Novel flame retardants containing cyclodextrin nanosponges and phosphorus compounds to enhance EVA combustion properties

A novel flame retardant intumescent system, aimed to improve the fire stability of ethylene vinyl acetate copolymer (EVA), has been prepared by melt blending of the copolymer and a complex of cyclodextrin nanosponge-phosphorus compounds. As compared to traditional systems, this complex, stable in processing conditions, has the advantage that nanosponges act as both carbon sources and foam forming agents while the phosphorus compounds are able to directly generate phosphoric acid in situ. In this context, cyclodextrin nanosponges undergo dehydration in presence of the acid source, generating water vapour and char, and thus protecting the copolymer against combustion. Different acid sources have been investigated in order to reach the optimum interaction with the nanosponges. Raman measurements and thermogravimetric analyses have shown that the cavities of nanosponges entrapped the phosphorus derivatives forming stable complexes at the temperature of EVA processing. Different amounts of these complexes (5, 10 and 15 wt.%) have been added to EVA via melt blending and their flame retardancy properties measured by UL94 test and cone calorimetry. Strongly modified burning kinetics, as compared to the behaviour of the neat copolymer, have been found by UL94 test: V2 classification has been achieved for every formulation regardless of the type and the amount of complex used. EVA combustion behaviour by cone calorimetry has also been significantly affected: the heat release rate decreased dramatically down to ca. 20% in the presence of these new additives.     

Continuous hydrothermal synthesis of AlO(OH) nanorods as a clean flame retardant agent

Aluminum-oxide-hydroxide (AlOOH) is a clean and non-toxic flame retardant. There have been many trials for the fabrication of ultrafine AlOOH. Two main approaches exist for nano-AlOOH synthesis: reactive precipitation and batch hydrothermal synthesis. Both approaches are laborious and time consuming with poor control of particle morphology. We report on the novel continuous flow manufacture of AlOOH nanorods with controlled morphology (particle size and shape) by hydrothermal synthesis. AlOOH was harvested from its mother liquor (colloidal solution) using poly(acrylamide-co-acrylic acid) copolymer as a flocculating agent. The developed AlOOH shape and size, crystalline phase, thermal stability, and endothermic heat sink action were investigated by transmission electron microscopy, X-ray diffractometry, thermogravimetric analysis, and differential scanning calorimetry, respectively. The phase transition of AlOOH to Al₂O₃ was demonstrated by conducting different X-ray diffractometry scans from 400 to 700 °C. These results may provide an option for the continuous synthesis of nano-AlOOH as a clean and non-toxic flame retardant with excellent thermal stability. Consequently, enhanced flammability properties can be achieved at low solids loading.     

凝胶渗透色谱结合气相色谱-负化学源质谱法分析鱼肉及鱼油中的多溴联苯醚和得克隆阻燃剂

建立了凝胶渗透色谱(GPC)结合气相色谱-负化学源质谱(GC-NCI/MS)检测鱼肉及鱼油中8种多溴联苯醚(PBDEs)同系物及2种得克隆阻燃剂(DP)的分析方法。试样中加入内标物BDE-77和13C12-BDE-209后进行索氏提取,提取液经自动GPC系统除脂,多层硅胶层析柱净化后,在15 m长的毛细管气相色谱柱上分离,NCI/MS以选择离子监测方式检测目标化合物。以鱼肉样品为基质,当PBDEs的加标水平为0.2 ng/g和2 ng/g、BDE-209和DP的加标水平相应提高10倍时,其平均加标回收率为71.1%～121.4%,相对标准偏差为2.96%～13.31%(n=5);以信噪比(S/N)为3计算方法的检出限(LOD)为2.2～39.8 ng/kg。用该方法检测市售鱼肉及鱼油样品,其中多溴联苯醚总含量为2.18～15.93 ng/g,以BDE-209、BDE-47为主,两种DP均未检出。该方法准确、灵敏度高,能够满足富含脂质的动物性样品中痕量DP和PBDEs残留的分析要求。     

电拓扑状态预测有机磷酸酯类化合物的气相色谱保留指数

以原子类型电拓扑状态指数(ETSI)有效表征35个有机磷酸酯类化合物(OP)的分子结构, 应用基于预测的变量选择与模型化(VSMP)方法建立OP化合物在3种不同固定相上的气相色谱保留指数(RI)与分子结构(ETSI)的定量相关模型. 结果表明, 影响不同固定相上OP色谱保留的主要结构因素都是由7个ETSI描述子对应的子结构碎片, 即: ＝CH₂,≡C—, aaC—, ＝O, —O—, Cl和Br. 其中子结构aaC—, ＝O和—O与OP化合物母体骨架密切相关, 而＝CH₂,≡C—, —Cl和—Br反映支链或取代基的变化. 通过多元线性回归法建立OP化合物在三个固定相上的定量结构-保留相关模型(QSRR)发现, 各QSAR模型的估计相关系数均在0.99以上, LOO检验相关系数在0.98以上, 表明模型具有良好估计能力与稳定性. 应用28个OP训练集样本构建的QSRR模型预测外部7个检验集RI结果表明训练集模型具有良好预测能力.     

阻燃剂废水的处理研究

阻燃剂生产过程中产生大量的工业废水,通过对比处理实验研究表明：电解Fenton法是处理阻燃剂生产中产生的高浓度有机废水（CODCr=17108mg／L）的有效方法,它既利用了电氧化、电气浮作用,又利用了Fenton试剂的强氧化作用和化学絮凝作用。其处理废水的条件实验结果表明：pH：2．0～2．6;电流密度10．8～14．3A/dm^2;H2O2初始浓度27～42mmol／L;FeSO4初始质量浓度660～990mg／L;电解5h。CODCr去除率达98．34％,色度去除率达74．19％。色质联用分析显示废水处理后的降解产物是无毒害的醋酸。     

The Structure and Function of Paraoxonase-1 and Its Comparison to Paraoxonase-2 and -3

Serum paraoxonase-1 (PON1) is the most studied member of the group of paraoxonases (PONs). This enzyme possesses three enzymatic activities: lactonase, arylesterase, and paraoxonase activity. PON1 and its isoforms play an important role in drug metabolism as well as in the prevention of cardiovascular and neurodegenerative diseases. Although all three members of the PON family have the same origin and very similar amino acid sequences, they have different functions and are found in different locations. PONs exhibit substrate promiscuity, and their true physiological substrates are still not known. However, possible substrates include homocysteine thiolactone, an analogue of natural quorum-sensing molecules, and the recently discovered derivatives of arachidonic acid—bioactive δ-lactones. Directed evolution, site-directed mutagenesis, and kinetic studies provide comprehensive insights into the active site and catalytic mechanism of PON1. However, there is still a whole world of mystery waiting to be discovered, which would elucidate the substrate promiscuity of a group of enzymes that are so similar in their evolution and sequence yet so distinct in their function.     

Biophysical aspects of cyclodextrin interaction with paraoxon

Cyclodextrins are torus‐shaped polymers of glucose that can bind organophosphorous compounds such as nerve agents and pesticides. We demonstrate here that cyclodextrin can bind up to two paraoxon molecules with a K_av of 6775 M^‐1. Molecular modeling shows that the paraoxon appears to bind in polar opposite orientation and have an average binding energy of ?89 Kcals/mol. Published 2013. This article is a U.S. Government work and is in the public domain in the USA.     

4,4,5,5-Tetra(3,5-dibromophenyl)-2,2-diphenyl-1,3-dioxa-2-silole and related compounds as precursors to flame retardant oligomers

Certain strained five-membered heterocycles undergo thermally-induced, carbon-carbon bond homolysis to generate diradicals capable of initiating vinyl polymerization. These compounds usually contain two oxygen atoms and a larger heteroatom (silicon, phosphorus, sulfur) in addition to carbon. If the heterocycle is suitably substituted with halogen (particularly bromine) containing moities it may function as a vehicle to permit incorporation of flame-retarding units into a polymer or oligomer. When an appropriate heterocycle is used as an initiator for radical polymerization each polymer chain formed contains at least one flame-retarding unit. One such heterocycle is 4,4,5,5-tetra(3,5-dibromophenyl)-2,2-diphenyl-1,3-dioxa-2-silole. In instances in which the heterocycle also acts as a monomer, i.e., it is reactive toward chain-propagating radicals, additional flame-retarding activity may be incorporated into the polymer.     

HPLC-MS/MS法同时测定果蔬中6种植物生长抑制剂残留

利用高效液相色谱-电喷雾串联质谱(HPLC-ESI MS/MS)技术,建立了果蔬中氯化胆碱、矮壮素、缩节胺、嘧啶醇、多效唑、烯效唑6种植物生长抑制剂残留的检测方法.考察了流动相组分和流动相添加剂对质谱离子化效率的影响以及提取溶剂、提取剂用量和固相萃取柱对萃取效率的影响.在优化条件下,6种目标化合物在1.0 ～200.0...     

Streamlined sample cleanup using combined dispersive solid-phase extraction and in-vial filtration for analysis of pesticides and environmental pollutants in shrimp

A new method of sample preparation was developed and is reported for the first time. The approach combines in-vial filtration with dispersive solid-phase extraction (d-SPE) in a fast and convenient cleanup of QuEChERS (quick, easy, cheap, effective, rugged, and safe) extracts. The method was applied to simultaneous analysis of 42 diverse pesticides and 17 environmental contaminants, including polycyclic aromatic hydrocarbons, polychlorinated biphenyls (PCBs), and flame retardants, in shrimp as the sample matrix. Final extracts were analyzed by both low-pressure gas chromatography – triple quadrupole tandem mass spectrometry (LPGC-MS/MS), and high-performance liquid chromatography – triple quadrupole tandem mass spectrometry (HPLC-MS/MS) to provide a wide scope of analysis for targeted analytes. During method development, several different commercial sorbents for d-SPE were investigated and compared with respect to analyte recoveries. The method was validated at 10, 50, and 100 ng g⁻¹ spiking levels (10-fold lower for PCBs), and the results for nearly all analytes were between 70 and 115% recoveries with ≤17% relative standard deviations. The method was shown to be simple, fast, and effective for multi-application analysis of chemical residues in the representative food and environmental marker matrix.