Excretion of Urinary 1-Hydroxypyrene in Relation to the Penetration Routes of Polycyclic Aromatic Hydrocarbons

In order to determine the respective contribution of cutaneous and respiratory exposure to urinary PyOH excretion, some experimental follow-ups were carried out during cathode relining in the aluminum industry, leading to qualitative (excretion profiles) and quantitative assessments (excreted PyOH/inhaled pyrene). The procedure was as follows: no exposure on Monday, Wednesday, and Friday; polluting operations on Tuesday and Thursday without or with different protections. For workers with cutaneous protection only, a significant peak of PyOH concentration is observed at the postshift, which is followed by a fast decrease to the background level. For workers with respiratory protection, the maximum is in the shape of a plateau which extends for several hours after the postshift and then decreases slowly. For people with contaminated working clothes, a significant amount of PyOH is excreted on the days with no exposition. The mean ratio of urinary excreted PyOH to inhaled pyrene dose is 15.3% for workers with cutaneous protection and 24.5% for workers with no protection.     

BiO（OH）/AC催化硼氢化钠还原法制备氧化偶氮苯类化合物

采用浸渍法制备了一系列BiO（OH）/AC催化剂,将其用于催化硼氢化钠还原芳香族硝基化合物制备氧化偶氮苯类化合物。以硝基苯为底物考察了催化剂中铋的负载量和硼氢化钠用量对反应的影响,结果表明催化剂中铋的负载量为10%是适宜的,硼氢化钠与硝基苯的摩尔比为1.1∶1是适宜的。以BiO（OH）/C催化硼氢化钠还原7种芳香族硝基化合物得到了相应的氧化偶氮苯类化合物,收率22%～97%。     

异丙醇还原芳硝基化合物制备芳胺

制备了氧化铁、氢氧化氧铁和氢氧化氧铁/C等催化剂,并考察了其对异丙醇还原芳硝基化合物制备芳胺的催化活性。结果表明氢氧化氧铁/C的活性最高。在适宜的条件下,芳硝基化合物10mmol,异丙醇15mL,氢氧化钾0.1g,氢氧化氧铁/C0.1g,回流反应一段时间,得到芳胺的收率为35%~53%。     

Antibody-Based Submicron Biosensor for Benzo[A]Pyrene DNA Adduct

Abstract

Fiberoptic-based sensors have been developed for monitoring human exposure and health effects associated with polycyclic aromatic compounds such as benzo[a]pyrene. These sensors take advantage of the physical properties of optical fibers including their relatively small size, remote sensing capabilities, and their inertness to electrical interferences. the recent development of submicron-sized optical fibers provides an opportunity to further reduce the size of fiberoptic-based sensors for application in submicron environments. This paper describes the development of an antibody based submicron fiber biosensor. the antibody-based biosensor is more selective and sensitive than a nonantibody sensor and has an absolute detection limit of ≈ 300 zeptomoles (10^?21 moles) for benzo pyrene tetrol, a product of the benzo[a]pyrene DNA adduct. This submicron-size biosensor could provide a useful tool for measurements of toxic chemicals and related metabolites in sub cellularsize environments.     

Butyl pyrene containing poly(arylene ethynylene)s for highly sensitive and selective sensing of TNT

A series of poly(arylene ethynylene)s (PAEs) containing ^tbutyl pyrene in the main chain were synthesized for nitroaromatic sensors. As control, similar polymers containing unsubstituted pyrene were also synthesized. The sensory properties of the polymers were studied towards various nitroaromatic compounds like trinitrotoluene (TNT), dinitrotoluene (DNT), nitrotoluene (NT), nitrobenzene (NB) and picric acid (PA) in solution as well as vapor state. Interestingly, all the ^tbutyl substituted pyrene containing polymers showed higher sensitivity than the corresponding unsubstituted pyrene containing polymers. Moreover, the polymers showed high sensitivity towards TNT as compared to the other nitroaromatic compounds. The sensitivity of one of the polymer PB was found several folds higher than that of the similar reported polymer containing unsubstituted pyrene ring. In addition, ^tbutyl pyrene containing polymers were found to have improved molecular weight, thermal stability, fluorescence quantum yield, film forming properties and solubility in common organic solvents as compared to the control polymers.     

Novel (phenylethynyl)pyrene-LNA constructs for fluorescence SNP sensing in polymorphic nucleic acid targets

We describe fluorescent oligonucleotide probes labeled with novel (phenylethynyl)pyrene dyes attached to locked nucleic acids. Furthermore, we prove the utility of these probes for the effective detection of single-nucleotide polymorphisms in natural nucleic acids. High-affinity hybridization of the probes and excellent fluorescence responses to single-base mismatches in DNA/RNA targets are demonstrated in model dual-probe and doubly labeled probe formats. This stimulated us to develop two diagnostic systems for the homogeneous detection of a drug-resistance-causing mutation in HIV-1 protease cDNA and RNA gene fragments. Target sequences were obtained by analysis of 200 clinical samples from patients currently receiving anti-HIV/AIDS combination therapy at the Russian Federal AIDS Center. Using these fluorescent oligonucleotides, we were able to detect the target mutation despite all the challenges of the natural targets, that is, the presence of additional mutations, neighboring sequence variation, and low target concentration, which typically reduce binding and effectiveness of sensing by fluorescent oligonucleotides.     

Development of thin layer polymers to concentrate and detect aquatic contaminants

Poly(dimethylsiloxane) (PDMS) and a poly(DMS‐styrene) block copolymer were compared as extraction and optical detection media for hydrophobic compounds in water and water/ethanol solutions. Partitioning to both polymers increased exponentially with increased percent water in ethanol. Partition coefficients to the copolymer were 10–30‐fold higher than to PDMS. Ultraviolet absorbance spectra of pyrene showed a 4‐nm red‐shift in copolymer versus PDMS, providing evidence of π–π interactions, accounting for greater partitioning. The extinction coefficient coefficient of pyrene at 334 nm was twice as high in the copolymer as in PDMS. The combination of higher affinity for polycyclic aromatic hydrocarbons with higher absorbance make poly(DMS‐styrene) copolymers promising material for extraction and in situ detection of hydrophobic aromatic compounds in water. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

树脂催化硼氢化钠还原法制备氧化偶氮苯类化合物

通过离子交换法制备了Ni（Ⅱ）树脂、Bi（Ⅲ）树脂、Fe（Ⅲ）树脂和Cu（Ⅱ）树脂等几种阳离子树脂,将其用于催化NaBH4还原芳香族硝基化合物制备氧化偶氮苯类化合物。实验结果表明Bi（Ⅲ）树脂的催化性能最好。考察了溶剂对反应的影响,结果表明甲醇是较好的溶剂。在室温下,以甲醇为溶剂,Bi（Ⅲ）树脂催化NaBH4还原几种芳香族硝基化合物制备相应氧化偶氮苯类化合物的收率为60%~97%。     

木质素磺酸钠荧光膜的制备及其在硝基爆炸物检测中的应用

以木质素磺酸钠(LS)为原料, 聚乙烯醇为黏合剂, 制备了木质素磺酸钠荧光膜。通过荧光光谱仪和激光粒度分析仪对LS的形态和光学性质进行了分析, 研究了硝基化合物和无硝基化合物对LS的荧光猝灭作用及猝灭机理, 并将木质素磺酸钠荧光膜应用于硝基爆炸物的检测。研究结果表明: LS随着制备溶剂中乙醇体积分数的增加, 其荧光发射峰强度增加, 分子之间发生缓慢聚集, 且聚集体颗粒变大, 具有聚集诱导发射(AIE)性质; 硝基苯和对硝基苯酚均对LS的荧光猝灭程度高达90%, 间二硝基苯对LS的荧光猝灭程度也有56%;苯、甲苯、苯酚、对苯二甲酸、对苯二甲醛和邻苯二甲醛等无硝基化合物对LS的荧光猝灭作用几乎没有。LS对硝基苯、间二硝基苯和对硝基苯酚等硝基化合物显示出专一、特异的高灵敏检测性能, 该现象主要由光诱导电子转移机制造成的。浸泡过硝基苯/乙醇溶液、间二硝基苯/乙醇溶液和对硝基苯酚/乙醇溶液的木质素磺酸钠荧光膜的荧光猝灭程度分别为89%、78%和100%。将硝基化合物溶液在荧光膜上涂写, 在日光下观察不到笔迹存在, 而在紫外光下能观察到笔迹部分有明显的荧光猝灭现象。     

Synthesis and characterization of Ni nanoparticles-polyvinylamine/SBA-15 catalyst for simple reduction of aromatic nitro compounds

This work concerns the preparation and characterization of Nickel nanoparticle-PVAm/SBA-15, a polymer-inorganic hybrid composite, which was effectively employed as a novel heterogeneous catalyst for reduction of aromatic nitro compounds in the presence of NaBH₄ as a reducing agent. The reaction was carried out in room temperature and an aqueous medium. The catalyst showed good activity for the reduction of a number of aromatic nitro compounds yielding the respective amine compounds in excellent yield (~ 98%) at room temperature along with good reusability.     

Free-standing nickel oxide nanoflake arrays: synthesis and application for highly sensitive non-enzymatic glucose sensors

We report a seed-mediated hydrothermal growth of free-standing nickel hydroxide [Ni(OH)(2)] and nickel oxide (NiO) nanoflake arrays and their implementation as electrodes for non-enzymatic glucose sensors. Ni(OH)(2) nanoflakes were converted into porous NiO nanoflakes upon thermal annealing in air at temperatures of 300 °C or above. NiO nanoflake-arrayed sensors achieve an excellent glucose sensitivity of ～8500 μA cm(-2) mM(-1) and a low detection limit of 1.2 μM glucose at an applied bias of 0.5 V vs. Ag/AgCl. The fabrication of the nanoflake electrode avoids the use of polymer binders representing additional advantage over the conventional powder based glucose sensors. Furthermore, they show good specificity to glucose in the presence of ascorbic acid, d-lactose and d-fructose.     

Synthesis,characterization and fluorescence quenching of conjugated polymer containing triphenylamine group

Poly(triphenylamine-p-phenylenevinylene)s with two different end-groups were obtained through a Wittig polycondensation. The structures of two copolymers were characterized. Ultraviolet and visible spectroscopy (UV-Vis) and photoluminescence (PL) spectra show the end-capped polymer emits intensive green light in both solution and film state. Their applications in the detection of nitro compounds were investigated, and the results show high fluorescence quenching sensitivity of the end-capped polymer towards o-nitrotoluene (o-NT). When the concentration of o-NT was 21.5 × 10^-3 mol/L, the fluorescence quenching reached 96%. Additionally, after the exposure of polymer film in three different quenchers such as dinitrotoluene (DNT), p-nitrobenzoquinone (p-BQ) and p-nitrotoluene (p-NT) for 600 s, its fluorescence quenching reached 93.6%, 11.5% and 77.9%, respectively. This kind of polymer has great advantages in preparation and may find applications in the detection of nitro explosives.     

The Pyreno-Triazinyl Radical – Magnetic and Sensor Properties

We report the first example of a stable pyrenotriazinyl radical, 1,3-diphenyl-1,2,4-pyrenotriazin-4-yl ( PyT ). Magnetic susceptibility measurements of the radical PyT show a transition from a paramagnetic state to an antiferromagnetic state. The pyrene moiety has a strong influence via π π interactions in 1D chain stacks that result in the observed magnetic properties. Unexpectedly, the pyrene unit has essentially no effect on the electronic structure of the triazinyl core. Chemical sensing studies on various nitrophenol-based compounds showed that the radical PyT exclusively senses picric acid ( PA ), as a pH sensor, with a detection limit of 5.0×10⁻⁶ M.     

OXIDATION OF HUMIC SUBSTANCES PRIOR TO THE DETECTION OF PCBs AND PAHs IN NATURAL WATERS BY FLUOROMETRY ON SOLID SORBENT

A method for the detection of PCBs in water, based on extraction/concentration with tab-shaped elements cut from C18 fiberglass SPE disks coupled with a fluorescence detection has been applied to natural waters. Due to the known complexing property of the naturally present Natural Organic Matter (NOM) with respect to non polar organic pollutants, NOM was shown to compete with the solid phase for PCB adsorption thus reducing the capability of the method.

In order to obviate the negative effect of NOM on the sensitivity of the method, a prior oxidation treatment with KMnO₄ was tested on PCB3, PCB77 and Aroclor 1221. This pretreatment was also tested for the detection of pyrene, perylene and benzo[a]pyrene taken as representative polycyclic aromatic compounds.

In all cases, with respect to the signal in pure water and depending on the dissolved organic carbon concentration (DOC), the signals with no treatment could be lowered to less than 20%, while the signals obtained following oxidative treatment was found to be very close with more than 90% of recovery.     

Pyrene functionalized side chain alanine and histidine containing copolyacrylates prepared by free radical copolymerization

An optically active copolyacrylate, poly(N‐acryloyl‐L‐alanine‐co‐N‐acryloyl‐L‐histidine), is prepared by classical radical copolymerization of N‐acryloyl‐L‐alanine and N‐acryloyl‐L‐histidine, and further chemically modified with 1‐pyrene‐methanol. The structures of the synthesized compounds are confirmed by spectral analysis (FTIR, ¹H/¹³C‐NMR, UV, fluorescence spectroscopy), thermal methods, and molecular weight measurements. Also, their optical activity is studied using circular dichroism (CD) spectroscopy and optical rotation measurements. The specific rotation values reveal that the direction of rotation of the parent copolymer is dictated by the monomer containing L‐alanine. CD data suggest negative and positive Cotton effects regarding the monomers with amino acids. In the case of the unmodified copolymer it is noted the changes of ellipticity values with increasing pH while the random‐coil conformation is preserved, which makes it suitable as a pH‐responsive system. Photochemical and photophysical investigations reveal that the pyrene‐functionalized chiroptical copolyacrylate can be used as a fluorescent chemosensor for the detection of nitro‐derivatives in organic media. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44457.     

PAH Profiles of Charbroiled Hamburgers: Pyrene/B[a]P Ratios and Presence of Reactive PAH

Abstract

Analysis of the polycyclic aromatic hydrocarbons (PAH) in charbroiled hamburgers, used in an earlier study of BaP-DNA adducts in peripheral white blood cells, has been accomplished using HPLC with UV diode array detection. The concentration data for one of these PAH, benzo[a]pyrene (BaP), are in excellent agreement with data obtained using a thin-layer chromatography (TLC)/fluorescence technique. There is significant interest in pyrene/BaP ratios in these samples and other sources of human exposure to PAH since urinary metabolites of both compounds have been used as biomarkers of exposure. In the food samples examined, this ratio is roughly 5. However, differences in cooking procedures between different studies suggest that this value can only be used semi-quantitatively. The BaP concentrations themselves vary by a factor of almost twenty in hamburgers prepared under very similar conditions. Some unstable PAH, including cyclopenteno[cd]pyrene and methylated PAH are found in the hamburger. This possibly reflects their decreased reactivity under conditions different from those which prevail in the outdoor atmosphere.     

Ozonation of polycyclic aromatic hydrocarbon in hexane and water: Identification of intermediates and pathway

The recalcitrant nature of pyrene and other polycyclic aromatic hydrocarbons (PAHs) lies in part in their low solubility in water, rendering them less susceptible to chemical and biological degradation. To overcome this remediation obstacle, this work investigates the use of a 2-stage ozonation process, first in nonpolar hexane phase then in polar aqueous phase, for the treatment of hydrophobic contaminants using pyrene as a model compound. The objectives of this research are to break down pyrene by using ozonation, identify the intermediates of pyrene, show a general degradation pathway of pyrene subject to ozonation and test the biodegradability of intermediates and byproducts of pyrene in the aqueous phase. The first stage briefly ozonates the contaminant at high concentration in organic solvent hexane, which facilitates very efficient conversion of the hydrophobic compounds into ring-opened polar intermediates containing alcohol, aldehyde, and acid functional groups.     

4-羟基-3,5-二溴苯胺及脂溶性芳胺的制备方法

在NH4Cl-H2O-CH3COCH3体系中,以铁为还原剂,4-羟基-3,5-二溴硝基苯转化成4-羟基-3,5-二溴苯胺的产率达97.2%;采用正交试验,探索了反应的最佳条件:反应物与NH4Cl的摩尔比为1:2,H2O-CH3COCH3的体积比为1:1,反应时间为6h。实验证明该方法也可用于其他硝基化合物的还原,并且不会导致C-Br的还原,该方法尤其适合于硝基化合物及其对应的胺都不溶于水的情况。     

结核分枝杆菌Rv0057-Rv1352融合蛋白的制备及其初步应用

目的制备结核分枝杆菌(Mycobacterium tuberculosis,M.tb)Rv0057-Rv1352融合蛋白,并通过化学发光酶免疫法分析其抗原性,以评价其应用价值。方法根据Rv0057和Rv1352蛋白序列,合成Rv0057和Rv1352基因片段并进行扩增,分别插入质粒pET30aSETB中,构建重组质粒Rv0057/pET30aSETB和Rv1352/pET30aSETB。用NheⅠ和XhoⅠ双酶切重组质粒Rv1352/pET30aSETB,SpeⅠ和XhoⅠ双酶切重组质粒Rv0057/pET30aSETB,将回收的Rv1352基因片段插入Rv0057/pET30aSETB质粒中,构建重组质粒Rv0057-Rv1352/pET30aSETB,转化感受态大肠埃希菌BL21(DE3),IPTG诱导表达。表达的包涵体蛋白经His.Bind蛋白纯化试剂盒纯化后,以其作为抗原建立化学发光酶免疫分析法,检测患者血清中抗结核抗体,并与市售M.tb抗体诊断试剂盒和痰涂片法进行比较。结果构建的重组质粒Rv0057-Rv1352/pET30aSETB的核苷酸序列与设计序列完全一致;表达的重组融合蛋白Rv0057-Rv1352相对分子质量约为30 500,主要以包涵体形式存在,表达量约占菌体总蛋白的30%;纯化的重组融合蛋白的浓度为1.6 mg/ml,纯度为95%;以其为抗原建立的化学发光酶免疫分析法检测患者血清中抗结核抗体的灵敏度和特异性分别为66.70%和90.00%,而市售M.tb抗体诊断试剂盒的灵敏度和特异性分别为80.00%和63.33%;30例活动性肺结核患者经痰涂片检测,灵敏度为20.0%,化学发光酶免疫分析法检测灵敏度为66.7%,二者差异有统计学意义(P<0.01)。结论成功制备了M.tb Rv0057-Rv1352融合蛋白,以其为抗原建立的化学发光酶免疫分析法检测抗结核抗体具有较高的灵敏度和特异性,在结核病血清学快速诊断方面具有广阔的应用前景。     

一些含硫、含氮化合物在卤化银成像过程中的作用

采用在曝光前后用不同浓度的化合物溶液分别处理硫增感立方乳剂样品方法,观察它们在感光特性上的差别,从而判断这些化合物在卤化银成像过程的不同阶段各自所起的作用．本工作中所选用的化合物有1-苯基-5-巯基四氮唑(PMT),6-硝基苯并咪唑(硝酸盐),5-硝基苯并咪唑,5-硝基吲唑,4-羟基-6-甲基-1,3,3a,7-四氮茚(TAI)和硫代乙酰胺．结果表明：PMT在一定的浓度范围内对潜影的形成有促进作用,但对显影有抑制作用;6-硝基苯并咪唑和5-硝基苯并咪唑的情况相似,对潜影的形成无显著影响,而对显影的抑制作用明显;5-硝基吲唑不仅对潜影的形成有明显阻滞作用,而且对显影也有抑制作用;TAI则对潜影的形成有明显的促进作用,对显影的影响较小;硫代乙酰胺在弱酸性介质中对潜影的形成有显著阻滞作用,对显影也有-定的抑制作用,但对灰雾的增长十分显著．