Synthesis and Biological Activity of Argiotoxin 636 and Analogues: Selective Antagonists for Ionotropic Glutamate Receptors

More discerning than the parent : Analogues of the polyamine toxin argiotoxin 636 (shown docked in the ion channel of an ionotropic glutamate (iGlu) receptor; N blue, O red) distinguish subtypes of iGlu receptors. Depending on which of the two internal amine groups is replaced with a methylene group, the analogue inhibits one or other of two receptor subtypes as potently as the natural compound, which itself inhibits both subtypes nonselectively.

     

An efficient and versatile synthesis of all structural types of acylpolyamine spider toxins

An efficient and versatile synthesis of acylpolyamine spider toxins of all structural types classified by extensive MS analysis has been achieved. By using 2-nitrobenzenesulfonamide as an effective activating and/or protecting group (the Nosyl strategy), the naturally occurring toxins 1-8 corresponding to Types A-F were concisely synthesized in high overall yield.     

石墨烯-管尖固相萃取-液相色谱-串联质谱法测定贝类中10种脂溶性贝类毒素

以石墨烯为吸附剂，制作了石墨烯-管尖固相萃取装置，结合液相色谱-串联质谱，建立了一种同时测定贝类中10种脂溶性贝类毒素的方法。实验对提取剂、石墨烯的用量、淋洗剂的种类和用量、洗脱剂的种类和用量等实验参数进行了详细优化。在最优的实验条件下，10种脂溶性贝类毒素在各自相应浓度范围内线性良好，相关系数均大于0.99，方法检出限（LOD）和定量限（LOQ）分别在0.1~1.1 μg/kg和0.3~3.2 μg/kg之间；对阴性牡蛎样品进行3个水平的加标回收实验，10种脂溶性贝类毒素的回收率在72.0%~101.2%之间，相对标准偏差小于15%。结果表明，该方法灵敏度高，操作简单高效，适用于贝类水产品中脂溶性贝类毒素的检测分析。     

Elucidation of the fragmentation pathways of azaspiracids, using electrospray ionisation, hydrogen/deuterium exchange, and multiple-stage mass spectrometry

Collision-induced dissociation (CID) mass spectra were generated for azaspiracids using electrospray ionisation (ESI), and hydrogen/deuterium (H/D) exchange was used to ascertain the number and type of replaceable hydrogens in the three predominant azaspiracid toxins. H/D exchange was conveniently achieved using deuterated solvents for liquid chromatography (LC). Using ion-trap mass spectrometry, multiple-stage CID experiments (MS(n)) on the protonated and fully exchanged ions were performed to decipher characteristic fragmentation pathways. The precursor and product ions from azaspiracids lost up to five water molecules from different regions during MS(n) experiments and it was possible to distinguish between the water losses from different molecular regions. These studies confirmed that the first water-loss ion in the spectra of azaspiracids resulted from dehydration at the vicinal diol at C20-C21. Five MS dissociation pathways were identified that resulted from fragmentation of the carbon skeleton of azaspiracids producing nitrogen-containing ions. Two pathways, involving cleavage of the E-ring and C27-C28, gave ions that were found in all azaspiracids. Three pathways, A-ring, C-ring and C19-C20 cleavages, were useful for distinguishing between azaspiracid analogues. The same product ions from backbone fragmentation were also observed using hybrid quadrupole time-of-flight mass spectrometry (QqTOFMS). The fragmentation of the A-ring was the most facile and was exploited in the development of LC/MS(n) methods for the analysis of azaspiracids.     

3种滩涂贝类对凡纳滨对虾养殖尾水净化效果的比较研究

以文蛤、缢蛏和泥蚶3种滩涂贝类为研究对象, 评估了3种滩涂贝类不同处理模式下的尾水处理效果. 在流水模式下比较不同贝类及密度对水质指标影响的结果表明 所有实验组均显著降低了水体总悬浮物; 泥蚶对氨氮和亚硝酸盐去除效果较好, 文蛤对弧菌有良好的去除效果. 静水模式下的结果表明 滩涂贝类对尾水处理效果与流水模式趋势相似, 静水模式下高密度(?m-2)贝类更能有效净化水质, 而适当降低贝类密度(?m-2)有利于去除养殖尾水中的弧菌总数. 静水模式下对水体菌群研究结果表明 高密度(?m-2)文蛤组和高密度(?m-2)缢蛏组水体菌群Chao1、可观测物种指数升高, 泥蚶组菌群丰度和多样性方面更趋于稳定.     

一种检测麻痹性贝毒的高效液相色谱法

提出了一种利用高效液相色谱法同时分析麻痹性贝毒GTX组分和NEO/dcSTX/STX组分的方法。本法仅使用了一种缓冲溶液作为流动相,在InertsilC8-3色谱柱(250mm×4.6mm,5μm)上,采用梯度改变乙腈在流动相中的比例和流速,一次进样可同时定性及定量待测试样中的上述全部毒素组分。该缓冲溶液为9.0mmol/L磷酸铵缓冲溶液(pH=7.2),含有2.8mmol/L的庚烷磺酸钠。色谱分离过程首先以纯水相缓冲溶液进行等度洗脱,在16.5~19min向流动相中梯度加入1.5%的乙腈,加速GTX3和GCX2的洗脱,以避免GTX2的色谱峰与乙腈的溶剂峰重叠,随后从19min开始加大流动相中乙腈的比例为8.5%,以缩短边缘组分的保留时间。荧光检测器的激发波长和发射波长分别设为330nm和390nm。用本方法分析染毒的华贵栉孔扇贝和近江牡蛎,证实了本方法对PSP毒素具有良好的分析测定效果。     

液相色谱-串联质谱检测贝类组织中5种脂溶性贝毒素

建立了液相色谱-串联质谱分析贝类组织中米氏裸甲藻(GYM)贝毒素、螺环内酯毒素(SPX1)、大田软骨酸(OA)贝毒素、蛤毒素(PTX2)、原多甲藻酸(AZA1)贝毒素的方法.用甲醇-水(4: 1, V/V)溶液对贝类组织中GYM, SPX1, OA, PTX2和AZA1进行提取,MAX阴离子交换柱净化后,采用液相色谱分离,除OA以负离子选择反应监测外,GYM, SPX1, PTX2和AZA1以电喷雾离子源正离子选择反应监测模式进行质谱分析.5种脂溶性贝毒素GYM, SPX1, OA, PTX2和AZA1在各自相应浓度范围内线性良好,相关系数＞0.99.扇贝闭壳肌空白样品添加5种贝毒素的提取率均为78.6%～94.4%(n=6); 精密度(RSD)为6.8%～14.9%.贝类组织中5种贝毒素GYM, SPX1, OA, PTX2和AZA1的检出限分别为0.10, 0.21, 2.00, 0.32和0.04 μg/kg.     

高效液相色谱-串联质谱法同时测定贝类中22种农药残留

建立了高效液相色谱-三重四极杆质谱（HPLC-MS/MS）同时测定贝类中22种农药残留的分析方法。样品经含0.1%（v/v）甲酸的乙腈提取，N-丙基乙二胺（PSA）和石墨化碳黑（GCB）净化，然后采用ACE UltraCore 2.5 SuperC18柱（100 mm×2.1 mm，2.5 μm）分离，以甲醇-0.1%（v/v）甲酸水溶液为流动相梯度洗脱，流速为0.4 mL/min，柱温为35 ℃，然后以电喷雾电离（ESI）源，在多反应监测（MRM）、正离子模式下，采用三重四极杆质谱检测。22种农药在各自的线性范围内线性关系良好，相关系数均大于0.997，检出限为0.1~0.3 μg/kg，定量限为0.3~1.0 μg/kg。在3个添加水平下，22种农药的平均回收率为65.2%~109.4%，相对标准偏差为1.3%~15.2%（n=6）。该方法操作简单，快速，准确度高，灵敏度高，可用于贝类中22种农药残留的同时检测。     

改性竹炭脱除贝类酶解液中的重金属镉

以蚶子贝肉酶解液为材料,利用聚天冬氨酸(PAsp)改性的竹炭吸附脱除酶解液中的重金属镉。考察了pH、脱除时间、竹炭投加量和温度对酶解液中镉脱除率的影响,并在单因素试验基础上通过响应面法确定了镉的最佳脱除条件。当pH为5.0、反应时间为25min、竹炭投加量(10m L酶解液)为0.26g,重金属镉的脱除率可达96.59%。研究表明,PAsp改性竹炭能显著提高吸附重金属的效率和能力,可用于脱除蚶子贝肉酶解液中的镉。     

A new lipophilic monosaccharide from Erigeron annggs

A new lipophilic monosaccharide,erigearide A(1),was isolated from the aerial parts of Erigeron annuus(Lima.)Pers.Its structure was elucidated by analysis of spectroscopic evidence.