Radiofluorinated Pyrimidine‐2,4,6‐triones as Molecular Probes for Noninvasive MMP‐Targeted Imaging

Matrix metalloproteinases (MMPs) are zinc‐ and calcium‐dependent endopeptidases. Representing a subfamily of the metzincin superfamily, MMPs are involved in the proteolytic degradation of components of the extracellular matrix. Unregulated MMP expression, MMP dysregulation and locally increased MMP activity are common features of various diseases, such as cancer, atherosclerosis, stroke, arthritis, and others. Therefore, activated MMPs are suitable biological targets for the specific visualization of such pathologies, in particular by using radiolabeled MMP inhibitors (MMPIs). The aim of this work was to develop a radiofluorinated molecular probe for noninvasive in vivo imaging for the detection of up‐regulated levels of activated MMPs in the living organism. Fluorinated MMPIs ( 26 , 31 and 38 ) based on the pyrimidine‐2,4,6‐trione lead structure RO 28‐2653 ( 1 ) were synthesized, and their MMP inhibition potency was evaluated in vitro. The radiosynthesis and the in vivo biodistribution of the first ¹⁸F‐labeled prototype, MMP‐targeted tracer [¹⁸F] 26 , suitable for molecular imaging by means of positron emission tomography (PET) were realized.     

Adsorption of 2,4,6-trichlorophenol by multi-walled carbon nanotubes as affected by Cu(II)

Adsorption equilibrium of 2,4,6-trichlorophenol (TCP) on multi-walled carbon nanotubes (MWCNTs) was investigated to explore the possibility of using MWCNTs for concentration, detection and removal of TCP from contaminated water. The adsorption of TCP on MWCNTs at pH 4 was nonlinear, reversible and best fit by a Polanyi-Manes model. Oxidation treatment increased surface area and introduced hydrophilic carboxylic groups to the defect sites of MWCNTs, hence increased the sorption of TCP and Cu(II) individually. Cu(II) suppressed the sorption of TCP on oxidized MWCNTs15A, but had little effect on as-grown MWCNTs15. TCP had no influence on Cu(II) sorption to either. The mechanisms of Cu(II) suppression effect on TCP adsorption are ascribed to the formation of surface complexes of Cu(II), which was verified by X-ray absorption spectroscopy. Cu(II) exerts a cross-linking effect of functional groups on adjacent tubes, creating a more tightly knit bundle and suppressing the condensation of TCP in the pore spaces between the tubes. The large hydration sphere around surface complexes of Cu(II) may also intrude or shield hydrophilic sites, leading to the “crowding out” of TCP around the Cu(II)-complexed sites.     

悬浮单滴微萃取-液相色谱法测定苹果酒中三种杀菌剂

采用悬浮单滴微萃取-液相色谱法测定苹果酒中三唑醇、2,4,6–三氯酚和咪酰胺3种杀菌剂。8μL正十二醇作萃取剂,反相C18色谱柱,甲醇-乙腈-水(70:2:30,v/v,甲酸调pH=3.8)流动相,检测波长225 nm。采用基质校准工作曲线,3种杀菌剂线性关系良好,相关系数大于0.9992,相对标准偏差小于3.8%。     

新型含三嗪结构氧杂膦菲阻燃剂的合成

以三聚氯氰、对羟基苯甲醛和9,10-二氢-9-氧杂-10-膦菲-10-氧化物(DOPO)为主要原料,经两步反应合成了一种新型含三嗪结构氧杂膦菲阻燃剂PN-FR。第一步反应以三聚氯氰、对羟基苯甲醛为原料,二氯甲烷和水为混合溶剂,相转移催化剂作用下回流反应2 h,得2,4,6-三(4-醛基苯氧基)-1,3,5-三嗪(ZJT),收率98.8%;第二步在n(DOPO)∶n(ZJT)∶n(催化剂)=3.2∶1∶0.8,66℃回流反应3 h条件下得目标产物PN-FR,收率95.8%。用FTIR、EA、1HNMR、LC/MS、TG和DSC对中间体和产物作了结构表征和热性能分析。将该阻燃剂初步应用于环氧树脂绝缘层压板的阻燃,当阻燃剂质量分数为15%时,绝缘层压板氧指数达到36.2,通过UL-94 V-0级测试。该文研究工作的新颖性,已为四川省科学技术信息研究所2006年10月26日出具的第A0601512号《科技查新报告》所证实。     

3,5-Diiodo- -tyrosine immobilized on bead cellulose

3,5-Diiodo- -tyrosine (DIT) was immobilized on bead cellulose activated by the reaction with 2,4,6-trichloro-1,3,5triazine (TCT). The amount of immobilized DIT depends on the TCT/DIT ratio in the reaction mixture up to the value 8 mol/mol, at higher values it becomes TCT/DIT-independent. Various sorbents containing 5–31 μtmol DIT/ml cellulose were prepared by varying the amount of DIT in the reaction mixture. The immobilization is also affected by pH. More DIT was bound in acid (pH 6.0) or neutral medium in comparison with the alkaline reaction conditions. Most of the experiments were performed at pH 9.1 equal to the ionization constant of NH₂ group of L-tyrosine. The DIT/bead cellulose materials were prepared for use as sorbents in affinity chromatography of proteases.     

VNS法合成TATB

以乙醇为溶剂,苦基氯与氨水反应得到了2,4,6-三硝基苯胺(TNA),再与4-氨基-1,2,4-三氮唑(ATA)经氢的亲核取代(VNS)反应生成了1,3,5-三氨基-2,4,6-三硝基苯(TATB),总收率大于95.7%.采用红外光谱、核磁、质谱以及元素分析等表征了TNA和TATB.研究了甲醇钠、ATA、反应时间对TA...     

三聚氰酸为基的2,4,6-三氧-[1,3,5]三嗪烷-1-三氨基胍盐的合成、晶体结构和热性能（英）

以三聚氰酸钠(CANa)和三氨基胍盐酸盐(TAG-HCl)为原料,通过一步复分解反应制备了一种富氮含能化合物——2,4,6-三氧-[1,3,5]三嗪烷-1-三氨基胍盐(1),收率91%.采用X-射线单晶衍射、UV-Vis、FTIR、1H NMR以及元素分析等对产物进行了结构表征.计算了产物的生成焓和爆轰参数.通过差示扫描量热法(DSC,10 K·min-1)和热重-傅里叶变换红外光谱联用分析了其热稳定性、非等温热分解动力学和热分解过程.通过落锤法测试了产物的撞击感度.结果表明,化合物1的晶体为单斜晶系,P21/n空间群,计算密度为1.676 g·cm-3,生成焓为327.9 kJ·mol-1,爆速为7900 m·s-1,爆压为26.5 GPa.化合物具1有良好的热稳定性,分解峰值温度为538.9 K,提出了N2气氛下可能的热分解机理.且化合物1对撞击非常钝感,撞击感度大于60 J,优于TATB(50 J).     

Removal of 2,4,6-trichlorophenol from a solution by humic acids repeatedly extracted from a peat soil

Humic acid (HA) is one of the major components of soil organic matter. It strongly affects the sorption behavior of organic and inorganic contaminants in soils. To obtain a better understanding of the interactions of contaminants with HA, a repeated extraction technique has been applied to a peat soil to obtain HA fractions with varying aliphaticity and aromaticity, which were subsequently correlated to the sorption properties of 2,4,6-trichlorophenol (TCP). HA fractions were extracted repeatedly using an alkaline solution and each HA fraction was separated into two portions with an air-drying or re-suspending (denoted as RSHAs) process. Solid-state (13)C NMR and elemental analysis demonstrated that the aromaticity and polarity of HAs decreased with extractions. Kinetic results indicated that air-dried HAs exhibited two-step first order sorption behavior with a rapid stage followed by a slower stage. The slower sorption is attributed to the diffusion of 2,4,6-TCP in the condensed aromatic domains of HAs. Conversely, sorption of 2,4,6-TCP on RSHAs was extremely rapid and could not be fitted with any kinetic model. For air-dried HAs the sorption capacity (K(oc)) was weakly correlated with the chemical compositions of HAs. However, a positive trend between K(oc) and aromaticity was observed for RSHAs. Compared with the results of air-dried HAs with their counterparts of RSHAs, it is therefore concluded that air-drying may alter the structure of HAs through artificially creating a more condensed domain in HAs. The structural alternation may result in an incorrect interpretation of the relationship between sorption capacity and chemical composition of HAs and a misjudgment of the transport behavior of 2,4,6-TCP in soils and sediments.     

Determination of melamine in infant formulas by fluorescence quenching based on the functionalized Au nanoclusters

An environmentally benign and cost-effective assay was developed for the fast determination of melamine (MA) with tiopronin-stabilized gold nanoclusters (TPN-AuNCs) as a fluorophore. The TPN-protected gold nanoclusters which exhibit strong fluorescence emission were prepared by a simple one-vessel procedure. Upon addition of melamine to TPN-AuNCs, a dramatic decrease in their fluorescence intensity was observed, attributing to the electrostatic attraction between the MA and the surface of the TPN-AuNCs which induces the aggregation of TPN-AuNCs. Parameters affecting the detection of MA were investigated including pH, amount of TPN-AuNCs, temperature as well as reaction time. Under the optimized experimental conditions, trace amounts of MA could be analyzed based on the reduction in the fluorescence intensity of TPN-AuNCs. A linear relationship was established at concentrations ranging from 0.09 μM to 100 μM. The detection limit at 32 nM was achieved for this method. The developed method has been successfully applied to the determination of MA in several spiked infant formulas samples purchased from a local supermarket. Excellent recoveries at 92.0–102.2% and precision (RSD: 1.14–2.80%) were attained, respectively, which confirmed the great potential of tiopronin-stabilized gold nanoclusters toward practical measurement of melamine in infant formulas of samples.