柱(碳纳米管量30 mg),甲醇洗脱,氮气浓缩并定容至0.6 mL(分散剂),将100 μL C6MIM[PF6]与分散剂的混合液注入到NaCl含量为25％的2.0 mL去离子水中,离心,移取20 μL下层有机相于样品瓶中,与4.0 mg衍生剂混合,在40℃水浴中衍生25 min;用0.1mL甲醇溶解过量的衍生剂颗粒,取20 μL进样分析.在优化条件下.4种雌激素的线性范围为0.05～5.00 μg/L,相关系数R2=0.9966～0.9999;,检出限介于0.13～6.33 ng/L(S/N=3)之间.不同加标浓度条件下,雌激素的加标回收率在83.1％～122.4％范围内(RSD=1.7％～9.6％).在实际水样中E3和BPA检出率较高.与其它方法相比,本方法虽然萃取时间长、水样量大、步骤多,但具有检出限低、操作简便、环境友好等优点.     

气相色谱-串联质谱法测定动物性食品中的9种N-亚硝胺类化合物

称取样品10.00g,加入100μL由N-二甲基亚硝胺-d6和N-亚硝基二丙胺-d14组成的混合内标溶液(1.00mg·L~(-1)),加入20mL乙腈,涡旋1min,于-20℃冷冻20min,再加入萃取盐(4g硫酸镁、1g氯化钠),迅速振荡30s,以8 000r·min~(-1)在0℃离心10min,取上清液加入10mL乙腈饱和的正己烷,涡旋1min,以6 000r·min~(-1)在0℃离心3min,去除正己烷层,加入净化填料(50mg N-丙基乙二胺、150mg封端十六烷基键合硅胶、900mg Na2SO_4),涡旋1min,以8 000r·min~(-1)在0℃离心5min,取上清液用氮吹浓缩(不吹干),用乙腈定容至1.0mL,采用气相色谱-串联质谱法测定其中的9种N-亚硝胺类化合物。色谱分析中选用VF-WAXms色谱柱(0.25mm×30m,0.25μm),质谱中选择电子轰击离子源和多反应监测模式。9种N-亚硝胺类化合物的质量浓度在5.0～150μg·L~(-1)内与其峰面积呈线性关系,检出限为0.1μg·kg~(-1),测定下限为0.5μg·kg~(-1)。加标回收率在89.0%～117%之间,测定值的相对标准偏差(n=6)在0.6%～8.0%之间。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Microwave-assisted copper-catalyzed stereoselective ring expansion of three-membered heterocycles with α-diazo-β-dicarbonyl compounds

Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular S_N2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.